Sample records for diol thermoset composites

  1. Studies on Poly(propylene fumarate-co-caprolactone diol Thermoset Composites towards the Development of Biodegradable Bone Fixation Devices

    M. Jayabalan


    Full Text Available The effect of reinforcement in the cross-linked poly(propylene fumarate-co-caprolactone diol thermoset composites based on Kevlar fibres and hydroxyapatite was studied. Cross-linked poly(propylene fumarate-co-caprolactone diol was also studied without any reinforcement for comparison. The reinforcing fibre acts as a barrier for the curing reaction leading to longer setting time and lesser cross-link density. The fibre and HA reinforced composites have almost the same compressive strength. Nonreinforced material undergoes greater degree of swelling. Among the reinforced materials, the hydroxyapatite reinforced composite has a much higher swelling percentage than the fibre reinforced one. The studies on in vitro degradation of the cured materials reveal hydrolytic degradation in Ringer's solution and PBS medium during aging. All the three materials are found to swell initially in Ringer's solution and PBS medium during aging and then undergo gradual degradation. Compression properties of these cross-linked composites increase with aging; HA reinforced composite has the highest compressive strength and compressive modulus, whereas the aged fibre-reinforced composite has the least compressive strength and modulus.

  2. Soy-based fillers for thermoset composites

    Watt, Paula

    Considerable work has been done with bio-based fillers in thermoplastics. Wood dust has been used for decades in wood plastic composites in conjunction with recycled high HDPE and PET. In recent years rapidly renewable fillers derived from dried distillery grains and from wood have been introduced commercially for thermoset polymers. These fillers provide bio-content and weight reduction to thermoset molding compounds but issues with moisture absorption and polymerization inhibition have limited their commercial acceptance. The intent of this research was to develop a bio-based filler suitable for thermoset composites. This filler would provide a low density alternative to mined mineral filler, such as CaCO3 or clay. Composites made with these fillers would be lighter in weight, which is desirable for many markets, particularly transportation. Cost parity to the mineral fillers, on a volume basis, was desirable and the use of green chemistry principles was a key objective of the project. This work provides a basis from which further development of modified soy flours as fillers for thermoset composites will continue. Biomass has been evaluated as fillers for thermoset composites since the early 1980s but failed to gain commercial acceptance due to excessive water absorption and inhibition issues with free radical curing. Biomass, with a large percentage of carbohydrates, are very hydrophilic due to their abundance of hydroxyl groups, while biomass, high in lignin, resulted in inhibition of the free radical cure of the unsaturated styrenated polyester matrix systems. Generally protein use as a filler is not desirable due to its food value. Torrefaction has proved to be a good, cost effective, process to reduce hydrophilicity of high cellulose feedstock. Surprising, however, some levels of torrefaction were found to induce the inhibition effect of the filler. Scientific inquiry into this problem proved that aromatics form during the torrefaction process and can

  3. Flax reinforced thermoset composites from polyfurfuryl alcohol

    Kumar, R


    Full Text Available Water insoluble poly(furfuryl alcohol) (PFA) is an unexplored thermosetting resin which is synthesized from water-soluble furfuryl alcohol (FA). Commercially available FA has very low viscosity (6.9-7.0 cts at 25°C) and it is obtained from furfural...

  4. Thermoset composite recycling: Properties of recovered glass fiber

    Beauson, Justine; Fraisse, Anthony; Toncelli, C.


    Recycling of glass fiber thermoset polymer composite is a challenging topic and a process able to recover the glass fibers original properties in a limited cost is still under investigation. This paper focuses on the recycling technique separating the glass fiber from the matrix material. Four...... different recycling processes, mechanical, burn off, pyrolysis and glycolysis are selected are compared based on the properties of the glass fiber recovered. The intention is to use the same characterization methodology....

  5. Water Diffusion Modelling of CFB Fly Ash Thermoset Composite

    Villa Ralph P.


    Full Text Available The shift in coal-fired power plants from pulverized coal (PC boiler technology into the greener circulating fluidized bed (CFB boiler technology resulted into a major deviation in the properties of the waste fly ash generated making it less suitable for its previous application as additives for construction materials. A new market for CFB fly ash had to be found for it not to end up as a zero value by-product. Using CFB fly ash as filler for thermoset composites is a new and remarkable application. Only a few studies, however, have been done to characterize the properties of this new material. Further experimentation and analysis may be costly and time-consuming since common procedures are material destructive. A computer-aided modeling of the composite’s water sorption behavior was done. The effect of particle loading, size and shape were considered. These properties were varied and the resulting overall diffusivities were compared to previous experimental studies. The comparison of the model and experimental diffusivity values showed satisfactory results. This model may then provide a cheaper and more time-efficient method for the characterization of the water sorption properties of CFB fly ash thermoset composites. In the future, this may lead to further studies on its application as a green material.

  6. Improved fire retardancy of thermoset composites modified with carbon nanofibers

    Zhongfu Zhao and Jan Gou


    Full Text Available Multifunctional thermoset composites were made from polyester resin, glass fiber mats and carbon nanofiber sheets (CNS. Their flaming behavior was investigated with cone calorimeter under well-controlled combustion conditions. The heat release rate was lowered by pre-planting carbon nanofiber sheets on the sample surface with the total fiber content of only 0.38 wt.%. Electron microscopy showed that carbon nanofiber sheet was partly burned and charred materials were formed on the combusting surface. Both the nanofibers and charred materials acted as an excellent insulator and/or mass transport barrier, improving the fire retardancy of the composite. This behavior agrees well with the general mechanism of fire retardancy in various nanoparticle-thermoplastic composites.

  7. Healable thermoset polymer composite embedded with stimuli-responsive fibres.

    Li, Guoqiang; Meng, Harper; Hu, Jinlian


    Severe wounds in biological systems such as human skin cannot heal themselves, unless they are first stitched together. Healing of macroscopic damage in thermoset polymer composites faces a similar challenge. Stimuli-responsive shape-changing polymeric fibres with outstanding mechanical properties embedded in polymers may be able to close macro-cracks automatically upon stimulation such as heating. Here, a stimuli-responsive fibre (SRF) with outstanding mechanical properties and supercontraction capability was fabricated for the purpose of healing macroscopic damage. The SRFs and thermoplastic particles (TPs) were incorporated into regular thermosetting epoxy for repeatedly healing macroscopic damages. The system works by mimicking self-healing of biological systems such as human skin, close (stitch) then heal, i.e. close the macroscopic crack through the thermal-induced supercontraction of the SRFs, and bond the closed crack through melting and diffusing of TPs at the crack interface. The healing efficiency determined using tapered double-cantilever beam specimens was 94 per cent. The self-healing process was reasonably repeatable.

  8. High performance bio-based thermosets for composites and coatings

    Paramarta, Adlina Ambeg

    In the recent decade, there has been increasing interest in using renewable feedstocks as chemical commodities for composites and coatings application. Vegetable oils are promising renewable resources due to their wide availability with affordable cost. In fact, the utilization of vegetable oils to produce composite and coatings products has been around for centuries; linseed oil was widely used for wide variety of paints. However, due to its chemical structure, the application of vegetable oils for high-performance materials is limited; and thus chemical modification is necessary. One of the modification approaches is by substituting the glycerol core in the triglycerides with sucrose to form sucrose esters of vegetable oil fatty acids, in which this resin possesses a higher number of functional group per molecule and a more rigid core. In this research, thermosets of highly functionalized sucrose esters of vegetable oils were developed. Two crosslinking methods of epoxidized surcrose soyate (ESS) resins were explored: direct polymerization with anhydride moieties for composite applications and Michael-addition reaction of acrylated-epoxidized sucrose soyate (AESS) for coatings applications. In the first project, it was shown that the reaction kinetics, thermal and mechanical properties of the materials can be tuned by varying the molar ratio between the epoxide and anhydride, plus the type and amount of catalyst. Furthermore, the toughness properties of the ESS-based thermosets can be improved by changing the type of anhydride crosslinkers and incorporating secondary phase rubbers. Then, in the second system, the epoxy functionality in the ESS was converted into acrylate group, which then crosslinked with amine groups through the Michael-addition reaction to produce coatings systems. The high number of functional groups and the fast reactivity of the crosslinker results in coatings that can be cured at ambient temperature, yet still possess moderately high glass

  9. Thermosetting Polymer-Matrix Composites for Strucutral Repair Applications

    Goertzen, William Kirby [Iowa State Univ., Ames, IA (United States)


    Several classes of thermosetting polymer matrix composites were evaluated for use in structural repair applications. Initial work involved the characterization and evaluation of woven carbon fiber/epoxy matrix composites for structural pipeline repair. Cyanate ester resins were evaluated as a replacement for epoxy in composites for high-temperature pipe repair applications, and as the basis for adhesives for resin infusion repair of high-temperature composite materials. Carbon fiber/cyanate ester matrix composites and fumed silica/cyanate ester nanocomposites were evaluated for their thermal, mechanical, viscoelastic, and rheological properties as they relate to their structure, chemistry, and processing characteristics. The bisphenol E cyanate ester under investigation possesses a high glass transition temperature, excellent mechanical properties, and unique ambient temperature processability. The incorporate of fumed silica served to enhance the mechanical and rheological properties of the polymer and reduce thermal expansion without sacrificing glass transition or drastically altering curing kinetics. Characterization of the composites included dynamic mechanical analysis, thermomechanical analysis, differential scanning calorimetry, thermogravimetric analysis, rheological and rheokinetic evaluation, and transmission electron microscopy.

  10. High-temperature hybrid welding of thermoplastic (CF/Peek) to thermoset (CF/Epoxy) composites

    Fernandez Villegas, I.; Vizcaino Rubio, P.


    Thermoset composites are widely used for the manufacturing of modern composite aircrafts. The use of thermoplastic composites (TPC) in aerospace applications is, however, gradually increasing owing to their cost-effectiveness in manufacturing and improved damage tolerance. An example of the use of t

  11. High-temperature hybrid welding of thermoplastic (CF/Peek) to thermoset (CF/Epoxy) composites

    Fernandez Villegas, I.; Vizcaino Rubio, P.


    Thermoset composites are widely used for the manufacturing of modern composite aircrafts. The use of thermoplastic composites (TPC) in aerospace applications is, however, gradually increasing owing to their cost-effectiveness in manufacturing and improved damage tolerance. An example of the use of

  12. Composite panels made with biofiber or office wastepaper bonded with thermoplastic and/or thermosetting resin

    James H. Muehl; Andrzej M. Krzysik; Poo Chow


    The purpose of this study was to evaluate two groups of composite panels made from two types of underutilized natural fiber sources, kenaf bast fiber and office wastepaper, for their suitability in composite panels. All panels were made with 5% thermosetting phenol-formaldehyde (PF) resin and 1.5% wax. Also, an additional 10% polypropylene (PP) thermoplastic resin was...

  13. Bond and low cycle fatigue behavior of thermoset composite reinforcing for the concrete industry

    Barnes, B.


    This thesis encompasses two separate research projects. The first project, described in Chapter 2 was a project investigating the fatigue behavior of thermoset Fiber Composite (FC) sandwich wall ties. The second research project detailed in this thesis was a project studying the bond and tensile properties of FC rod and FC fibers.

  14. A novel biaxial specimen for inducing residual stresses in thermoset polymers and fibre composite material

    Jakobsen, Johnny; Andreasen, Jens Henrik; Jensen, Martin


    engineers when they challenge the material limits in present and future thermoset and composite component. In addition to the new specimen configuration, this paper presents an analytical solution for the residual stress state in the specimen. The analytical solution assumes linear elastic and isotropic......A new type of specimen configuration with the purpose of introducing a well-defined biaxial residual (axisymmetric) stress field in a neat thermoset or a fibre composite material is presented. The ability to experimentally validate residual stress predictions is an increasing need for design...... material behaviour. Experimental strain release measurements and the analytical solution determine the residual stress state present in the material. A demonstration on neat epoxy is conducted and residual stress predictions of high accuracy and repeatability have been achieved. The precise determination...

  15. Static and dynamic strain energy release rates in toughened thermosetting composite laminates

    Cairns, Douglas S.


    In this work, the static and dynamic fracture properties of several thermosetting resin based composite laminates are presented. Two classes of materials are explored. These are homogeneous, thermosetting resins and toughened, multi-phase, thermosetting resin systems. Multi-phase resin materials have shown enhancement over homogenous materials with respect to damage resistance. The development of new dynamic tests are presented for composite laminates based on Width Tapered Double Cantilevered Beam (WTDCB) for Mode 1 fracture and the End Notched Flexure (ENF) specimen. The WTDCB sample was loaded via a low inertia, pneumatic cylinder to produce rapid cross-head displacements. A high rate, piezo-electric load cell and an accelerometer were mounted on the specimen. A digital oscilloscope was used for data acquisition. Typical static and dynamic load versus displacement plots are presented. The ENF specimen was impacted in three point bending with an instrumented impact tower. Fracture initiation and propagation energies under static and dynamic conditions were determined analytically and experimentally. The test results for Mode 1 fracture are relatively insensitive to strain rate effects for the laminates tested in this study. The test results from Mode 2 fracture indicate that the toughened systems provide superior fracture initiation and higher resistance to propagation under dynamic conditions. While the static fracture properties of the homogeneous systems may be relatively high, the apparent Mode 2 dynamic critical strain energy release rate drops significantly. The results indicate that static Mode 2 fracture testing is inadequate for determining the fracture performance of composite structures subjected to conditions such as low velocity impact. A good correlation between the basic Mode 2 dynamic fracture properties and the performance is a combined material/structural Compression After Impact (CAI) test is found. These results underscore the importance of

  16. Thermal recycling and re-manufacturing of glass fibre thermosetting composites

    Fraisse, Anthony; Beauson, Justine; Brøndsted, Povl


    The impact of using thermally recycled glass fibre in re-manufactured composites was investigated. A unidirectional glass fibre thermosetting composite laminate was manufactured. The matrix in one part of the laminate was burnt off to recover the glass fibres. These recycled glass fibres were used...... to manufacture a new composite laminate with the same fibre architecture as the pristine one. The fibres, the matrix and the composite laminates were thoroughly characterised and analysed. The results show that good materials quality was obtained for both laminates. A difference in fibre packing behaviour...... was observed in the composites with the pristine and the recycled fibres, which lead to a lower fibre volume fraction in the latter one. The Young's modulus of the composites was not changed by the recycling process, if the lower fibre volume fraction is taken into account. However, a marked drop...

  17. High performance hyperbranched polymers for improved processing and mechanical properties in thermoset composites

    Marsh, Timothy

    Hyperbranched polymers, specifically hyperbranched poly(arylene ether ketone imide)s (HBPAEKI), are here studied as blend additives in thermoset composites to improve processing and ultimate performance properties of the composite. Monomer synthesis for HBPAEKI was further advanced in this work leading to higher yields, fewer reactions, and shorter production times. A five step synthetic method with an overall yield of 12% was reduced to a three step process with an overall yield of 38%. Polymer was synthesized under varying conditions and end group chemistry for use in thermoset blends. NMR characterization allowed for the assignment of chemical shifts in monomer and cataloguing of shifts in polymer for use in future work to characterize degree of branching. Cure kinetics of blends of HBPAEKI are explored through the use of differential scanning calorimetry (DSC) and chemorheology using small angle oscillatory shear. In a phenylethynyl terminated imide oligomer (PETI) thermoset resin, reactive phenylethynyl endcapped PAEKI (PEPAEKI) was found to retard cure while non reactive alkyl endcapped PAEKI was found to accelerate cure in DGEBA/DAH epoxy systems. Minimal effect was seen on early stage blend viscosity. Composite properties tested focused on the effect on bulk fracture and interfacial shear strength. No significant effect was seen in fracture toughness by SENB. XPS was used to verify that PEPAEKI was surface active to DGEBA/DDS epoxy/air interfaces to the complete exclusion of the epoxy at the surface. Evidence was also seen consistent with surface activity in alkyl endcapped PAEKI in DGEBA/DAH systems, although the contrast is much lower. Effect of alkyl endcapped HBPAEKI on interfacial shear strength was examined through the use of t-peel and single fiber fracture (SFF) techniques. In some systems, t-peel indicates a clear improvement in peel force, proportional to the blend concentration. In SFF, interfacial shear strength was found to be equal or slightly

  18. Numerical prediction of temperature distribution in thermoset composites during laser curing process

    吴存真; 孙志坚; 徐剑锋; 秦悦慧


    The temperature distribution in the advanced thermoset composite during the laser curing process was predicted with the use of the two-dimensional thermo-chemical model presented in this paper which also gives the governing equations based on the thermal history of the curing process. The finite-difference method was used to get the temperature distribution. This paper also deals with the effect of some factors (such as the winding velocity, the tape thickness and the laser heat source) on the temperature distribution.

  19. Self-Healing Composite of Thermoset Polymer and Programmed Super Contraction Fibers

    Li, Guoqiang (Inventor); Meng, Harper (Inventor)


    A composition comprising thermoset polymer, shape memory polymer to facilitate macro scale damage closure, and a thermoplastic polymer for molecular scale healing is disclosed; the composition has the ability to resolve structural defects by a bio-mimetic close-then heal process. In use, the shape memory polymer serves to bring surfaces of a structural defect into approximation, whereafter use of the thermoplastic polymer for molecular scale healing allowed for movement of the thermoplastic polymer into the defect and thus obtain molecular scale healing. The thermoplastic can be fibers, particles or spheres which are used by heating to a level at or above the thermoplastic's melting point, then cooling of the composition below the melting temperature of the thermoplastic. Compositions of the invention have the ability to not only close macroscopic defects, but also to do so repeatedly even if another wound/damage occurs in a previously healed/repaired area.

  20. Thermal recycling and re-manufacturing of glass fibre thermosetting composites

    Fraisse, A.; Beauson, J.; Brøndsted, P.; Madsen, B.


    The impact of using thermally recycled glass fibre in re-manufactured composites was investigated. A unidirectional glass fibre thermosetting composite laminate was manufactured. The matrix in one part of the laminate was burnt off to recover the glass fibres. These recycled glass fibres were used to manufacture a new composite laminate with the same fibre architecture as the pristine one. The fibres, the matrix and the composite laminates were thoroughly characterised and analysed. The results show that good materials quality was obtained for both laminates. A difference in fibre packing behaviour was observed in the composites with the pristine and the recycled fibres, which lead to a lower fibre volume fraction in the latter one. The Young's modulus of the composites was not changed by the recycling process, if the lower fibre volume fraction is taken into account. However, a marked drop in the maximum stress of the composites was reported, which was found to be related to the loss in maximum stress of the fibres.

  1. Maxwell-Wagner-Silars relaxations due to glass occlusions in a thermoset composite

    Aldrich, P. D.; McGee, R. L.; Yalvaç, S.; Bonekamp, J. E.; Thurow, S. W.


    Maxwell-Wagner-Silars (MWS) dielectric relaxations have been studied in thermoset composites made with hollow glass microspheres and reinforced with aramid fiber. Over the temperature range reported (140-230 °C) the glass microspheres show a conductivity of 10-10-10-5 (Ω cm)-1 so that MWS loss peaks fall in the 102-105 Hz frequency range. The apparent activation energy for the relaxation is about 20 kcal/mole. The observed MWS relaxation times depend only on temperature and not on volume fraction of microspheres as predicted by MWS theory. Also, the enhancement of activation energy for the relaxation over the activation energy for conduction of the glass seems to be explainable from the standpoint of the frequency and temperature dependence of the glass dielectric constant.

  2. Regenerated thermosetting styrene-co-acrylonitrile sandwich composite panels reinforced by jute fibre: structures and properties

    Jinglong Li; Qin Peng; Anrong Zeng; Junlin Li; Xiaole Wu; Xiaofei Liu


    Jute fibres-reinforced sandwich regenerated composite panels were fabricated using industrial waste thermosetting styrene-co-acrylonitrile (SAN) foam scraps via compression moulding for the purpose of recycling waste SAN foam and obtaining high physical performance. The jute fibres were, respectively, treated by heat, sodium hydroxide (NaOH) solution (5.0 wt%), and N,N-dimethylacetamide (DMAc) in order to improve the mechanical properties of the composites. The structures and mechanical properties of the composites were studied. The SAN matrix got compact and some crystalline region formed in SAN matrix via compression moulding. The composite reinforced by DMAc-treated jute fibres performed optimum mechanical properties among the regenerated panels whose impact strength, flexural strength, and compressive strength were 19.9 kJ m−2, 41.7 MPa, and 61.0 MPa, respectively. Good interfacial bonding between DMAc-treated fibres and SAN matrix was verified by peel test and exhibited in SEM photographs. Besides, the water absorption of DMAc-treated fibres composite was lower than other SAN/jute fibre-reinforced sandwich composite panels.

  3. Solvent Free Low-Melt Viscosity Imide Oligomers And Thermosetting Polyimide Composites

    Chuang, CHun-Hua (Inventor)


    This invention relates to the composition and a solvent-free process for preparing novel imide oligomers and polymers specifically formulated with effective amounts of a dianhydride such as 2,3,3',4-biphenyltetra carboxylic dianydride (a-BPDA), at least one aromatic diamine' and an endcapped of 4-phenylethynylphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260-280" C. When the imide oligomer melt is cured at about 371 C. in a press or autoclave under 100-500 psi, the melt resulted in a thermoset polyimide having a glass transition temperature (T(sub g)) equal to and above 310 C. A novel feature of this process is that the monomers; namely the dianhydrides, diamines and the endcaps, are melt processable to form imide oligomers at temperatures ranging between 232-280 C. (450-535 F) without any solvent. These low-melt imide oligomers can be easily processed by resin transfer molding (RTM), vacuum-assisted resin transfer molding (VARTM) or the resin infusion process with fiber preforms e.g. carbon, glass or quartz preforms to produce polyimide matrix composites with 288-343C (550-650 F) high temperature performance capability.

  4. Optoelectronic characterization of the curing process of thermoset-based composites

    Cusano, A.; Breglio, G.; Giordano, M.; Calabrò, A.; Cutolo, A.; Nicolais, L.


    In this paper, the optoelectronic characterization of the polymerization process of thermoset-based composites is described. As is well known, in the last decade, these kinds of material in the light of their low weight/mechanical strength ratio have been widely used in many industrial areas such as automotive, aeronautic and aerospace. Because of the dependence of their properties on the manufacturing stage, real-time monitoring of the curing process has been indicated as the key point for improving the quality and reducing manufacturing process costs. In fact, in situ identification of the status of the processed material would allow the implementation of an on-line control of the manufacturing stage, leading to the transformation of the classical process in a real scientific operation. Based on this line of argument, a less-contact optical technique has been used to monitor the refractive index variation of an epoxy-based resin due to the polymerization process. Starting from preliminary experimental results, a fibre optic sensor has been designed and developed in order to perform in situ cure monitoring by refractive index measurement. A theoretical model has been developed and validated by comparison with calorimetric characterization.

  5. Solvent free low-melt viscosity imide oligomers and thermosetting polymide composites

    Chuang, Chun-Hua (Inventor)


    .[.This invention relates to the composition and a solvent-free process for preparing novel imide oligomers and polymers specifically formulated with effective amounts of a dianhydride such as 2,3,3',4-biphenyltetra carboxylic dianydride (a-BPDA), at least one aromatic diamine and an endcapped of 4-phenylethynylphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at C. When the imide oligomer melt is cured at about C. in a press or autoclave under 100-500 psi, the melt resulted in a thermoset polyimide having a glass transition temperature (T.sub.g) equal to and above C. A novel feature of this process is that the monomers; namely the dianhydrides, diamines and the endcaps, are melt processable to form imide oligomers at temperatures ranging between C. ( F.) without any solvent. These low-melt imide oligomers can be easily processed by resin transfer molding (RTM), vacuum-assisted resin transfer molding (VARTM) or the resin infusion process with fiber preforms e.g. carbon, glass or quartz preforms to produce polyimide matrix composites with C. ( F.) high temperature performance capability..]. .Iadd.This invention relates to compositions and a solvent-free reaction process for preparing imide oligomers and polymers specifically derived from effective amounts of dianhydrides such as 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA), at least one aromatic polyamine and an end-cap such as 4-phenylethynyphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at C..Iaddend.

  6. Thermosetting composite matrix materials based on allyl and/or propargyl substituted cyclopentadiene, indene and fluorene

    Tregre, Gregory Jude

    A series of all-hydrocarbon thermoset composite matrix resins was synthesized via electrophilic substitution of cyclopentadiene, indene, and fluorene ring systems with allyl and/or propargyl halides under phase transfer conditions. Reaction of cyclopentadiene with allyl chloride (ACP resin), propargyl bromide (PCP resin) or various feed ratios of allyl chloride and propargyl bromide (APCP resins) yielded mixtures of products with 2-6 substituents per cyclopentadiene ring. Reaction of indene with allyl chloride (Al resins) or propargyl bromide (PI resins) yielded mixtures of products with 2-4 substituents per indene. In both sets of resins the allyl functionality obtained a greater average degree of substitution than the analogous propargyl species. Differential scanning calorimetric (DSC) analysis of the multifunctional resins showed broad, high-energy thermal cures in all cases. The enthalpies of cure for ACP and PCP were 750 J/g and 805 J/g, respectively, with peak cure energies occurring at 310 and 248sp°C. The enthalpy of cure for APCP resins ranged from 750 J/g to 800 J/g with higher propargyl-functional resins yielding higher enthalpies of cure. Physically mixed ACP/PCP resin systems gave peak cure temperatures and energy values comparable to APCP resins. The enthalpies of cure for Al and PI-resins were 480 J/g and 630 J/g, respectively. Peak cure temperature for Al resin was 320sp°C, while the peak cure for PI resin occurred at 282sp°C. Infrared spectroscopy (IR) and nuclear magnetic resonance spectroscopy (NMR) were used to evaluate mechanisms of cure in the experimental resins. The allyl functional resins cured through a combination of ene reactions and polyaddition reactions. The propargyl functional resins cured through ene reactions and polyadditions but also underwent some cyclotrimerization of the propargyl functionalities. A small amount of autoxidation was seen in all of the resins. Thermal stability and carbon yields of the cured resins were

  7. The effect of calcining temperature on the properties of 0-3 piezoelectric composites of PZT and a liquid crystalline thermosetting polymer

    Ende, D.A. van den; Groen, W.A.; Zwaag, S. van der


    We report on the optimisation of a recently developed high performance 0-3 piezoelectric composite comprising of the piezoelectric Lead Zirconate Titanate (PZT) powder and a liquid crystalline thermosetting matrix polymer (LCT). The matrix polymer is a liquid crystalline polymer comprising of an HBA

  8. Recycling of shredded composites from wind turbine blades in new thermoset polymer composites

    Beauson, Justine; Madsen, Bo; Toncelli, Chiara


    As the energy produced from wind increases every year, a concern has raised on the recycling of wind turbine blades made of glass fibre composites. In this context, the present study aims to characterize and understand the mechanical properties of polyester resin composites reinforced with shredded...... an analytical model, and fibre orientation parameters for strength modelling were established. The stress-strain curves revealed composite failure at unusual low strain values, and micrographs of the fracture surface indicated poor adhesion between SC and matrix. To tackle this problem, chemical treatment of SC...

  9. Thermosetting polyimide resin matrix composites with interpenetrating polymer networks for precision foil resistor chips based on special mechanical performance requirements

    Wang, X.Y., E-mail: [School of Electronic Information Engineering, Tianjin University, Tianjin 300072 (China); Ma, J.X.; Li, C.G. [School of Electronic Information Engineering, Tianjin University, Tianjin 300072 (China); Wang, H.X. [ZHENGHE electronics Co., Ltd, Jining 272023 (China)


    Highlights: • Macromolecular materials were chosen to modify thermosetting polyimide (TSPI). • The formation of IPN structure in TSPI composite polymers was discussed. • The special mechanical properties required were the main study object. • The desired candidate materials should have proper hardness and toughness. • The specific mechanical data are quantitatively determined by experiments. - Abstract: Based on interpenetrating networks (IPNs) different macromolecular materials such as epoxy, phenolic, and silicone resin were chosen to modify thermosetting polyimide (TSPI) resin to solve the lack of performance when used for protecting precision foil resistor chips. Copolymerization modification, controlled at curing stage, was used to prepare TSPI composites considering both performance and process requirements. The mechanical properties related to trimming process were mainly studied due to the special requirements of the regularity of scratch edges caused by a tungsten needle. The analysis on scratch edges reveals that the generation and propagation of microcracks caused by scratching together with crack closure effect may lead to regular scratch traces. Experiments show that the elongation at break of TSPI composites is the main reason that determines the special mechanical properties. The desired candidate materials should have proper hardness and toughness, and the specific mechanical data are that the mean elongation at break and tensile strength of polymer materials are in the range of 9.2–10.4% and 100–107 MPa, respectively. Possible reasons for the effect of the modifiers chosen on TSPI polymers, the reaction mechanisms on modified TSPI resin and the IPN structure in TSPI composite polymers were discussed based on IR and TG analysis.

  10. Performance of Integrated Fiber Optic, Piezoelectric, and Shape Memory Alloy Actuators/Sensors in Thermoset Composites

    Trottier, C. Michael


    Recently, scientists and engineers have investigated the advantages of smart materials and structures by including actuators in material systems for controlling and altering the response of structural environments. Applications of these materials systems include vibration suppression/isolation, precision positioning, damage detection and tunable devices. Some of the embedded materials being investigated for accomplishing these tasks include piezoelectric ceramics, shape memory alloys, and fiber optics. These materials have some benefits and some shortcomings; each is being studied for use in active material design in the SPICES (Synthesis and Processing of Intelligent Cost Effective Structures) Consortium. The focus of this paper concerns the manufacturing aspects of smart structures by incorporating piezoelectric ceramics, shape memory alloys and fiber optics in a reinforced thermoset matrix via resin transfer molding (RTM).

  11. Composite coating with synergistic effect of biomimetic epoxy thermoset morphology and incorporated superhydrophobic silica for corrosion protection

    W. F. Ji


    Full Text Available In this work, potential anticorrosive coating resulted from the composite with synergistic effect of biomimetic epoxy thermoset (BET morphology and incorporated superhydrophobic silica microspheres was presented. First of all, superhydrophobic methyl-modified silica (MS microspheres were synthesized by performing the conventional base-catalyzed sol-gel process of MTMS and APTMS. The as-prepared MS microspheres were identified as having an average particle size of ~1 µm in diameter. The as-prepared MS microspheres were characterized by Fourier transform infrared spectrometry (FTIR, 29Si and 13C solid-state nuclear magnetic resonance (NMR spectroscopy. Morphological properties of MS microspheres and BET-silica composite coating were studied by scanning electron microscopy (SEM. Subsequently, 3 wt% of MS microspheres were incorporated into an epoxy slurry of DGEBA/T-403 in dimetyl acetamide (DMAc, followed by performing the programmed heating through nanocasting technique with PDMS as soft template materials for pattern transfer by using leaf of Xanthosoma Sagittifolium as natural template, leading to the formation of artificial biomimetic composite coating. The appearance/dispersion capability of silica microspheres in BET coating was confirmed by the energy dispersive X-ray spectroscopy (EDX and Si-mapping. The roughness level of BET and BEC-3% were detected by AFM. The BETsilica composite was found to exhibit a contact angle (CA of ~153°, revealing the synergistic effect of biomimetic epoxy morphology and incorporated superhydrophobic MS microspheres, which is found to be more hydrophobic than that of neat epoxy thermoset (CA = 81°. Corrosion protection of as-prepared coatings was demonstrated by performing a series of electrochemical measurements (Tafel, Nyquists and Bode plots upon CRS electrodes in saline condition. It should be noted that the BET coatings upon CRS electrode revealed an effectively enhanced corrosion protection as compared

  12. Aromatic Thermosetting coPolyester Composites for High Temperature and Cryogenic Applications Project

    National Aeronautics and Space Administration — Advanced composite materials processable by cost-effective manufacturing play an important role in developing lightweight structures for future exploratory missions....

  13. Influence of Cure Shrinkage on Process-Induced Stress and Deformation in Thick Thermosetting Composites


    unidirectional composite micromechanics model The constituent fiber properties (constant), the resin properties and chemical shrinkage (cure dependent...during cure. Changes in the resin properties directly influence the mechanical properties in the composite, and chemical shrinkage represents a...xA (5) The expansion coefficients, otL and or, are based on the micromechanics model utilizing constant fiber properties. cure dependent resin


    Sudhir Kumar Saw


    Full Text Available Natural fibres are partly replacing currently used synthetic fibres as reinforcement for polymer composites. Jute fibre bundles were high-cellulose-content modified by alkali treatment, while the bagasse fibre bundles were modified by creating quinones in the lignin portions of fibre surfaces and reacting them with furfuryl alcohol (FA to increase their adhesiveness. The effects of different fibre bundle loading and modification of bagasse fibre surfaces in hybrid fibre reinforced epoxy composites have been studied. The role of fibre/matrix interactions in chemically modified hybrid composites were investigated using Differential Scanning Calorimeter, Differential Thermo Gravimetry, and a Universal Tensile Machine and compared with those of unmodified bagasse fibre bundles incorporated with modified jute fibre bundles reinforced hybrid composites. Fibre surface modification reduced the hydrophilicity of fibre bundles, and significantly increased mechanical properties of hybrid composites were observed in conjunction with SEM images. The SEM analysis of the fibre and the composite fractured surfaces have confirmed the FA grafting and shown a better compatibility at the interface between chemically modified fibre bundles and epoxy resin. This paper incorporates interesting results of thermomechanical properties and evaluation of fibre/matrix interactions.

  15. Optimization of the Temperature-Time Curve for the Curing Process of Thermoset Matrix Composites

    Aleksendrić, Dragan; Carlone, Pierpaolo; Ćirović, Velimir


    An intelligent optimization model aiming at off-line or pre-series optimization of the thermal curing cycle of polymer matrix composites is proposed and discussed. The computational procedure is based on the coupling of a finite element thermochemical process model, dynamic artificial neural networks and genetic algorithms. Objective of the optimization routine is the maximization of the composite degree of cure by the definition of the autoclave temperature. Obtained outcomes evidenced the capability of the method as well as its efficiency with respect to hard computing or experimental procedures.

  16. Properties of compression moulded new fully biobased thermoset composites with aligned flax fibre textiles

    Pohl, Th.; Bierer, M.; Natter, E.


    into composites using an industrial scale compression moulding machine, and their material properties were analysed. The density was calculated by using a computed microtomography system, and tensile tests were carried out. Besides the mechanical properties, the burning and the moisture absorption behaviour have...

  17. Processing and characterization of natural cellulose fibers/thermoset polymer composites.

    Thakur, Vijay Kumar; Thakur, Manju Kumari


    Recently natural cellulose fibers from different biorenewable resources have attracted the considerable attraction of research community all around the globe owing to their unique intrinsic properties such as biodegradability, easy availability, environmental friendliness, flexibility, easy processing and impressive physico-mechanical properties. Natural cellulose fibers based materials are finding their applications in a number of fields ranging from automotive to biomedical. Natural cellulose fibers have been frequently used as the reinforcement component in polymers to add the specific properties in the final product. A variety of cellulose fibers based polymer composite materials have been developed using various synthetic strategies. Seeing the immense advantages of cellulose fibers, in this article we discuss the processing of biorenewable natural cellulose fibers; chemical functionalization of cellulose fibers; synthesis of polymer resins; different strategies to prepare cellulose based green polymer composites, and diverse applications of natural cellulose fibers/polymer composite materials. The article provides an in depth analysis and comprehensive knowledge to the beginners in the field of natural cellulose fibers/polymer composites. The prime aim of this review article is to demonstrate the recent development and emerging applications of natural cellulose fibers and their polymer materials.

  18. Modelling heat generation and transfer during cure of thermoset composites processed by resin transfer moulding (RTM)

    Skordos, Alexandros A.; Maistros, George M.; Turmel, Denis J-P; Partridge, Ivana K


    The development of a heat transfer model for the curing stage of the RTM process is presented. Despite the intense interest in the modelling and simulation of this process the relevant work is currently limited to development of flow models of the filling stage. The principles of heat transfer modelling of composites cure have already been reported and applied to the autoclave process by many investigators. In the present investigation, the same concept is used for the imple...

  19. Biobased Carbon Fibers and Thermosetting Resins for Use in DoD Composites Applications


    Standards and Technology (NIST)-grade silicon standard powder for accurate identification of 2θ position on integrated azimuthal scan. The exposure time ... time , and 25 washing cycles were established as standard protocol for each batch of SKL purification. After washing under these conditions, the ash...the automotive companies ’ desire to enhance fuel efficiency (50 mpg by 2025) by changing from a metal to a lightweight composite materials platform

  20. Shape recovery in a thermoset shape memory polymer and its fabric-reinforced composites


    Full Text Available A shape memory polymer (SMP can be deformed from a permanent to a temporary shape above their transformation temperature. Upon reheating, the SMP spontaneously returns to the permanent shape. SMP’s show high deformability, but the recovery stresses are very low, thus limiting the size of the components. This paper presents the first results of an ongoing research to develop large sized components based on SMP. To achieve higher recovery stresses, asymmetric fibre reinforced shape memory composites were produced (SMPC using resin transfer moulding. The results show a 30-fold increase in recovery stress, compared to the neat SMP resin. The recovery stress is independent of the deformation temperature, but is strongly affected by the degree of deformation. At higher deformation levels, crazing occurs. Even though the visible effects of the crazing disappear during reheating, it does influence the recovery stress. This indicates that the ability to recover the permanent shape might change in cyclic loading. All composites tested show complete recovery upon reheating. The rate of shape recovery is higher when the fibre reinforcement is loaded in compression.

  1. Reversible Thermoset Adhesives

    Mac Murray, Benjamin C. (Inventor); Tong, Tat H. (Inventor); Hreha, Richard D. (Inventor)


    Embodiments of a reversible thermoset adhesive formed by incorporating thermally-reversible cross-linking units and a method for making the reversible thermoset adhesive are provided. One approach to formulating reversible thermoset adhesives includes incorporating dienes, such as furans, and dienophiles, such as maleimides, into a polymer network as reversible covalent cross-links using Diels Alder cross-link formation between the diene and dienophile. The chemical components may be selected based on their compatibility with adhesive chemistry as well as their ability to undergo controlled, reversible cross-linking chemistry.

  2. Conducting Thermoset Polymers.


    polymers conducting. The acetylene-terminated Schiff base and acetylene-terminated polythiophene monomers were first cured, then doped with iodine... Schiff base thermoset was implanted with high energy argon ions using a commercial ion implanter. Electron spin resonance, photoluminescence, and...photoabsorption data suggest that polarons can form in the doped and undoped forms of the acetylene-terminated Schiff base and polythiophene thermoset

  3. Bis-propargyl thermosets

    Douglas, Elliot P.; Langlois, David A.; Benicewicz, Brian C.


    The present invention provides (1) curable bispropargyl-containing monomers represented by the formula: B.sup.1 --A.sup.1.sub.m --R--A.sup.2.sub.n --B.sup.2 wherein R is a radical selected from the group consisting of 1,4-phenylene, 4,4'-biphenyl, 2,6-naphthalene, --C.sub.6 H.sub.4 --CR.sup.2 .dbd.CR.sup.2 --C.sub.6 H.sub.4 -- wherein R.sup.2 is H or CH.sub.3, and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, fluoroalkyl or fluoroalkoxy, A.sup.1 and A.sup.2 are selected from the group consisting of --C.sub.6 H.sub.4 --C(O)--O-- and --C.sub.6 H.sub.4 --O--C(O)--, m and n are 0 or 1, m+n is 0, 1 or 2, and B.sup.1 and B.sup.2 are --OCH.sub.2 --C.tbd.C--H, (2) thermoset compositions comprised of cured segments derived from monomers represented by the formula: B.sup.1 --A.sup.1.sub.m --R--A.sup.2.sub.n --B.sup.2 as described above, and (3) curable blends of at least two of the monomers.

  4. Kinetics and mechanics of photo-polymerized triazole-containing thermosetting composites via the copper(I)-catalyzed azide-alkyne cycloaddition.

    Song, Han Byul; Wang, Xiance; Patton, James R; Stansbury, Jeffrey W; Bowman, Christopher N


    Several features necessary for polymer composite materials in practical applications such as dental restorative materials were investigated in photo-curable CuAAC (copper(I)-catalyzed azide-alkyne cycloaddition) thermosetting resin-based composites with varying filler loadings and compared to a conventional BisGMA/TEGDMA based composite. Tri-functional alkyne and di-functional azide monomers were synthesized for CuAAC resins and incorporated with alkyne-functionalized glass microfillers for CuAAC composites. Polymerization kinetics, in situ temperature change, and shrinkage stress were monitored simultaneously with a tensometer coupled with FTIR spectroscopy and a data-logging thermocouple. The glass transition temperature was analyzed by dynamic mechanical analysis. Flexural modulus/strength and flexural toughness were characterized in three-point bending on a universal testing machine. The photo-CuAAC polymerization of composites containing between 0 and 60wt% microfiller achieved ∼99% conversion with a dramatic reduction in the maximum heat of reaction (∼20°C decrease) for the 60wt% filled CuAAC composites as compared with the unfilled CuAAC resin. CuAAC composites with 60wt% microfiller generated more than twice lower shrinkage stress of 0.43±0.01MPa, equivalent flexural modulus of 6.1±0.7GPa, equivalent flexural strength of 107±9MPa, and more than 10 times higher energy absorption of 10±1MJm(-3) when strained to 11% relative to BisGMA-based composites at equivalent filler loadings. Mechanically robust and highly tough, photo-polymerized CuAAC composites with reduced shrinkage stress and a modest reaction exotherm were generated and resulted in essentially complete conversion. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  5. 热固性树脂基复合材料的回收方法研究进展%Recycling Progress on Thermosetting Resin Based Composites

    徐平来; 李娟; 李晓倩


    The physical and chemical methods for fiber reinforced thermosetting resin based composites recycling were reviewed.It was emphasized that the progress and achievements of some conventional technologies and innovative processes,including pyrolysis at high temperature,fluidized bed processing,microwave heating,oxidation using nitric acid,solvolysis,supercritical fluid technology,green oxidation,source design,etc.The prospects for the application of chemical recycling carbon fiber with high quality were also discussed.It was concluded that there was no universal method to recycle all of the composites.It was also suggested that the systemic recycling approach should be developed according to the specific characteristics of each composites.%从物理法和化学法角度对热固性树脂基复合材料国内外回收方法的研究进展进行了综述,重点介绍了高温热解法、流化床热解法、微波热解法、硝酸氧化法、溶剂分解法及近几年兴起的超/亚临界流体技术、绿色氧化法和源头设计法等化学回收方法及所取得的进展和成果,对碳纤维增强复合材料的高值回收前景进行了展望.指出没有一种方法能解决所有复合材料的回收问题,必须根据复合材料本身的特点发展合适的系统解决方案.

  6. Liquid crystal polyester thermosets

    Benicewicz, Brian C.; Hoyt, Andrea E.


    The present invention provides (1) curable liquid crystalline polyester monomers represented by the formula: R.sup.1 --A.sup.1 --B.sup.1 --A.sup.2 --B.sup.2 --A.sup.3 --R.sup.2 where R.sup.1 and R.sup.2 are radicals selected from the group consisting of maleimide, substituted maleimide, nadimide, substituted naimide, ethynyl, and (C(R.sup.3).sub.2).sub.2 where R.sup.3 is hydrogen with the proviso that the two carbon atoms of (C(R.sup.3).sub.2).sub.2 are bound on the aromatic ring of A.sup.1 or A.sup.3 to adjacent carbon atoms, A.sup.1 and A.sup.3 are 1,4-phenylene and the same where said group contains one or more substituents selected from the group consisting of halo, e.g., fluoro, chloro, bromo, or iodo, nitro lower alkyl, e.g., methyl, ethyl, or propyl, alkoxy, e.g., methoxy, ethoxy, or propoxy, and fluoroalkyl, e.g., trifluoromethyl, pentafluoroethyl and the like, A.sup.2 is selected from the group consisting of 1,4-phenylene, 4,4'-biphenyl, 2,6-naphthylene and the same where said groups contain one or more substituents selected from the group consisting of halo, e.g., fluoro, chloro, bromo, or iodo, nitro, lower alkyl, e.g., methyl, ethyl, and propyl, lower alkoxy, e.g., methoxy, ethoxy, or propoxy, and fluoroalkyl or fluoroalkoxy, e.g., trifluoromethyl, pentafluoroethyl and the like, and B.sup.1 and B.sup.2 are selected from the group consisting of --C(O)--O-- and --O--C(O)--, (2) thermoset liquid crystalline polyester compositions comprised of heat-cured segments derived from monomers represented by the formula: R.sup.1 --A.sup.1 --B.sup.1 --A.sup.2 --B.sup.2 --A.sup.3 --R.sup.2 as described above, (3) curable blends of at least two of the polyester monomers and (4) processes of preparing the curable liquid crystalline polyester monomers.

  7. Pentane-1,5-diol as a percutaneous absorption enhancer.

    Faergemann, Jan; Wahlstrand, Björn; Hedner, Thomas; Johnsson, Jörgen; Neubert, Reinhard H H; Nyström, Lena; Maibach, Howard


    Propylene glycol (propane-1,2-diol) is the only diol widely used in dermatology. Pentane-1,5-diol is mainly used as a plasticizer in cellulose products and adhesives, in dental composites and in brake fluid compositions and as a preservative for grain. However, pentane-1,5-diol is also an effective solvent, water-binding substance, antimicrobial agent and preservative and may therefore replace several ingredients in a skin composition. The release of tri-iodothyroacetic acid (TRIAC) and percutaneous absorption of hydrocortisone and mometasone furoate with either pentane-1,5-diol or propane-1,2-diol and 2-methyl-pentane-2,4-diol (hexylene glycol), respectively, as enhancers was compared. The release of TRIAC was 21% higher when pentane-1,5-diol was used as an enhancer instead of propane-1,2-diol. The percutaneous absorption of hydrocortisone through the skin was increased 12 times with propane-1,2-diol compared to 4.4 times with pentane-1,5-diol. However, the percutaneous absorption of hydrocortisone into the skin was 50% higher with pentane-1,5-diol compared to propane-1,2-diol. There was no significant difference, between the original mometasone furoate cream, with 2-methyl-pentane-2,4-diol, and the new cream with pentane-1,5-diol in the amount of mometasone furoate that was absorbed into the skin and through the skin. However, the cosmetic properties of the new mometasone furoate cream was superior to the original mometasone furoate cream, for examples, no bad odour, more even texture, goes better into the skin and has less greasiness. Pentane-1,5-diol can be used as a technology platform, which adds a series of desirable properties to dermatological preparations and enhances product usability. This will result in improved formulations for a series of major and commonly used dermatological drugs. When used in pharmaceutical topical preparations, pentane-1,5-diol will increase the percutaneous absorption of the active substance and it is an efficient antimicrobial

  8. Effects of Processing Parameters on the Forming Quality of C-Shaped Thermosetting Composite Laminates in Hot Diaphragm Forming Process

    Bian, X. X.; Gu, Y. Z.; Sun, J.; Li, M.; Liu, W. P.; Zhang, Z. G.


    In this study, the effects of processing temperature and vacuum applying rate on the forming quality of C-shaped carbon fiber reinforced epoxy resin matrix composite laminates during hot diaphragm forming process were investigated. C-shaped prepreg preforms were produced using a home-made hot diaphragm forming equipment. The thickness variations of the preforms and the manufacturing defects after diaphragm forming process, including fiber wrinkling and voids, were evaluated to understand the forming mechanism. Furthermore, both interlaminar slipping friction and compaction behavior of the prepreg stacks were experimentally analyzed for showing the importance of the processing parameters. In addition, autoclave processing was used to cure the C-shaped preforms to investigate the changes of the defects before and after cure process. The results show that the C-shaped prepreg preforms with good forming quality can be achieved through increasing processing temperature and reducing vacuum applying rate, which obviously promote prepreg interlaminar slipping process. The process temperature and forming rate in hot diaphragm forming process strongly influence prepreg interply frictional force, and the maximum interlaminar frictional force can be taken as a key parameter for processing parameter optimization. Autoclave process is effective in eliminating voids in the preforms and can alleviate fiber wrinkles to a certain extent.

  9. A study of the kinetic, dielectric, and rheological properties of thermosetting resins used in pultruded polymer composites

    Shanku, Reshma

    A comprehensive analysis has been conducted of the curing behavior of AOC VIBRINRTM E-606-6 (medium reactivity isophthalic), E-964 (high reactivity isophthalic), and P-341 (highest reactivity) polyester resins, and Shell EPON 9310 resin/EPON 9360 curing agent/EPON 537 accelerator resin system using calorimetric, dielectric, and rheological methods. The unsaturated polyester resins were cured with two different catalysts at three levels of concentration. Calorimetry and dielectrometry were employed to obtain polyester resin curing properties for the resin formulations studied. Rheological characterization of selected polyester resin formulations and the EPON 9310 resin system were also conducted. Kinetic parameters for all resin formulations were determined using a differential scanning calorimeter (DSC) by dynamic and isothermal methods. The dynamic and isothermal kinetic parameters obtained were used to generate heat flow values which were compared to the experimental DSC heat flow recorded; kinetic parameters that accurately modeled the pultrusion process were selected. The kinetic parameters were used in a numerical model to predict temperatures and degrees of cure under pultrusion processing conditions. The results obtained from the in-situ dielectric tests conducted on the pultruder in the Composites Material Laboratory at the University of Mississippi were compared to the degree of cure predictions from the numerical model and the experimental degree of cure from calorimetric analysis. Prior to the in-situ pultrusion studies, small quantities of resin formulations were tested for their dielectric cure properties when heated in an oven simulating pultrusion processing temperatures and rate of heating. This technique allowed small quantities of resins to be tested for degrees of cure. It was determined that such screening tests can be effectively conducted and can aid in pultrusion process planning. Complex viscosity profiles until gelation were generated for

  10. Liquid crystalline thermosetting polyimides. Final report

    Hoyt, A.E.; Huang, S.J. [Connecticut Univ., Storrs, CT (United States). Inst. of Materials Science


    Phase separation of rodlike reinforcing polymers and flexible coil matrix polymers is a common problem in formulating molecular composites. One way to reduce phase separation might be to employ liquid crystalline thermosets as the matrix material. In this work, functionally terminated polyimide oligomers which exhibit lyotropic liquid crystalline behavior were successfully prepared. Materials based on 2,2{prime}-bis(trifluoromethyl)-4,4{prime}-diaminobiphenyl and 3,3{prime},4,4{prime}-biphenylenetetra-carboxylic dianhydride have been synthesized and characterized.

  11. Thermoset epoxy polymers from renewable resources

    East, Anthony; Jaffe, Michael; Zhang, Yi; Catalani, Luiz H


    Novel thermoset epoxy polymers using the bisglycidyl ethers of anhydrosugars, such as isosorbide, isomannide, and isoidide, are disclosed. The bisglycidyl ethers are useful as substitutes for bisphenol A in the manufacture of thermoset epoxy ethers. The anhydrosugars are derived from renewable sources and the bisglycidyl ethers are not xenoestrogenic and the thermoset curing agents are likewise derived form renewable resources.

  12. Matriz termofixa fenólica em compósitos reforçados com fibras de bagaço de cana-de-açúcar Thermoset phenolic matrix in sugar cane bagasse fiber-reinforced composites

    Jane Maria F. de Paiva


    Full Text Available Neste trabalho, a lignina extraída pelo processo organossolve do bagaço de cana-de-açúcar substituiu parcialmente fenol (40% em massa em matrizes termofixas reforçadas com fibras curtas de bagaço de cana-de-açúcar (30, 40, 50, 60 e 70%, v/v. Os compósitos obtidos foram caracterizados por TG, DSC, DMTA, Resistência ao Impacto Charpy, Dureza Shore D. Os resultados obtidos mostraram ser viável a substituição de fenol por lignina em matrizes fenólicas. No entanto, para que se obtenha compósitos com propriedades compatíveis com às exigidas para aplicações industriais, modificações devem ser feitas: modificação de fibras por meio de reações químicas, diversificação do comprimento das fibras vegetais, realização de etapas de cura em temperaturas superiores as consideradas no presente trabalho.In this work the performance of thermoset phenolic/sugar cane bagasse composites were ascertained as a function of fiber content and matrix modification. The matrix was modified by using lignin, extracted from sugar cane bagasse, as a partial (40% wt phenol substitute. The thermoset polymer matrices and related composites were compression moulded and the products were characterized by TG, DSC, DMTA, Impact Strength, Shore D Hardness. Our results indicate that phenol can be substituted by lignin in the synthesis of phenolic resins. However, further work is necessary if one is to obtain composites complying with the performance demanded for industrial applications. In this case, chemical modification of the fibers, varying lengths of the vegetables fibers and cure steps at higher temperatures than the ones considered here must be performed.

  13. Thermoset Blends of an Epoxy Resin and Polydicyclopentadiene

    Rohde, Brian J.; Le, Kim Mai; Krishnamoorti, Ramanan; Robertson, Megan L.


    The mechanical properties of two chemically distinct and complementary thermoset polymers were manipulated through development of thermoset blends. The thermoset blend system was composed of an anhydride-cured diglycidyl ether of bisphenol A (DGEBA)-based epoxy resin, contributing high tensile strength and modulus, and polydicyclopentadiene (PDCPD), which has a higher toughness and impact strength as compared to other thermoset polymers. Ultra-small-angle and small-angle X-ray scattering analysis explored the morphology of concurrently cured thermoset blends, revealing a macroscopically phase separated system with a surface fractal structure across blended systems of varying composition. The epoxy resin rich and PDCPD rich phases exhibited distinct glass transitions (Tg’s): the Tg observed at higher temperature was associated with the epoxy resin rich phase and was largely unaffected by the presence of PDCPD, whereas the PDCPD rich phase Tg systematically decreased with increasing epoxy resin content due to inhibition of dicyclopentadiene ring-opening metathesis polymerization. The mechanical properties of these phase-separated blends were in reasonable agreement with predictions by the rule of mixtures for the blend tensile strength, modulus, and fracture toughness. Scanning electron microscopy analysis of the tensile and fracture specimen fracture surfaces showed an increase in energy dissipation mechanisms, such as crazing, shear banding, and surface roughness, as the fraction of the more ductile component, PDPCD, increased. These results present a facile method to tune the mechanical properties of a toughened thermoset network, in which the high modulus and tensile strength of the epoxy resin can be largely retained at high epoxy resin content in the blend, while increasing the fracture toughness.

  14. Mechanical characterization and modeling of curing thermosets

    Van 't Hof, C.


    Chemical shrinkage and simultaneous build-up of mechanical properties in curing thermosets leads to the build-up of residual stresses and strains. Depending on the constraints these may cause interface failure, dimensional inaccuracy or failure in the thermoset or its surrounding structure. The pre

  15. Synthese De Diols Copolyesters (Synthesis of Copolyester Diols)


    solidos . ’.os propr4.Et~s a6caniques sont sp&-.ioiires I cellos obtenuos avoc los diols polycaprolactones (tableau IX).I 4.0 RESULTATS ET DISCUSSIONS...sont solidos A o0 C. 4.3 Les dio1s ou triols Capol1yosters obtonus A 1partir des diols ou trioJ~i~~juM et dol’ c-caprolactone is ~~La copolya~risation do...propergols Quelquos-uns seulement des co-polymares do synth~se ont 6t6 utilisgs dans los propergols solidos . Souls los diols copolyesters Empol dimaro

  16. Recyclable, strong thermosets and organogels via paraformaldehyde condensation with diamines.

    García, Jeannette M; Jones, Gavin O; Virwani, Kumar; McCloskey, Bryan D; Boday, Dylan J; ter Huurne, Gijs M; Horn, Hans W; Coady, Daniel J; Bintaleb, Abdulmalik M; Alabdulrahman, Abdullah M S; Alsewailem, Fares; Almegren, Hamid A A; Hedrick, James L


    Nitrogen-based thermoset polymers have many industrial applications (for example, in composites), but are difficult to recycle or rework. We report a simple one-pot, low-temperature polycondensation between paraformaldehyde and 4,4'-oxydianiline (ODA) that forms hemiaminal dynamic covalent networks (HDCNs), which can further cyclize at high temperatures, producing poly(hexahydrotriazine)s (PHTs). Both materials are strong thermosetting polymers, and the PHTs exhibited very high Young's moduli (up to ~14.0 gigapascals and up to 20 gigapascals when reinforced with surface-treated carbon nanotubes), excellent solvent resistance, and resistance to environmental stress cracking. However, both HDCNs and PHTs could be digested at low pH (self-healing properties.

  17. Chemorheology of highly filled thermosets: Effects of fillers

    Halley, P.J. [Univ. of Queensland, Brisbane (Australia)


    Highly filled thermosets are utilised in the manufacture of many high value added products in the aerospace, communication, computer and automobile industries. A fundamental understanding of the processing of these materials has, however, been hindered by the inherent complexities of the flow and cure properties of these composite thermoset materials. A chemorheological (gel point and chemoviscosity) testing procedure is described here that uses dynamic multiwave tests on a modified Rheometrics RDSII system, using a filled epoxy moulding compound (EMC). Data from this testing procedure has been combined with physical property and kinetic data to produce realistic simulation results using flow simulation software (TSET; MOLDFLOW Pty Ltd). This chemorheological testing procedure has now been successfully implemented commercially by MOLDFLOW Pty Ltd.

  18. Thermoset elastomers derived from carvomenthide.

    Yang, Jinyoung; Lee, Sangjun; Choi, Woo Jin; Seo, Howon; Kim, Pilhan; Kim, Geon-Joong; Kim, Young-Wun; Shin, Jihoon


    Renewable thermoset elastomers were prepared using the plant-based monomer carvomenthide. Controlled ring-opening transesterification polymerization of carvomenthide using diethylene glycol as an initiator gave α,ω-dihydroxyl poly(carvomenthide) (HO-PCM-OH), which was subsequently converted to carboxy-telechelic poly(carvomenthide) (HOOC-PCM-COOH) by esterification with excess succinic anhydride through a one-pot, two-step process, leading to no crystallinity, high viscosity, strong thermal resistance, and low glass transition temperature of the resulting functionalized polyester. Thermal curing processes of the resulting 3, 6, and 12 kg mol(-1) prepolymers were achieved with trifunctional aziridine to give cross-linked PCM elastomers. The thermal properties, mechanical behavior, and biocompatibility of the rubbery thermoset products were investigated by differential scanning calorimetry, thermal gravimetric analysis, dynamic mechanical analysis, tensile tests under static and cyclic loads, and cell adherence. These new materials are useful candidates to satisfy the design objective for the engineering of a variety of soft tissues.

  19. Thermosetting epoxy resin/thermoplastic system with combined shape memory and self-healing properties

    Yao, Yongtao; Wang, Jingjie; Lu, Haibao; Xu, Ben; Fu, Yongqing; Liu, Yanju; Leng, Jinsong


    A novel and facile strategy was proposed to construct a thermosetting/thermoplastic system with both shape memory and self-healing properties based on commercial epoxy resin and poly(ɛ-caprolactone)-PCL. Thermoplastic material is capable of re-structuring and changing the stiffness/modulus when the temperature is above melting temperature. PCL microfiber was used as a plasticizer in epoxy resin-based blends, and served as a ‘hard segment’ to fix a temporary shape of the composites during shape memory cycles. In this study, the electrospun PCL membrane with a porous network structure enabled a homogenous PCL fibrous distribution and optimized interaction between fiber and epoxy resin. The self-healing capability is achieved by phase transition during curing of the composites. The mechanism of the shape memory effect of the thermosetting (rubber)/thermoplastic composite is attributed to the structural design of the thermoplastic network inside the thermosetting resin/rubber matrix.

  20. Nanocomposites with thermosetting matrix: structure formation at the interphase boundary

    KOROLEV Evgenij Valerjevich


    Full Text Available Composites with thermosetting matrix are often characterized by elevated values of operational properties – flexural and compressive strength, resistance to aggressive environments, etc. At the same time the cost of most thermosets (particularly – epoxy resins is quite high. Because of this the area of application of polymer composites in construction is limited. One of such application is the creation of multifunctional coatings. The high cost of resin dictates the need to improve the operational properties to ensure economic efficiency. So far, the known way to improve the operational properties is to produce nanoscale interfacial layer between fine filler and matrix in block. This way proved to be effective, but mechanism of the improvement is still uncertain. There areat least two different theories – so-called «adhesion theory» and «theory of deformable layer». The investigation is complicated by the variety of oligomers, hardeners (crosslinking agents and precursors of nanomodifiers. It is becoming more common lately to use adducts of aliphatic amines and epoxy oligomers as hardeners. As precursors of nanomodifiers the organosilicon compounds with siloxane bond in the main chain can be successfully used. In this paper we present results of investigation of a model system comprised of oligomer, crosslinking agent and precursor. The analysis of structure is carried out by means of Raman spectroscopy and atomic force microscopy. It is shown that at gelation point modifier has no significant effect on the chemical composition of the curing products; nevertheless, the admixture of modifier reduces the regularity of the emerging three-dimensional spatial net of thermoset. After completion of curing process the irregular spatial grid is still present. This indicates that in composites admixture of organosilicon precursors may lead to the formation of transition layer with reduced modulus of elasticity. Such layer, in turn, causes stress

  1. Thermoset phenolic matrices reinforced with unmodified and surface-grafted furfuryl alcohol sugar cane bagasse and curaua fibers: properties of fibers and composites.

    Trindade, W G; Hoareau, W; Megiatto, J D; Razera, I A T; Castellan, A; Frollini, E


    Composites based on phenolic matrices and unmodified and chemically modified sugar cane bagasse and curaua fibers were prepared. The fibers were oxidized by chlorine dioxide, mainly phenolic syringyl and guaiacyl units of the lignin polymer, followed by grafting furfuryl alcohol (FA), which is a chemical obtained from a renewable source. The fibers were widely characterized by chemical composition analysis, crystallinity, UV-vis diffuse reflectance spectroscopy, SEM, DSC, TG, tensile strength, and 13C CP-MAS NMR. The composites were analyzed by SEM, impact strength, and DMA. The SEM images and DMA results showed that the oxidation of sugar cane bagasse fibers followed by reaction with FA favored the fiber/matrix interaction at the interface. The same chemical modification was less effective for curaua fibers, probably due to its lower lignin content, since the reaction considered touches mainly the lignin moiety. The tensile strength results obtained showed that the fibers were partially degraded by the chemical treatment, decreasing then the impact strength of the composites reinforced with them. In the continuity of the present project, efforts has been addressed to the optimization of fiber surface modification, looking for reagents preferably obtained from renewable resources and for chemical modifications that intensify the fiber/matrix interaction without loss of mechanical properties.


    Elisabete Frollini


    Full Text Available Cellulose fibers obtained from the textile industry (lyocell were investigated as a potential reinforcement for thermoset phenolic matrices, to improve their mechanical properties. Textile cotton fibers were also considered. The fibers were characterized in terms of their chemical composition and analyzed using TGA, SEM, and X-ray. The thermoset (non-reinforced and composites (phenolic matrices reinforced with randomly dispersed fibers were characterized using TG, DSC, SEM, DMTA, the Izod impact strength test, and water absorption capacity analysis. The composites that were reinforced with lyocell fibers exhibited impact strengths of nearly 240 Jm-1, whereas those reinforced with cotton fibers exhibited impact strengths of up to 773 Jm-1. In addition to the aspect ratio, the higher crystallinity of cotton fibers compared to lyocell likely plays a role in the impact strength of the composite reinforced by the fibers. The SEM images showed that the porosity of the textile fibers allowed good bulk diffusion of the phenolic resin, which, in turn, led to both good adhesion of fiber to matrix and fewer microvoids at the interface.

  3. Evaluation of Nanoclay Exfoliation Strategies for Thermoset Polyimide Nanocomposite Systems

    Ginter, Michael J.; Jana, Sadhan C.; Miller, Sandi G.


    Prior works show exfoliated layered silicate reinforcement improves polymer composite properties. However, achieving full clay exfoliation in high performance thermoset polyimides remains a challenge. This study explores a new method of clay exfoliation, which includes clay intercalation by lower molecular weight PMR monomer under conditions of low and high shear and sonication, clay treatments by aliphatic and aromatic surfactants, and clay dispersion in primary, higher molecular weight PMR resin. Clay spacing, thermal, and mechanical properties were evaluated and compared with the best results available in literature for PMR polyimide systems.

  4. Highly stretchable thermoset fibers and nonwovens using thiol-ene photopolymerization.

    Shanmuganathan, Kadhiravan; Elliot, Steven M; Lane, Austin P; Ellison, Christopher J


    In this report, we describe the preparation and characterization of a new class of thermoset fibers with high elongation and elastic recovery. Integrating UV-activated thiol-ene photopolymerization and electrospinning, we demonstrate an environmentally friendly single step approach to convert small monomeric precursor molecules into highly elastic fibers and nonwoven mats. The fibers were derived by in situ photopolymerization of a trifunctional vinyl ether monomer and a tetrafunctional thiol. Although thermosets often offer good chemical and thermal stability, these fibers also have a high average elongation at break of 62%. The elastomeric nature of these vinyl-ether based fibers can be partly attributed to their subambient Tg and partly to the cross-link density, monomer structure, and resulting network homogeneity. Nonwoven mats of these fibers were also stretchable and exhibited a much higher elongation at break of about 85%. These thermoset stretchable fibers could have potential applications as textile, biomedical, hot chemical filtration, and composite materials.

  5. Poly (ricinoleic acid) based novel thermosetting elastomer.

    Ebata, Hiroki; Yasuda, Mayumi; Toshima, Kazunobu; Matsumura, Shuichi


    A novel bio-based thermosetting elastomer was prepared by the lipase-catalyzed polymerization of methyl ricinoleate with subsequent vulcanization. Some mechanical properties of the cured carbon black-filled polyricinoleate compounds were evaluated as a thermosetting elastomer. It was found that the carbon black-filled polyricinoleate compounds were readily cured by sulfur curatives to produce a thermosetting elastomer that formed a rubber-like sheet with a smooth and non-sticky surface. The curing behaviors and mechanical properties were dependent on both the molecular weight of the polyricinoleate and the amount of the sulfur curatives. Cured compounds consisting of polyricinoleate with a molecular weight of 100,800 showed good mechanical properties, such as a hardness of 48 A based on the durometer A measurements, a tensile strength at break of 6.91 MPa and an elongation at break of 350%.

  6. Microbial production of short chain diols.

    Jiang, Yudong; Liu, Wei; Zou, Huibin; Cheng, Tao; Tian, Ning; Xian, Mo


    Short chain diols (propanediols, butanediols, pentanediols) have been widely used in bulk and fine chemical industries as fuels, solvents, polymer monomers and pharmaceutical precursors. The chemical production of short chain diols from fossil resources has been developed and optimized for decades. Consideration of the exhausting fossil resources and the increasing environment issues, the bio-based process to produce short chain diols is attracting interests. Currently, a variety of biotechnologies have been developed for the microbial production of the short chain diols from renewable feed-stocks. In order to efficiently produce bio-diols, the techniques like metabolically engineering the production strains, optimization of the fermentation processes, and integration of a reasonable downstream recovery processes have been thoroughly investigated. In this review, we summarized the recent development in the whole process of bio-diols production including substrate, microorganism, metabolic pathway, fermentation process and downstream process.

  7. An SCFT Study of Nanostructuring in Epoxy Thermosets

    Oyerokun, Folusho; Fredrickson, Glenn; Leibler, Ludwik


    Increasing fracture resistance of epoxy thermosets via self assembly of block copolymers has generated significant interest in the past decade. Nanostructuring occurs because of the selectivity of the epoxy precursors to the different blocks of the block copolymer, i.e. one block is miscible (before curing), while the other block remains immiscible. The size and geometry of the nanostructures formed depends on the copolymer composition, solvent concentration and selectivity. Understanding the conditions at which nanostructuring occurs is important for rational design of high impact thermoset materials. A self-consistent field based study of blends of polystyrene-b-polybutadiene-b-polymethylmethacrylate (SBM) triblock and the reactive solvent DGEBA has been performed. At low copolymer concentration, the theory predicts micelles of PS and PB in the PMMA/DGEBA matrix. Increasing the copolymer concentration above a threshold value leads to formation of core-shell cylindrical or ``sphere-on-sphere'' morphologies, depending on the length of PB midblock. The theoretical predictions are in reasonable agreement with experiments.

  8. Epoxy thermoset networks derived from vegetable oils and their blends

    Ryu, Chang; Ravalli, Matthew


    Epoxidized vegetable oils (EVOs), such as epoxidized soybean oil and linseed oils were prepared by the partial oxidation of the unsaturated double bonds in vegetable oils and used as monomers for preparing epoxy thermoset materials based on the cationic polymerization. These EVOs have been used to prepare epoxy thermosets of different network densities by cationic polymerization using onium salt catalyst. The crosslinked epoxy thermosets provide an ideal platform to study the structure-property-relationships of networked polymers. In particular, rheological studies on the epoxidized vegetable oil thermosets have been performed to measure the molecular weights between crosslinks (Mx) in the epoxy thermosets and to ultimately elucidate the role of functionality of epoxy groups in EVO on the mechanical and thermophysical properties of the epoxy thermoset materials. NSF DMR POLYMERS 1308617.

  9. A comparison of pentane-1,5-diol to other diols for use in dermatology.

    Sundberg, Jeanette Jacobsson; Faergemann, Jan


    The use of pentane-1,5-diol in topical pharmaceutical products is relatively new compared with, e.g., propane-1,2-diol (propylene glycol), also an aliphatic diol, which has been used for many years. Yet, what are the differences between diols in clinical efficacy, safety and other characteristics? The objective of this overview was to compare the efficacy, safety, chemical and pharmaceutical characteristics of pentane-1,5-diol with other aliphatic diols used in pharmaceutical formulations in dermatology. A survey of the literature was carried out based on searches limited to aliphatic diols. Pentane-1,5-diol was found to be safe and more effective than several other diols with respect to drug delivery-enhancing potency, pharmaceutical and cosmetic properties, antimicrobial spectrum and toxicity. Results from formal clinical trials with pentane-1,5-diol verify its efficacy and safety. These characteristics together with its low cost make pentane-1,5-diol an attractive substance for use in pharmaceutical formulations for topical administration.

  10. Rapid synthesis of macrocycles from diol precursors

    Wingstrand, Magnus; Madsen, Charlotte Marie; Clausen, Mads Hartvig


    A method for the formation of synthetic macrocycles with different ring sizes from diols is presented. Reacting a simple diol precursor with electrophilic reagents leads to a cyclic carbonate, sulfite or phosphate in a single step in 25-60% yield. Converting the cyclization precursor to a bis-ele...

  11. Fluxional Monomers for Enhanced Thermoset Materials.

    Jones, Brad Howard; Alam, Todd M.; Black, Hayden T; Celina, Mathias C.; Wheeler, David R.


    This report catalogues the results of a project exploring the incorporation of organometallic compounds into thermosetting polymers as a means to reduce their residual stress. Various syntheses of polymerizable ferro cene derivatives were attempted with mixed success. Ultimately, a diamine derivative of ferrocene was used as a curing agen t for a commercial epoxy resin, where it was found to give similar cure kinetics and mechanical properties in comparison to conventional curing agents. T he ferrocen e - based material is uniquely able to relax stress above the glass transition, leading to reduced cure stress. We propose that this behavior arises from the fluxional capacity of ferrocene. In support of this notion, nuclear magnetic resonance spectroscopy indicates a substantial increase in chain flexibility in the ferrocene - containing network. Although t he utilization of fluxionality is a novel approach to stress management in epoxy thermosets, it is anticipated to have greater impact in radical - cured ther mosets and linear polymers.

  12. Isothermal transitions of a thermosetting system

    Gillham, J. K.; Benci, J. A.; Noshay, A.


    A study of the curing reactions of a cycloaliphatic epoxy resin/anhydride system by torsional braid analysis showed the existence of two critical isothermal temperatures - namely, the maximum glass transition temperature of the thermoset system and the glass transition temperature of the material at its gel point. Two rheologically active kinetic transitions occur during isothermal cure which correspond to gelation and vitrification. Three types of isothermal behavior occur. Methods for determining the time to gel and the time to vitrify, and also the two above-mentioned critical isothermal temperatures, have been developed. The time to gel obeyed the Arrhenius relationship, whereas the time to vitrify passed through a minimum. Application of these results to thermosetting systems in general is discussed in terms of the influence of molecular structure on the values of the critical isothermal temperatures.

  13. Iridium catalysed synthesis of piperazines from diols

    Nordstrøm, Lars Ulrik Rubæk; Madsen, Robert


    A green and atom-economical method has been developed for the synthesis of piperazines by cyclocondensation of diols and amines in aqueous media in the presence of a catalytic amount of [Cp*IrCl2]2....

  14. 40 CFR 414.50 - Applicability; description of the thermosetting resins subcategory.


    ... thermosetting resins subcategory. 414.50 Section 414.50 Protection of Environment ENVIRONMENTAL PROTECTION... Thermosetting Resins § 414.50 Applicability; description of the thermosetting resins subcategory. The provisions... the products classified under SIC 28214 thermosetting resins including those resins and resin...

  15. Epoxy Sol-Gel Hybrid Thermosets

    Angels Serra


    Full Text Available Sol-gel methodologies are advantageous in the preparation of hybrid materials in front of the conventional addition of nanoparticles, because of the fine dispersion of the inorganic phase that can be reached in epoxy matrices. In addition, the use of organoalkoxysilanes as coupling agents allows covalent linkage between organic and inorganic phases, which is the key point in the improvement of mechanical properties. The sol-gel process involves hydrolysis and condensation reactions under mild conditions, starting from hydrolysable metal alkoxides, generally alkoxy silanes. Using the sol-gel procedure, the viscosity of the formulation is maintained, which is an important issue in coating applications, whereas the transparency of the polymer matrix is also maintained. However, only the proper combination of the chemistries and functionalities of both organic and inorganic structures leads to thermosets with the desired characteristics. The adequate preparation of hybrid epoxy thermosets enables their improvement in characteristics such as mechanical properties (modulus, hardness, scratch resistance, thermal and flame resistance, corrosion and antimicrobial protection, and even optical performance among others.

  16. Kinetics and mechanism of the oxidation of some vicinal and non-vicinal diols by tetrabutylammonium tribromide

    Jaya Gosain; Pradeep K Sharma


    Kinetics of oxidation of five vicinal and four non-vicinal diols, and two of their monoethers, by tetrabutylammonium tribromide (TBATB) has been studied. The vicinal diols yield products arising out of glycol-bond fission, while the non-vicinal diols produce the hydroxycarbonyl compounds. The reaction is first-order with respect to TBATB. Michaelis-Menten type kinetics is observed with respect to diols. The reaction fails to induce the polymerization of acrylonitrile. There is no effect of tetrabutylammonium chloride on the reaction rate. The proposed reactive oxidizing species is the tribromide ion. The effect of solvent composition indicates that the rate increases with increase in the polarity of the solvent. The oxidation of [1,1,2,2-2H4] ethanediol shows the absence of any primary kinetic isotope effect. Values of solvent isotope effect, (H2O)/(D2O), at 288 K for the oxidation of ethanediol, propane-1,3-diol and 3-methoxybutan-1-ol are 3.41, 0.98 and 1.02 respectively. A mechanism involving a glycol-bond fission has been proposed for the oxidation of vicinal diols. Non-vicinal diols are oxidised by a hydride-transfer mechanism, as they are monohydric alcohols.

  17. Effects of carbon nanoparticles on properties of thermoset polymer systems

    Movva, Siva Subramanyam

    Polymer nanocomposites are novel materials in which at least one of the dimensions of the reinforcing material is on the order of 100 nm or less. While thermoplastic nanocomposites have been studied very widely, there are fewer studies concerning the effect of nanoparticles on thermoset systems. Low temperature cure thermoset systems are very important for many important applications. In this study, the processing, mechanical and thermal properties and reaction kinetics of carbon nanofiber (CNF) and/or carbon nanotubes (CNT) reinforced low temperature vinyl ester and epoxy nanocomposites were studied. In the first part, the processing challenge of incorporating CNFs into conventional fiber reinforced composites made by Vacuum infusion resin transfer molding (VARTM) was addressed by a new technique. The CNFs are pre-bound on the long fiber mats, instead of mixing them in the polymer resin, thereby eliminating several processing drawbacks. The resulting hybrid nanocomposites showed significant improvements in tensile, flexural and thermal properties. The effect of CNFs on the mold filling in VARTM was also studied and shown to follow the Darcy's law. In the second part, the effect of CNFs on the low temperature cure kinetics of vinyl ester and epoxy resins is studied using a thermal analysis technique, namely Differential scanning calorimetry (DSC). The effect of CNFs on the free radical polymerization of vinyl esters was found to be very complex as the CNFs interact with the various curing ingredients in the formulation. Specifically, the interaction effects of CNFs and the inhibitor were studied and a reaction mechanism was proposed to explain the observed phenomenon. The effect of surface modification of the carbon nanoparticles on the cure kinetics of wind-blade epoxy was studied. The surface functionalization reduced the activation energy of the epoxy reaction and was found to have an acceleration effect on the cure kinetics of epoxy resin at room temperature

  18. Terminal sterilization of BisGMA-TEGDMA thermoset materials and their bioactive surfaces by supercritical CO2.

    Donati, Ivan; Benincasa, Monica; Foulc, Marie-Pierre; Turco, Gianluca; Toppazzini, Mila; Solinas, Dario; Spilimbergo, Sara; Kikic, Ireneo; Paoletti, Sergio


    The development of biomaterials endowed with bioactive features relies on a simultaneous insight into a proper terminal sterilization process. FDA recommendations on sterility of biomaterials are very strict: a sterility assurance level (SAL) of 10(-6) must be guaranteed for biomaterials to be used in human implants. In the present work, we have explored the potential of supercritical CO(2) (scCO(2)) in the presence of H(2)O(2) as a low-temperature sterilization process for thermoset materials and their bioactive surfaces. Different conditions allowing for terminal sterilization have been screened and a treatment time-amount of H(2)O(2) relationship proposed. The selected terminal sterilization conditions did not notably modify the mechanical properties of the thermoset nor of their fiber-reinforced composites. This was confirmed by μCT analyses performed prior to and after the treatment. On the contrary, terminal sterilization in the presence of H(2)O(2) induced a slight decrease in the surface hardness. The treatment of the thermoset material with scCO(2) led to a reduction in the residual unreacted monomers content, as determined by means of high performance liquid chromatography (HPLC) analyses. Finally, it was found that a thermoset coated with a polysaccharide layer containing silver nanoparticles maintained a very high antimicrobial efficacy even after the scCO(2)-based terminal sterilization.

  19. Formation of nanophases in epoxy thermosets containing amphiphilic block copolymers with linear and star-like topologies.

    Wang, Lei; Zhang, Chongyin; Cong, Houluo; Li, Lei; Zheng, Sixun; Li, Xiuhong; Wang, Jie


    In this work, we investigated the effect of topological structures of block copolymers on the formation of the nanophase in epoxy thermosets containing amphiphilic block copolymers. Two block copolymers composed of poly(ε-caprolactone) (PCL) and poly(2,2,2-trifluoroethyl acrylate) (PTFEA) blocks were synthesized to possess linear and star-shaped topologies. The star-shaped block copolymer composed a polyhedral oligomeric silsesquioxane (POSS) core and eight poly(ε-caprolactone)-block-poly(2,2,2-trifluoroethyl acrylate) (PCL-b-PTFEA) diblock copolymer arms. Both block copolymers were synthesized via the combination of ring-opening polymerization and reversible addition-fragmentation chain transfer/macromolecular design via the interchange of xanthate (RAFT/MADIX) process; they were controlled to have identical compositions of copolymerization and lengths of blocks. Upon incorporating both block copolymers into epoxy thermosets, the spherical PTFEA nanophases were formed in all the cases. However, the sizes of PTFEA nanophases from the star-like block copolymer were significantly lower than those from the linear diblock copolymer. The difference in the nanostructures gave rise to the different glass transition behavior of the nanostructured thermosets. The dependence of PTFEA nanophases on the topologies of block copolymers is interpreted in terms of the conformation of the miscible subchain (viz. PCL) at the surface of PTFEA microdomains and the restriction of POSS cages on the demixing of the thermoset-philic block (viz. PCL).

  20. A Model for Tow Impregnation and Consolidation for Partially Impregnated Thermoset Prepregs

    John J. Gangloff Jr; Shatil Sinha; Suresh G. Advani


    The formation and transport of voids in composite materials remains a key research area in composite manufacturing science. Knowledge of how voids, resin, and fiber reinforcement propagate throughout a composite material continuum from green state to cured state during an automated tape layup process is key to minimizing defects induced by void-initiated stress concentrations under applied loads for a wide variety of composite applications. This paper focuses on modeling resin flow in a deforming fiber tow during an automated process of partially impregnated thermoset prepreg composite material tapes. In this work, a tow unit cell based model has been presented that determines the consolidation and impregnation of a thermoset prepreg tape under an input pressure profile. A parametric study has been performed to characterize the behavior of varying tow speed and compaction forces on the degree of consolidation. Results indicate that increased tow consolidation is achieved with slower tow speeds and higher compaction forces although the relationship is not linear. The overall modeling of this project is motivated to address optimization of the 'green state' composite properties and processing parameters to reduce or eliminate 'cured state' defects, such as porosity and de-lamination. This work is partially funded by the Department of Energy under Award number DE-EE0001367.

  1. Molybdenum-catalyzed deoxydehydration of vicinal diols

    Dethlefsen, Johannes Rytter; Lupp, Daniel; Oh, Byung Chang


    The commercially available (NH4)6Mo7O24 and other molybdenum compounds are shown to be viable substitutes for the typically employed rhenium compounds in the catalytic deoxydehydration of aliphatic diols into the corresponding alkenes. The transformation, which represents a model system for the v......The commercially available (NH4)6Mo7O24 and other molybdenum compounds are shown to be viable substitutes for the typically employed rhenium compounds in the catalytic deoxydehydration of aliphatic diols into the corresponding alkenes. The transformation, which represents a model system...... for the various hydroxyl groups found in biomass-derived carbohydrates, can be conducted in an inert solvent (dodecane), under solvent-free conditions, and in a solvent capable of dissolving biomass-derived polyols (1,5-pentanediol). The reaction is driven by the simultaneous oxidative deformylation of the diol...

  2. Thermoset polymers via ring opening metathesis polymerization of functionalized oils

    Larock, Richard C; Henna, Phillip H; Kessier, Michael R


    The invention provides a method for producing a thermosetting resin from renewable oils, the method comprising supplying renewable oil molecules containing strained ring alkene moieties; reacting the alkene moieties with cyclic alkenes to create a polymer; and repeating the above two steps until the resin having desired characteristics are obtained. Also provided is a thermoset resin comprising functionalized renewable oil polymerized with a co-monomer.

  3. Investigation of glassy state molecular motions in thermoset polymers

    Tu, Jianwei

    This dissertation presents the investigation of the glassy state molecular motions in isomeric thermoset epoxies by means of solid-state deuterium (2H) NMR spectroscopy technique. The network structure of crosslinked epoxies was altered through monomer isomerism; specifically, diglycidyl ether of bisphenol A (DGEBA) was cured with isomeric amine curatives, i.e., the meta-substituted diaminodiphenylsulfone (33DDS) and para-substituted diaminodiphenylsulfone (44DDS). The use of structural isomerism provided a path way for altering macroscopic material properties while maintaining identical chemical composition within the crosslinked networks. The effects of structural isomerism on the glassy state molecular motions were studied using solid-state 2H NMR spectroscopy, which offers unrivaled power to monitor site-specific molecular motions. Three distinctive molecular groups on each isomeric network, i.e., the phenylene rings in the bisphenol A structure (BPA), the phenylene rings in the diaminodiphenylsulfone structure (DDS), and the hydroxypropoyl ether group (HPE) have been selectively deuterated for a comprehensive study of the structure-dynamics- property relationships in thermoset epoxies. Quadrupolar echo experiments and line shape simulations were employed as the main research approach to gain both qualitative and quantitative motional information of the epoxy networks in the glassy state. Quantitative information on the geometry and rate of the molecular motions allows the elucidation of the relationship between molecular motions and macro physical properties and the role of these motions in the mechanical relaxation. Specifically, it is revealed that both the BPA and HPE moieties in the isomeric networks have almost identical behaviors in the deep glassy state, which indicates that the molecular motions in the glassy state are localized, and the correlation length of the motions does not exceed the length of the DGEBA repeat unit. BPA ring motions contribute

  4. Monitoring the Cure State of Thermosetting Resins by Ultrasound

    Alfonso Maffezzoli


    Full Text Available The propagation of low intensity ultrasound in a curing resin, acting as a high frequency oscillatory excitation, has been recently proposed as an ultrasonic dynamic mechanical analysis (UDMA for cure monitoring. The technique measures sound velocity and attenuation, which are very sensitive to changes in the viscoelastic characteristics of the curing resin, since the velocity is related to the resin storage modulus and density, while the attenuation is related to the energy dissipation and scattering in the curing resin. The paper reviews the results obtained by the authors’ research group in the last decade by means of in-house made ultrasonic set-ups for both contact and air-coupled ultrasonic experiments. The basics of the ultrasonic wave propagation in polymers and examples of measurements of the time-evolution of ultrasonic longitudinal modulus and chemical conversion of different thermosetting resins are presented. The effect of temperature on the cure kinetics, the comparison with rheological, low frequency dynamic mechanical and calorimetric results, and the correlation between ultrasonic modulus and crosslinking density will be also discussed. The paper highlights the reliability of ultrasonic wave propagation for monitoring the physical changes taking place during curing and the potential for online monitoring during polymer and polymer matrix composite processing.

  5. Thermally reversible thermoset materials based on the chemical modification of alternating aliphatic polyketones

    Araya Hermosilla, Rodrigo Andrés


    This thesis focused on the synthesis and characterization of different kinds of reversible thermosets and thermoset nanocomposite materials by using alternating aliphatic polyketone (PK) as raw material. Fundamental knowledge was generated regarding the molecular design of new polymers via chemical

  6. Method for bonding a thermoplastic polymer to a thermosetting polymer component

    Van Tooren, M.J.L.


    The invention relates to a method for bonding a thermoplastic polymer to a thermosetting polymer component, the thermoplastic polymer having a melting temperature that exceeds the curing temperature of the thermosetting polymer. The method comprises the steps of providing a cured thermosetting polym

  7. Method for bonding a thermoplastic polymer to a thermosetting polymer component

    Van Tooren, M.J.L.


    The invention relates to a method for bonding a thermoplastic polymer to a thermosetting polymer component, the thermoplastic polymer having a melting temperature that exceeds the curing temperature of the thermosetting polymer. The method comprises the steps of providing a cured thermosetting

  8. Bio-based thermosetting copolymers of eugenol and tung oil

    Handoko, Harris

    There has been an increasing demand for novel synthetic polymers made of components derived from renewable sources to cope with the depletion of petroleum sources. In fact, monomers derived vegetable oils and plant sources have shown promising results in forming polymers with good properties. The following is a study of two highly viable renewable sources, eugenol and tung oil (TO) to be copolymerized into fully bio-based thermosets. Polymerization of eugenol required initial methacrylate-functionalization through Steglich esterification and the synthesized methacrylated eugenol (ME) was confirmed by 1H-NMR. Rheological studies showed ideal Newtonian behavior in ME and five other blended ME resins containing 10 -- 50 wt% TO. Free-radical copolymerization using 5 mol% of tert-butyl peroxybenzoate (crosslinking catalyst) and curing at elevated temperatures (90 -- 160 °C) formed a series of soft to rigid highly-crosslinked thermosets. Crosslinked material (89 -- 98 %) in the thermosets were determined by Soxhlet extraction to decrease with increase of TO content (0 -- 30%). Thermosets containing 0 -- 30 wt% TO possessed ultimate flexural (3-point bending) strength of 32.2 -- 97.2 MPa and flexural moduli of 0.6 -- 3.5 GPa, with 3.2 -- 8.8 % strain-to-failure ratio. Those containing 10 -- 40 wt% TO exhibited ultimate tensile strength of 3.3 -- 45.0 MPa and tensile moduli of 0.02 GPa to 1.12 GPa, with 8.5 -- 76.7 % strain-to-failure ratio. Glass transition temperatures ranged from 52 -- 152 °C as determined by DMA in 3-point bending. SEM analysis on fractured tensile test specimens detected a small degree of heterogeneity. All the thermosets are thermally stable up to approximately 300 °C based on 5% weight loss.

  9. Effects of fiber pre-strain on the healing efficiency of thermoset polymers

    Ajisafe, Oludayo

    One major challenge that has been facing material self healing is how to heal bigger macroscopic or structural scale damage autonomously, repeatedly, efficiently and at molecular length scale. Different approaches have been used to heal materials. However, none of them can heal macroscopic cracks. Our research group has proposed a novel shape-memory polymer (SMP) based, bio-inspired Close-Then-Heal (CTH) scheme to heal macroscopic cracks in SMP matrix. The most recent development in our group is to use SMP fibers to heal conventional thermosetting polymers according to the CTH scheme. The aim of this study is to further investigate the effect of pre-tension of SMP fibers during the cold-drawing programming on the self-healing efficiency of the conventional thermosetting polymer composites. This was done by fabricating a composite with thermoplastic particles (polycaprolactone) dispersed in a thermosetting polymer matrix (Epon 828). Shape memory fiber pre-tensioned into 3 different groups of 0%, 50% and 100% prestrain, was also embedded into the composite in the longitudinal direction. In this composite, the shape memory effect of the shape memory fibers is utilized for sealing (closing) the cracks and the thermoplastic particles are used for molecular-length scale healing. In this study, 7% by volume of thermoplastic particles was used. Beam specimens were prepared and controlled structural length scale damage was created prior to curing by inserting an aluminum foil of designed thickness in a perpendicular direction to the shape memory fibers before the matrix was allowed to cure. The aluminum sheet was removed post cure to leave a controlled damage. The specimen was healed by fixing the two ends of the beam and heating the sample above the Tg of the shape memory fiber. The recovery force of the sample was recorded and then the beam was tested again to fracture. This fracture healing cycle lasted 7 times. The healing efficiency was evaluated per the peak

  10. Rhenium-Catalyzed Deoxydehydration of Diols and Polyols

    Dethlefsen, Johannes Rytter; Fristrup, Peter


    , is the heniumcatalyzeddeoxydehydration (DODH) of a vicinal diol into analkene; this is a model system for abundant polyols like glyceroland sugar alcohols. The present contribution includesa review of early investigations of stoichiometric reactions involvingrhenium, diols, and alkenes followed by a discussion ofthe various catalytic...... systems that have been developed withemphasis on the nature of the reductant, the substrate scope,and mechanistic investigations....

  11. New applications of the interaction between diols and boronic acids

    Duval, F.L.


    Florine Duval - New applications of the interaction between diols and boronic acids – Summary Chapter 1 introduces the theory and known applications of the interaction between boronic acids and diols, and explains the context of this thesis. Diagnosis of depre

  12. New applications of the interaction between diols and boronic acids

    Duval, F.L.


    Florine Duval - New applications of the interaction between diols and boronic acids – Summary Chapter 1 introduces the theory and known applications of the interaction between boronic acids and diols, and explains the context of this thesis. Diagnosis of

  13. Synthesis and complexation characteristics of phenanthroline and bipyridine diols

    Koning, B.; Boer, J.W. de; Meetsma, A.; Kellogg, R.M.


    Neocuproine (2,9-dimethyl-1,10-phenanthroline) 1 was converted to achiral and chiral tetradentate phenanthroline diols 3a-c by addition to benzophenone, adamantanone and camphor, respectively. Analogously 6,6'-dimethyl-2,2'-bipyridine 2 was converted to diol 7a on base-induced addition to benzopheno

  14. Thermally reversible thermoset materials based on the chemical modification of alternating aliphatic polyketones

    Araya Hermosilla, Rodrigo Andrés


    This thesis focused on the synthesis and characterization of different kinds of reversible thermosets and thermoset nanocomposite materials by using alternating aliphatic polyketone (PK) as raw material. Fundamental knowledge was generated regarding the molecular design of new polymers via chemical modification of PK with aliphatic and aromatic amine compounds. The resulting thermally reversible thermoset systems were investigated to outline the benefits for the synergistic cooperation betwee...

  15. Effect of pentane-1,5-diol and propane-1,2-diol on percutaneous absorption of terbinafine.

    Evenbratt, Hanne; Faergemann, Jan


    The aim of this study was to compare pentane-1,5-diol and propane-1,2-diol used as absorption enhancers for cutaneously administered terbinafine. Fresh human skin samples were placed in a continuous flow diffusion cell with a gel containing terbinafine on top of the skin. Receptor fluid samples were analysed using high - performance liquid chromatography. The quantity of gel remaining on the skin surface after completion of each test was weighed and the amount of drug in the skin was analysed. Addition of pentane-1,5-diol or propane-1,2-diol to the gel increased the percutaneous absorption of the drug. The most efficient absorption enhancer in this comparison was 5% pentane-1,5-diol.

  16. Synthesis and characterization of phenylethynylcarbonyl terminated novel thermosetting imide compound

    H. Kimura


    Full Text Available Phenylethynyl terminated novel imide compound based on 1,3-bis(3-aminophenoxybenzene (APB and phenylethynyl trimellitic anhydride (PETA were prepared. The curing behavior of phenylethynyl terminated imide compound was investigated by differential scanning calorimetry and Fourier transform infrared spectrometry. The curing reaction of phenylethynylcarbonyl end group completed at 220°C, and proceeded much faster than that of phenylethynyl end group. Glass transition temperature of the thermosetting resin from phenylethynylcarbonyl terminated novel imide compound determined by dynamic mechanical analysis was almost the same as that of o-cresolnovolac type epoxy resin. In addition, the thermosetting resin from phenylethynylcarbonyl terminated novel imide compound exhibited excellent thermal and dimensional stabilities. These excellent properties of these phenylethynyl terminated imide compound might be due to the incorporation of alkene group or aromatic ring substitutes in the backbones, which might enhance the chain interaction (molecular packing and reduce the molecular chain mobility.

  17. Ionic Liquid-Modified Thermosets and Their Nanocomposites: Dispersion, Exfoliation, Degradation, and Cure

    Throckmorton, James A.

    This dissertation explores the application of a room temperature ionic liquid (RTIL) to problems in the chemistry, processing, and modification of thermosetting polymers. In particular, the solution properties and reaction chemistry of 1-ethyl-3-methyl imidazolium dicyanamide (EMIM-DCN) are applied to problems of nanoparticle dispersion and processing, graphite exfoliation, cyanate ester (CE) cure, and the environmental degradation of CEs. Nanoparticle Dispersion: Nanocomposite processing can be simplified by using the same compound as both a nanoparticle solvent and an initiator for polymerization. This dual-function molecule can be designed both for solvent potential and reaction chemistry. EMIM-DCN, previously shown by our lab to act as an epoxy initiator, is used in the synthesis of silica and acid expanded graphite composites. These composites are then characterized for particle dispersion and physical properties. Individual particle dispersion of silica nanocomposites is shown, and silica nanocomposites at low loading show individual particle dispersion and improved modulus and fracture toughness. GNP nanocomposites show a 70% increase in modulus along with a 10-order of magnitude increase in electrical conductivity at 6.5 vol%, and an electrical percolation threshold of 1.7 vol%. Direct Graphite Exfoliation By Laminar Shear: This work presents a laminar-shear alternative to chemical processing and chaotic flow-fields for the direct exfoliation of graphite and the single-pot preparation of nanocomposites. Additionally, we develop the theory of laminar flow through a 3-roll mill, and apply that theory to the latest developments in the theory of graphite interlayer shear. The resulting nanocomposite shows low electrical percolation (0.5 vol%) and low thickness (1-3 layer) graphite/graphene flakes. Additionally, the effect of processing conditions by rheometry and comparison with solvent-free conditions reveal the interactions between processing and matrix

  18. Research Progress in Thermoset Shape Memory Epoxy Resin%热固性环氧树脂形状记忆聚合物的研究进展

    魏堃; 朱光明; 唐玉生; 田光明; 谢建强


    The thermoset shape memory epoxy resin was viewed as a hot issue in the field of shape memory polymers(SMP).The latest progress of thermoset shape memory epoxy resin was reviewed and summarized.The characteristics and shape memory properties of all kinds of thermoset shape memory epoxy resin were discussed in detail in the paper.The effects of temperature,radiation and degree of curing on the shape memory properties of thermoset shape memory epoxy resin were also discussed.The mechanical and shape memory properties of thermoset shape memory epoxy based composites were systematically discussed in the paper.At last,some hot issues about themoset shape memory epoxy resin were summed up.%热固性环氧树脂形状记忆聚合物是目前形状记忆聚合物研究领域的热点之一,文中介绍了热固性环氧树脂形状记忆聚合物的最新研究进展,详细探讨了各种热固性环氧树脂形状记忆聚合物的特点与性能,以及温度、辐射、固化程度对环氧树脂形状记忆聚合物性能的影响,并对环氧树脂形状记忆复合材料的性能进行了讨论,最后分析了热固性环氧树脂形状记忆聚合物研究中存在的问题。

  19. Bio-Based Aromatic Epoxy Monomers for Thermoset Materials.

    Ng, Feifei; Couture, Guillaume; Philippe, Coralie; Boutevin, Bernard; Caillol, Sylvain


    The synthesis of polymers from renewable resources is a burning issue that is actively investigated. Polyepoxide networks constitute a major class of thermosetting polymers and are extensively used as coatings, electronic materials, adhesives. Owing to their outstanding mechanical and electrical properties, chemical resistance, adhesion, and minimal shrinkage after curing, they are used in structural applications as well. Most of these thermosets are industrially manufactured from bisphenol A (BPA), a substance that was initially synthesized as a chemical estrogen. The awareness on BPA toxicity combined with the limited availability and volatile cost of fossil resources and the non-recyclability of thermosets implies necessary changes in the field of epoxy networks. Thus, substitution of BPA has witnessed an increasing number of studies both from the academic and industrial sides. This review proposes to give an overview of the reported aromatic multifunctional epoxide building blocks synthesized from biomass or from molecules that could be obtained from transformed biomass. After a reminder of the main glycidylation routes and mechanisms and the recent knowledge on BPA toxicity and legal issues, this review will provide a brief description of the main natural sources of aromatic molecules. The different epoxy prepolymers will then be organized from simple, mono-aromatic di-epoxy, to mono-aromatic poly-epoxy, to di-aromatic di-epoxy compounds, and finally to derivatives possessing numerous aromatic rings and epoxy groups.

  20. Bio-Based Aromatic Epoxy Monomers for Thermoset Materials

    Feifei Ng


    Full Text Available The synthesis of polymers from renewable resources is a burning issue that is actively investigated. Polyepoxide networks constitute a major class of thermosetting polymers and are extensively used as coatings, electronic materials, adhesives. Owing to their outstanding mechanical and electrical properties, chemical resistance, adhesion, and minimal shrinkage after curing, they are used in structural applications as well. Most of these thermosets are industrially manufactured from bisphenol A (BPA, a substance that was initially synthesized as a chemical estrogen. The awareness on BPA toxicity combined with the limited availability and volatile cost of fossil resources and the non-recyclability of thermosets implies necessary changes in the field of epoxy networks. Thus, substitution of BPA has witnessed an increasing number of studies both from the academic and industrial sides. This review proposes to give an overview of the reported aromatic multifunctional epoxide building blocks synthesized from biomass or from molecules that could be obtained from transformed biomass. After a reminder of the main glycidylation routes and mechanisms and the recent knowledge on BPA toxicity and legal issues, this review will provide a brief description of the main natural sources of aromatic molecules. The different epoxy prepolymers will then be organized from simple, mono-aromatic di-epoxy, to mono-aromatic poly-epoxy, to di-aromatic di-epoxy compounds, and finally to derivatives possessing numerous aromatic rings and epoxy groups.

  1. Friction and bending in thermoplastic composites forming processes

    Sachs, Ulrich


    With the demand for better fuel economy in the aerospace and automotive industries, lightweight polymer matrix composites became an attractive alternative for metal structures. Despite the inherently higher toughness and impact damage resistance of thermoplastics, thermoset matrix composites are use

  2. Composites

    Taylor, John G.

    The Composites market is arguably the most challenging and profitable market for phenolic resins aside from electronics. The variety of products and processes encountered creates the challenges, and the demand for high performance in critical operations brings value. Phenolic composite materials are rendered into a wide range of components to supply a diverse and fragmented commercial base that includes customers in aerospace (Space Shuttle), aircraft (interiors and brakes), mass transit (interiors), defense (blast protection), marine, mine ducting, off-shore (ducts and grating) and infrastructure (architectural) to name a few. For example, phenolic resin is a critical adhesive in the manufacture of honeycomb sandwich panels. Various solvent and water based resins are described along with resin characteristics and the role of metal ions for enhanced thermal stability of the resin used to coat the honeycomb. Featured new developments include pultrusion of phenolic grating, success in RTM/VARTM fabricated parts, new ballistic developments for military vehicles and high char yield carbon-carbon composites along with many others. Additionally, global regional market resin volumes and sales are presented and compared with other thermosetting resin systems.

  3. Probabilistic analysis of a thermosetting pultrusion process

    Baran, Ismet; Tutum, Cem C.; Hattel, Jesper H.


    In the present study, the effects of uncertainties in the material properties of the processing composite material and the resin kinetic parameters, as well as process parameters such as pulling speed and inlet temperature, on product quality (exit degree of cure) are investigated for a pultrusion p

  4. Probabilistic analysis of a thermosetting pultrusion process

    Baran, Ismet; Tutum, Cem C.; Hattel, Jesper Henri


    process. A new application for the probabilistic analysis of the pultrusion process is introduced using the response surface method (RSM). The results obtained from the RSM are validated by employing the Monte Carlo simulation (MCS) with Latin hypercube sampling technique. According to the results......In the present study, the effects of uncertainties in the material properties of the processing composite material and the resin kinetic parameters, as well as process parameters such as pulling speed and inlet temperature, on product quality (exit degree of cure) are investigated for a pultrusion...

  5. Synthesis and characterization of triglyceride based thermosetting polymers

    Can, Erde


    Plant oils, which are found in abundance in all parts of the world and are easily replenished annually, have the potential to replace petroleum as a chemical feedstock for making polymers. Within the past few years, there has been growing interest to use triglycerides as the basic constituent of thermosetting polymers with the necessary rigidity, strength and glass transition temperatures required for engineering applications. Plant oils are not polymerizable in their natural form, however various functional groups that can polymerize can easily be attached to the triglyceride structure making them ideal cross-linking monomers for thermosetting liquid molding resins. Through this research project a number of thermosetting liquid molding resins based on soybean and castor oil, which is a specialty oil with hydroxyls on its fatty acids, have been developed. The triglyceride based monomers were prepared via the malination of the alcoholysis products of soybean and castor oil with various polyols, such as pentaerythritol, glycerol, and Bisphenol A propoxylate. The malinated glycerides were then cured in the presence of a reactive diluent, such as styrene, to form rigid glassy materials with a wide range of properties. In addition to maleate half-esters, methacrylates were also introduced to the glyceride structure via methacrylation of the soybean oil glycerolysis product with methacrylic anhydride. This product, which contains methacrylic acid as by-product, and its blends with styrene also gave rigid materials when cured. The triglyceride based monomers were characterized via conventional spectroscopic techniques. Time resolved FTIR analysis was used to determine the curing kinetics and the final conversions of polymerization of the malinated glyceride-styrene blends. Dynamic Mechanical Analysis (DMA) was used to determine the thermomechanical behavior of these polymers and other mechanical properties were determined via standard mechanical tests. The use of lignin

  6. Thermosetting SMC resin characterization using linear and nonlinear ultrasonics

    Santos, S. Dos; Teston, F.; Matar, O. Bou; Meulen, F. Vander; Gouin, E.; Lethiecq, M.


    The material properties of viscous pastes used for the fabrication of thermosetting SMC (Sheet Molding Compound) have been investigated with ultrasonic spectroscopy working in linear and nonlinear modes. Attenuation versus frequency curves exhibit variations due to the time evolution of unsaturated polyester (UP) resin. A power amplifier was needed because of the high attenuation coefficient of resins. Different ultrasonic responses were measured versus the age and the proportion of gas bubbles and clusters in the paste. We present experimental results and show the interest of using nonlinear acoustics for nondestructive characterization of SMC.

  7. Antimicrobial polyurethane thermosets based on undecylenic acid: synthesis and evaluation.

    Lluch, Cristina; Esteve-Zarzoso, Braulio; Bordons, Albert; Lligadas, Gerard; Ronda, Juan C; Galià, Marina; Cádiz, Virginia


    In the present study, plant oil-derived surface-modifiable polyurethane thermosets are presented. Polyol synthesis is carried out taking advantage of thiol-yne photopolymerization of undecylenic acid derivatives containing methyl ester or hydroxyl moieties. The prepared methyl ester-containing polyurethanes allow surface modification treatment to enhance their hydrophilicity and impart antimicrobial activity through the following two steps: i) grafting poly(propylene glycol) monoamine (Jeffamine M-600) via aminolysis and ii) Jeffamine M-600 layer complexation with iodine. The antimicrobial activity of the iodine-containing polyurethanes is demonstrated by its capacity to inhibit the growth of Staphylococcus aureus, and Candida albicans in agar media.

  8. Kinetic features of foaming thermosetting polymers in the preparation of thermal insulation materials in the presence of a mineral filler

    A.E. Burdonov


    Full Text Available This article presents the research of dependencies with a filler in the form of fly ash, the mixture temperature and other factors influencing the kinetic characteristics of composite foaming based on the mixture of thermosetting resin (phenol-formaldehyde resins of different brands, fly ash and special modifiers. The article shows the duration and multiplicity of foaming, as well as the induction period of the composition depending on the amount of the filler used and other process parameters. It was found out that to obtain a homogeneous composite, the minimum thickness of the upper layer in the wooden form (S = 1m2 should be not less than 4 mm. The reaction with fly ash Thermal Power Station-9 (Open joint-stock company “Irkutskenergo”, Angarsk starts by 27% earlier than the use of fly ash in Ust-Ilimsk Hydroelectric Power Station. Using the obtained data, we developed mathematical models, expressed by regression equations.

  9. Dynamic Deformation of Thermosetting Polymers---All Atomistic Simulations

    Tsige, Mesfin; Shenogina, Natalia; Mukhopadhyay, Sharmila; Patnaik, Soumya


    We are using all-atom molecular dynamics simulations to investigate the interconnection between structural and mechanical properties of highly cross-linked polymer networks. In this study we focused on the widely used resin-hardener system composed of DGEBA epoxy oligomers and aromatic amine hardener DETDA. Accurate cross-linked models were developed using the effective cross-linking procedure that enables to generate thermoset structures with realistic structural characteristics. These models were used to examine the elastic properties of thermosetting networks with various degrees of curing and length of resin strands both in glassy and rubbery states. In our recent study we employed static deformation approach to estimate potential energy contribution to the mechanical response. In the present work we are using dynamic deformation approach which takes into account both potential energy and thermal motions in the structure. Uniaxial, volumetric and shear dynamic deformation modes were used to obtain Young's, bulk, shear moduli and Poisson's ratio directly. We also calculated elastic constants using formulae of linear elasticity and analyzed the results obtained by direct deformation and interconversion methods. The elastic properties determined from these two approaches are in good agreement with each other and also with experimental data.

  10. Vegetable Oil-Based Hyperbranched Thermosetting Polyurethane/Clay Nanocomposites

    Deka Harekrishna


    Full Text Available Abstract The highly branched polyurethanes and vegetable oil-based polymer nanocomposites have been showing fruitful advantages across a spectrum of potential field of applications.Mesua ferreaL. seed oil-based hyperbranched polyurethane (HBPU/clay nanocomposites were prepared at different dose levels by in situ polymerization technique. The performances of epoxy-cured thermosetting nanocomposites are reported for the first time. The partially exfoliated structure of clay layers was confirmed by XRD and TEM. FTIR spectra indicate the presence of H bonding between nanoclay and the polymer matrix. The present investigation outlines the significant improvement of tensile strength, scratch hardness, thermostability, water vapor permeability, and adhesive strength without much influencing impact resistance, bending, and elongation at break of the nanocomposites compared to pristine HBPU thermoset. An increment of two times the tensile strength, 6 °C of melting point, and 111 °C of thermo-stability were achieved by the formation of nanocomposites. An excellent shape recovery of about 96–99% was observed for the nanocomposites. Thus, the formation of partially exfoliated clay/vegetable oil-based hyperbranched polyurethane nanocomposites significantly improved the performance.

  11. Vegetable Oil-Based Hyperbranched Thermosetting Polyurethane/Clay Nanocomposites

    Deka, Harekrishna; Karak, Niranjan


    The highly branched polyurethanes and vegetable oil-based polymer nanocomposites have been showing fruitful advantages across a spectrum of potential field of applications. Mesua ferrea L. seed oil-based hyperbranched polyurethane (HBPU)/clay nanocomposites were prepared at different dose levels by in situ polymerization technique. The performances of epoxy-cured thermosetting nanocomposites are reported for the first time. The partially exfoliated structure of clay layers was confirmed by XRD and TEM. FTIR spectra indicate the presence of H bonding between nanoclay and the polymer matrix. The present investigation outlines the significant improvement of tensile strength, scratch hardness, thermostability, water vapor permeability, and adhesive strength without much influencing impact resistance, bending, and elongation at break of the nanocomposites compared to pristine HBPU thermoset. An increment of two times the tensile strength, 6 °C of melting point, and 111 °C of thermo-stability were achieved by the formation of nanocomposites. An excellent shape recovery of about 96-99% was observed for the nanocomposites. Thus, the formation of partially exfoliated clay/vegetable oil-based hyperbranched polyurethane nanocomposites significantly improved the performance.

  12. Molecular Description of Yield in Densely Crosslinked Epoxy Thermosets

    Chattaraj, Sandipan; Pant, Prita; Pawaskar, Dnyanesh; Nanavati, Hemant

    In densely crosslinked networks, macroscopic yield is a transition from deformations of bond lengths and angles, to cooperative deformation of multiple effective network chains via bond torsions. In this work, we examine this yield in terms of the ''activation number'', ν, of microscopic effective chains between crosslinks. ν is the number of effective network chains, in one Eyring activation volume, V*. It is thus a measure of the number of network chains 'activated' at yield, for cooperative deformation. Microcompression experiments have been performed on SU-8 micropillars, to determine its V* value. SU-8 is an important epoxy thermoset, which is used extensively in the microelectronics industry, in microfluidics and microelectromechanical systems (MEMS). The effective chain length based on Arruda and Boyce's 8-chain model, compares well with the rms length, obtained by chain conformer analyses. We find that ν ~ 2-4, at room temperature, for DGEBA-based epoxies including SU-8 and DGEBA-amine networks, over a range of network junction functionalities and V*. That ν corresponds very well with the reduced temperature, T/Tg, also demonstrates its viability as a molecular descriptor of yield in densely crosslinked thermosets.

  13. Novel bio-based thermoset resins based on epoxidized vegetable oils for structural adhesives

    Sivasubramanian, Shivshankar

    Conventional engineered wood composites are bonded for the most part through formaldehyde-based structural adhesives such as urea formaldehyde (UF), melamine formaldehyde (MF), phenol formaldehyde (PF) and resorcinol formaldehyde (RF). Formaldehyde is a known human carcinogen; the occupational exposure and emission after manufacturing of these binders is raising more and more concern. With increasing emphasis on environmental issues, there is clear incentive to replace these hazardous conventional formaldehyde-based binders with cco-friendly resins having similar properties but derived from renewable sources, bearing in mind the economics of the structural wood composite industry. In this thesis, the curing reaction of bio-derived epoxy thermosets with inexpensive, low-toxicity precursors, including polyimines and amino acids was investigated. Epoxidized linseed oil (ELO) and epoxidized soybean oil (ESO) were successfully crosslinked with both branched polyethyleneimine (PEI) and triethylenetetramine (fETA). Epoxidized castor oil (ECO) was crosslinked with polyethyleneimine (PEI), having different molecular weights. Curing conditions were optimized through solvent uptake and soluble fraction analysis. Finally, the mechanical properties of the optimized compositions of rigid bioepoxies were evaluated using dynamic mechanical rheological testing (DMRT). While not as stiff as conventional materials, optimized materials have sufficient room temperature moduli to show promise for coatings and as binders in engineered wood products.

  14. Quantification of simultaneous solvent evaporation and chemical curing in thermoset coatings

    Kiil, Søren


    The mechanisms of simultaneous solvent evaporation and film formation in high-solids thermoset coatings are considered. The relevant phenomena, chemical reactions, solvent diffusion and evaporation, gelation, vitrification, network mobility restrictions, and crosslinking, are quantified and a mat...

  15. Synthesis and reinforcement of peroxide-cured butyl rubber thermosets

    Rodrigo, Antonio Cillero

    Isobutylene-rich elastomers provide the oxidative stability and impermeability required by many industrial applications. Halogenated derivatives support a wide range of chemical modification processes that can overcome most performance limitations. This research involves the modification of brominated butyl rubber (BIIR) to introduce peroxide-curable functionality in addition to aminotrialkoxysilyl groups that improve interactions with siliceous fillers, and anthraquinone functionality that serves as a polymer-bound chromophore. The thesis also describes detailed studies of the influence of counter anions on imidazolium ionomer derivatives of brominated poly(isobutylene-co-p-methylstyrene) (BIMS). Exchanging bromide with dodecyl sulfate, styrene sulfonate and montmorillonite clay platelets provided new ionomer thermosets whose rheological, tensile and adhesive properties varied considerably from their parent material.

  16. Influence of melt mixer on injection molding of thermoset elastomers

    Rochman, Arif; Zahra, Keith


    One of the drawbacks in injection molding is that the plasticizing screw is short such that polymers having high concentrations of additives, such as thermoset elastomers, might not mix homogeneously within the short period of time during the plasticizing stage. In this study, various melt mixers inside the nozzle chamber, together forming a mixing nozzle, were developed. Three different materials were investigated, namely nitrile butadiene rubber (NBR), ethylene propylene-diene monomer (EPDM) and fluorocarbon (FKM). The use of these melt mixers resulted in better homogeneity and properties of the molded parts despite a curing time reduction of 10 s. This was due to the increase in mixing and shearing introduced a higher rate of crosslinking formation in the molded parts.

  17. Silver-polysaccharide nanocomposite antimicrobial coatings for methacrylic thermosets.

    Travan, Andrea; Marsich, Eleonora; Donati, Ivan; Benincasa, Monica; Giazzon, Marta; Felisari, Laura; Paoletti, Sergio


    Bisphenol A glycidylmethacrylate (BisGMA)/triethyleneglycol dimethacrylate (TEGDMA) thermosets are receiving increasing attention as biomaterials for dental and orthopedic applications; for both these fields, bacterial adhesion to the surface of the implant represents a major issue for the outcome of the surgical procedure. Moreover, the biological behaviour of these materials is influenced by their ability to establish proper interactions between their surface and the eukaryotic cells of the surrounding tissues, which is important for good implant integration. The aim of this work was to develop an antimicrobial non-cytotoxic coating for methacrylic thermosets by means of a nanocomposite material based on a lactose-modified chitosan and antibacterial silver nanoparticles. The coating was characterized by UV-vis spectrophotometry, optical microscopy, transmission electron microscopy (TEM) and scanning electron microscopy (SEM). In vitro tests were employed for a biological characterization of the material: antimicrobial efficacy tests were carried out with both Gram+ and Gram- strains. Osteoblast-like cell-lines, primary human fibroblasts and adipose-derived stem cells, were used for LDH cytotoxicity assays and Alamar blue cell proliferation assays. Cell morphology and distribution were evaluated by SEM and confocal laser scanning microscopy. In vitro results showed that the nanocomposite coating is effective in killing both bacterial strains and that this material does not exert any significant cytotoxic effect towards tested cells, which are able to firmly attach and proliferate on the surface of the coating. Such biocompatible antimicrobial polymeric films containing silver nanoparticles may have good potential for surface modification of medical devices, especially for prosthetic applications in orthopedics and dentistry.

  18. Selective discrimination of cyclodextrin diols using cyclic sulfates

    Petrillo, Marta; Marinescu, Lavinia; Rousseau, Cyril


    A method for selective monofunctionalition of readily available cyclodextrin diols (2(A-F),3(A-F),6(B,C,E,F)-hexadeca-O-benzyl-alpha-cyclodextrin and 2(A-G),3(A-G),6(B,C,E-G)-nonadeca-O-benzyl-beta-cyclodextrin) by regioselective nucleophilic opening of their cyclic sulfates is presented. Althoug...

  19. Synthesis of new diverse macrocycles from diol precursors

    Madsen, Charlotte Marie; Hansen, Martin; Thrane, Marie V.;


    The formation of a library of diverse macrocycles with different ring sizes from two easily accessible building blocks is presented. Reacting diol precursors with electrophilic reagents lead to 17-membered sulfites and 19-membered malonates in 34–79% yield. Double-reductive amination of dialdehyd...

  20. Molecular dynamics simulations of the effect of waviness and agglomeration of CNTs on interface strength of thermoset nanocomposites.

    Alian, A R; Meguid, S A


    Most existing molecular dynamics simulations in nanoreinforced composites assume carbon nanotubes (CNTs) to be straight and uniformly dispersed within thermoplastics. In reality, however, CNTs are typically curved, agglomerated and aggregated as a result of van der Waal interactions and electrostatic forces. In this paper, we account for both curvature and agglomeration of CNTs in extensive molecular dynamic (MD) simulations. The purpose of these simulations is to evaluate the influence of waviness and agglomeration of these curved and agglomerated CNTs on the interfacial strength of thermoset nanocomposite and upon their load transfer capability. Two aspects of the work were accordingly examined. In the first, realistic carbon nanotubes (CNTs) of the same length but varied curvatures were embedded in thermoset polymer composites and simulations of pull-out tests were conducted to evaluate the corresponding interfacial shear strength (ISS). In the second, the effect of the agglomerate size upon the ISS was determined using bundles of CNTs of different diameters. The results of our MD simulations revealed the following. The pull-out force of the curved CNTs is significantly higher than its straight counterpart and increases further with the increase in the waviness of the CNTs. This is attributed to the added pull-out energy dissipated in straightening the CNTs during the pull-out process. It also reveals that agglomeration of CNTs leads to a reduction in the ISS and poor load transferability, and that this reduction is governed by the size of the agglomerate. The simulation results were also used to develop a generalized relation for the ISS that takes into consideration the effect of waviness and agglomeration of CNTs of CNT-polymer composites.

  1. Curing of polymer thermosets via click reactions and on demand processes

    Brei, Mark Richard

    In the first project, an azide functional resin and tetra propargyl aromatic diamines were fabricated for use as a composite matrix. These systems take already established epoxy/amine matrices and functionalize them with click moieties. This allows lower temperatures to be used in the production of a thermoset part. These new systems yield many better mechanical properties than their epoxy/amine derivatives, but their Tgs are low in comparison. The second project investigates the characterization of a linear system based off of the above azide functional resin and a difunctional alkyne. Through selectively choosing catalyst, the linear system can show regioselectivity to either a 1,4-disubstituted triazole, or a 1,5-disubstituted triazole. Without the addition of catalyst, the system produces both triazoles in almost an equal ratio. The differently catalyzed systems were cured and then analyzed by 1H and 13C NMR to better understand the structure of the material. The third project builds off of the utility of the aforementioned azide/alkyne system and introduces an on-demand aspect to the curing of the thermoset. With the inclusion of copper(II) within the azide/alkyne system, UV light is able to catalyze said reaction and cure the material. It has been shown that the copper(II) loading levels can be extremely small, which helps in reducing the copper's effect on mechanical properties The fourth project takes a look at polysulfide-based sealants. These sealants are normally cured via an oxidative reaction. This project took thiol-terminated polysulfides and fabricated alkene-terminated polysulfides for use as a thiol-ene cured material. By changing the mechanism for cure, the polysulfide can be cured via UV light with the use of a photoinitiator within the thiol/alkene polysulfide matrix. The final chapter will focus on a characterization technique, MALDI-TOF, which was used to help characterize the above materials as well as many others. By using MALDI-TOF, the

  2. Phase separation time/temperature dependence of thermoplastics-modified thermosetting systems

    Xiujuan ZHANG; Xiaosu YI; Yuanze XU


    The cure-induced phase separation processes of various thermoplastics(TP)-modified thermosetting systems which show upper critical solution temperature (UCST) or lower critical solution temperature (LCST) were studied with emphasis on the temperature depend-ency of the phase separation time and its potential application in the cure time-temperature processing win-dow.We found that the phase separation time/temper-ature relationship follows the simple Arrhenius equation.The cure-induced phase separation activation energy Ea(ps) generated from the linear fitting of the Arrhenius equation is irrelevant to the detection means of phase separation time.We also found that Ea(ps) is insensitive to TP content,TP molecular weight and curing rate,but it changes with the cure reaction kinetics and the chemical environment of the systems.With the established phase separation time-temperature dependence relation,we can easily establish the whole cure time-temperature transformation (TTT) diagram with morphology information which is a useful map for the TP/TS compo-sites processing industry.

  3. Heat-resistant thermosetting resins and maleimido prepolymers based on a novel tetrakisaminophenoxycyclotriphosphazene

    Kumar, D.; Gupta, A.D.; Khullar, M. [Univ. of Delhi (India)


    A novel monomer, 2,2,4,4-tetrakis(4`-aminophenoxy)-6,6-diphenylcyclotriphosphazene (IV), useful for producing a variety of heat- and fire-resistant polymers, has been synthesized in good yield. Its synthesis involve Friedel-Frafts reaction of hexachlorocyclotriphosphazene (I) with benzene followed by the reaction of 2,2,4,4-tetrachloro-6,6-diphenylcyclotriphosphazene (II) with potassium 4-nitrophenoxide. The reduction of the obtained 2,2,4,4-tetrakis(4`-nitrophenoxy)-6, 6-diphenylcyclotriphosphazene (III) with molecular hydrogen in presence of PtO{sub 2} gave the tetrakisamine (IV). Heat-resistant thermosetting resins (X) and (XI) were synthesized by the reaction of tetrakisamine (IV) with maleic anhydride followed by insitu cyclodehydration and polymerization of the prepolymers (VIII) and (IX) at 235{+-}5{degrees}C for 1.5 and 290{degrees}C for 0.5 h. The TGA analysis of the developed cyclotriphosphazene containing cyclomatrix resins showed their thermal-stability up to 350{degrees}C and char yield of 71% in nitrogen at 800{degrees}C and 65% in air at 700{degrees}C. The structure of the synthesized monomer and intermediates were characterized by FT-IR, {sup 1}H-NMR, {sup 31}P-NMR, mass spectroscopy, DSC and elemental analysis. These resins are potential candidates for the development of heat-resistant composites, laminates, and adhesives in space, aerospace, and electronic industry.

  4. ROMP-based thermosetting polymers from modified castor oil with various cross-linking agents

    Ding, Rui

    Polymers derived from bio-renewable resources are finding an increase in global demand. In addition, polymers with distinctive functionalities are required in certain advanced fields, such as aerospace and civil engineering. In an attempt to meet both these needs, the goal of this work aims to develop a range of bio-based thermosetting matrix polymers for potential applications in multifunctional composites. Ring-opening metathesis polymerization (ROMP), which recently has been explored as a powerful method in polymer chemistry, was employed as a unique pathway to polymerize agricultural oil-based reactants. Specifically, a novel norbornyl-functionalized castor oil alcohol (NCA) was investigated to polymerize different cross-linking agents using ROMP. The effects of incorporating dicyclopentadiene (DCPD) and a norbornene-based crosslinker (CL) were systematically evaluated with respect to curing behavior and thermal mechanical properties of the polymers. Isothermal differential scanning calorimetry (DSC) was used to investigate the conversion during cure. Dynamic DSC scans at multiple heating rates revealed conversion-dependent activation energy by Ozawa-Flynn-Wall analysis. The glass transition temperature, storage modulus, and loss modulus for NCA/DCPD and NCA/CL copolymers with different cross-linking agent loading were compared using dynamic mechanical analysis. Cross-link density was examined to explain the very different dynamic mechanical behavior. Mechanical stress-strain curves were developed through tensile test, and thermal stability of the cross-linked polymers was evaluated by thermogravimetric analysis to further investigate the structure-property relationships in these systems.

  5. Ytterbium triflate as a new catalyst on the curing of epoxy-isocyanate based thermosets

    Flores, Marjorie; Fernandez-Francos, Xavier [Departament de Quimica Analitica i Quimica Organica, Universitat Rovira i Virgili, Marcelli Domingo s/n, 43007 Tarragona (Spain); Morancho, Josep M. [Laboratori de Termodinamica, ETSEIB, Universitat Politecnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain); Serra, Angels [Departament de Quimica Analitica i Quimica Organica, Universitat Rovira i Virgili, Marcelli Domingo s/n, 43007 Tarragona (Spain); Ramis, Xavier, E-mail: [Laboratori de Termodinamica, ETSEIB, Universitat Politecnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain)


    Highlights: Black-Right-Pointing-Pointer Ytterbium triflate is an active catalyst for diepoxides/diisocyanate formulations. Black-Right-Pointing-Pointer Ytterbium triflate promotes the formation of oxazolidone, isocyanurate, urethane and allophanate groups and the polyetherification of epoxides. Black-Right-Pointing-Pointer Diepoxides/diisocyanate formulations catalyzed by ytterbium triflate show higher pot-life than equivalent formulations catalyzed by benzyldimethylamine. - Abstract: Networks containing oxazolidone, isocyanurate, urethane, allophanate and ether groups were prepared by copolymerization of mixtures of diglycidylether of bisphenol A and toluene-2,4-diisocyanate in presence of ytterbium triflate. It has been demonstrated that ytterbium triflate promotes six elemental reactions that coexist during curing and yield the aforementioned groups. Changes during curing, fraction of different groups present in the network and final properties of the cured materials were investigated by thermal analysis and infrared spectroscopy. The influence of the molar ratio of isocyanate to epoxide groups on the properties and curing has been studied. The curing kinetics were analyzed by means of an integral isoconversional non-isothermal procedure. The results obtained were compared with those obtained by using a common catalyst such as the benzyldimethylamine. The structure and the properties of the resulting thermosets are controlled by the initial composition of the formulation and the catalyst used.

  6. Influence of cure via network structure on mechanical properties of a free-radical polymerizing thermoset

    Ganglani, Manisha Sachin

    The matrix of a composite material exerts influence over composite properties. The hypothesis is that control of molecular architecture of the matrix allows for the control of resin properties and therefore impacts composite properties. The objective of this research is to define the relationship between cure chemistry, network structure, and final physical properties of vinyl ester-styrene (VE/S) resin, a free-radical polymerizing thermoset polymer often used as the matrix of fiber reinforced polymers. Tensile and fracture properties of the polymer are found to depend on both cure schedule and cure formulation. The possibilities of phase separation and microgel formation being the cause for the differences in mechanical properties are examined. This research shows that the VE/S system does not phase separate under the conditions studied. This proven, the research examines changes in network architecture under different cure conditions. It is found that though bulk properties of the resin are unaffected by the details of the cure, the microscopic morphology, in particular the type of crosslink formed (intermolecular bond or intramolecular bond), is sensitive to both cure temperature and initiation mechanism as determined by cure formulation. Thus, the molecular architecture of the network is responsible for the bulk mechanical properties of the resin. A kinetic analysis shows that both temperature and initiation mechanism affect the apparent "reaction order" of the VE/S system as determined by the autoacceleration equation. This apparent reaction order is interpreted as being an indication of the degree of heterogeneity in the resin. By controlling cure temperature and cure formulation, it is possible to minimize the apparent reaction order and thereby optimize physical properties. Finally, a theory is adapted from other non-network polymer systems to describe qualitatively how cure temperature and initiation mechanism may alter the heterogeneity in network

  7. Structure - Property Relationships of Furanyl Thermosetting Polymer Materials Derived from Biobased Feedstocks

    Hu, Fengshuo

    Biobased thermosetting polymers have drawn significant attention due to their potential positive economic and ecological impacts. New materials should mimic the rigid, phenylic structures of incumbent petroleum-based thermosetting monomers and possess superior thermal and mechanical properties. Furans and triglycerides derived from cellulose, hemicellulose and plant oils are promising candidates for preparing such thermosetting materials. In this work, furanyl diepoxies, diamines and di-vinyl esters were synthesized using biobased furanyl materials, and their thermal and mechanical properties were investigated using multiple techniques. The structure versus property relationship showed that, compared with the prepared phenylic analogues, biobased furanyl thermosetting materials possess improved glassy storage modulus (E '), advanced fracture toughness, superior high-temperature char yield and comparable glass transition temperature (Tg) properties. An additive molar function analysis of the furanyl building block to the physical properties, such as Tg and density, of thermosetting polymers was performed. The molar glass transition function value (Yg) and molar volume increment value (Va,i) of the furanyl building block were obtained. Biobased epoxidized soybean oil (ESO) was modified using different fatty acids at varying molar ratios, and these prepared materials dramatically improved the critical strain energy release rate (G1c) and the critical stress intensity factor (K1c) values of commercial phenylic epoxy resins, without impairing their Tg and E ' properties. Overall, it was demonstrated that biobased furans and triglycerides possess promising potential for use in preparing high-performance thermosetting materials, and the established methodologies in this work can be utilized to direct the preparation of thermosetting materials with thermal and mechanical properties desired for practical applications.

  8. Acetylene-chromene terminated resins as high temperature thermosets

    Godschalx, J. P.; Inbasekaran, M. N.; Bartos, B. R.; Scheck, D. M.; Laman, S. A.


    A novel phase transfer catalyzed process for the preparation of propargyl ethers has been developed. The propargyl ethers serve as precursors to a new class of thermosetting resins called acetylene-chromene terminated (ACT) resins. Heat treatment of a solution of propargyl ethers with various catalysts, followed by removal of solvent leads to the ACT resins via partial conversion of the propargyl ether groups to chromenes. This process reduces the energy content of the resin systems and reduces the amount of shrinkage found during cure. Due to the presence of the solvent the process is safe and gives rise to low viscosity products suitable for resin transfer molding and filament winding type applications. Due to the high glass transition temperature, high modulus, and low moisture uptake the cured resins display better than 232 C/wet performance. The thermal stability of the ACT resins in air at 204 C is superior to that of conventional bismaleimide resins. The resins also display excellent electrical properties.

  9. Heating Process of Thermosetting Insulation Materials for Buildings

    SUN Shibing; MA Baoguo; CHEN Meng; WANG Zhaojun


    Polyurethane (PU) and phenolic (PF) foams used for building isolation were analyzed by thermal gravity/differential thermal analysis to determine their pyrolysis behavior,including the decomposition point and the maximum reaction rate point.Besides,the shape deformations of PU and PF foams were observed,and their oxygen index and the calorific value in combustion were also studied.The results showed that the pyrolysis of both PU and PF can be divided into three stages from room temperature to 1 000 ℃ in the atmospheric air,with total mass loss of 94.345% for PF and 88.191% for PU,respectively.The oxygen index of PU and PF decreased with increasing the temperature and the duration of the heat treatment.With the temperature increasing,the calorific values of both materials were reduced remarkably.These results of the PU and PF could provide basic data of the thermal stability and fire safety design in the application of thermosetting insulation materials.

  10. Acetylene-chromene terminated resins as high temperature thermosets

    Godschalx, J. P.; Inbasekaran, M. N.; Bartos, B. R.; Scheck, D. M.; Laman, S. A.


    A novel phase transfer catalyzed process for the preparation of propargyl ethers has been developed. The propargyl ethers serve as precursors to a new class of thermosetting resins called acetylene-chromene terminated (ACT) resins. Heat treatment of a solution of propargyl ethers with various catalysts, followed by removal of solvent leads to the ACT resins via partial conversion of the propargyl ether groups to chromenes. This process reduces the energy content of the resin systems and reduces the amount of shrinkage found during cure. Due to the presence of the solvent the process is safe and gives rise to low viscosity products suitable for resin transfer molding and filament winding type applications. Due to the high glass transition temperature, high modulus, and low moisture uptake the cured resins display better than 232 C/wet performance. The thermal stability of the ACT resins in air at 204 C is superior to that of conventional bismaleimide resins. The resins also display excellent electrical properties.

  11. 21 CFR 177.2280 - 4,4′-Isopropyl-idenedi-phenol-epichloro-hydrin thermo-setting epoxy resins.


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true 4,4â²-Isopropyl-idenedi-phenol-epichloro-hydrin thermo-setting epoxy resins. 177.2280 Section 177.2280 Food and Drugs FOOD AND DRUG ADMINISTRATION...,4′-Isopropyl-idenedi-phenol-epichloro-hydrin thermo-setting epoxy resins....

  12. Characterizing mesh size distributions (MSDs) in thermosetting materials using a high-pressure system.

    Larché, J-F; Seynaeve, J-M; Voyard, G; Bussière, P-O; Gardette, J-L


    The thermoporosimetry method was adapted to determine the mesh size distribution of an acrylate thermoset clearcoat. This goal was achieved by increasing the solvent rate transfer by increasing the pressure and temperature. A comparison of the results obtained using this approach with those obtained by DMA (dynamic mechanical analysis) underlined the accuracy of thermoporosimetry in characterizing the macromolecular architecture of thermosets. The thermoporosimetry method was also used to analyze the effects of photoaging on cross-linking, which result from the photodegradation of the acrylate thermoset. It was found that the formation of a three-dimensional network followed by densification generates a modification of the average mesh size that leads to a dramatic decrease of the meshes of the polymer.


    Kun Xu; Shu-xue Zhou; Li-min Wu


    Thermosetting acrylic coatings were prepared by using carboxyl acid group-containing acrylic oligomer and curing with titanium-oxo-clusters which were first pre-hydrolyzed from titanium n-butoxide. The curing ability of the titanium-oxo-cluster was examined using a microdielectric analytical (DEA) curing monitor, Fourier transformed infrared spectroscopy (FTIR), and Soxhlet extraction experiments, and the properties of the resulted coatings were investigated with pendulum hardness tester, dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA) and ultraviolet-visible spectrometer. The effect of titania-oxo-cluster in leading acrylic oligomers to form thermosetting acrylic coatings was confirmed. An increasing pendulum hardness and modulus of acrylic coatings with increasing titania content was observed, which resulted from the increment of crosslinking degree rather than of the titania content. The thermosetting acrylic/titania coatings also showed better thermal stability and higher UV-blocking properties than those coatings using organic curing agent.

  14. Thermoset Shape-Memory Polyurethane with Intrinsic Plasticity Enabled by Transcarbamoylation.

    Zheng, Ning; Fang, Zizheng; Zou, Weike; Zhao, Qian; Xie, Tao


    Thermoset polymers are known for their superior thermomechanical properties, but the chemical crosslinking typically leads to intractability. This is reflected in the great differences between thermoset and thermoplastic shape-memory polymers; the former exhibit a robust shape memory but are not capable of redefining the permanent shape. Contrary to current knowledge, we reveal here that a classical thermoset shape-memory polyurethane is readily capable of permanent reshaping (plasticity) after a topological network rearrangement that is induced by transcarbamoylation. By employing the Jianzhi technique (also known as kirigami), unexpected shape-shifting versatility was observed for this otherwise classical material. As the essential carbamate moiety in polyurethanes is one of the most common polymer building units, we anticipate that our finding will have significant benefits beyond shape shifting.

  15. Kinetics and mechanism of the oxidation of some diols by benzyltrimethylammonium tribromide

    Garima Goswami; Seema Kothari; Kalyan K Banerji


    The kinetics of oxidation of five vicinal and four non-vicinal diols, and two of their monoethers by benzyltrimethylammonium tribromide (BTMAB) have been studied in 3:7 (/) acetic acid-water mixture. The vicinal diols yield the carbonyl compounds arising out of the glycol bond fission while the other diols give the hydroxycarbonyl compounds. The reaction is first-order with respect to BTMAB. Michaelis-Menten type kinetics is observed with respect to diol. Addition of benzyltrimethylammonium chloride does not affect the rate. Tribromide ion is postulated to be the reactive oxidizing species. Oxidation of [1,1,2,2-2H4] ethanediol shows the absence of a kinetic isotope effect. The reaction exhibits substantial solvent isotope effect. A mechanism involving a glycol-bond fission has been proposed for the oxidation of the vicinal diols. The other diols are oxidized by a hydride ion transfer to the oxidant, as are the monohydric alcohols.

  16. A reactive polystyrene-block-polyisoprene star copolymer as a toughening agent in an epoxy thermoset

    Francis, Raju


    © 2015 Springer-Verlag Berlin Heidelberg A polystyrene-block-polyisoprene ((PS-b-PI)3) star polymer was synthesized by photochemical reversible addition fragmentation chain transfer (RAFT) polymerization. The obtained star polymer was epoxidized and used as a toughening agent in an epoxy thermoset. The incorporation of the epoxidized star polymer resulted in the formation of nanostructures and it was fixed by a crosslinking reaction. The formation of nanostructures in the thermosets follows the mechanism of reaction-induced microphase separation. The mechanical properties such as toughness and tensile strength were considerably increased due to the nanostructures formed by reactive blending.

  17. Preliminary Design and Experimental Investigation of a Novel Pneumatic Conveying Method to Disperse Natural Fibers in Thermoset Polymers

    Mahi Fahimian


    Full Text Available Natural fibers can be attractive reinforcing materials in thermosetting polymers due to their low density and high specific mechanical properties. Although the research effort in this area has grown substantially over the last 20 years, manufacturing technologies to make use of short natural fibers in high volume fraction composites; are still limited. Natural fibers, after retting and preprocessing, are discontinuous and easily form entangled bundles. Dispersion and mixing these short fibers with resin to manufacture high quality, high volume fraction composites presents a significant challenge. In this paper, a novel pneumatic design for dispersion of natural fibers in their original discontinuous form is described. In this design, compressed air is used to create vacuum to feed and convey fibres while breaking down fibre clumps and dispersing them in an aerosolized resin stream. Model composite materials, made using proof-of-concept prototype equipment, were imaged with both optical and X-ray tomography to evaluate fibre and resin dispersion. The images indicated that the system was capable of providing an intimate mixture of resin and detangled fibres for two different resin viscosities. The new pneumatic process could serve as the basis of a system to produce well-dispersed high-volume fraction composites containing discontinuous natural fibres drawn directly from a loosely packed source.

  18. Asbestos free friction composition for brake linings

    Arnab Ganguly; Raji George


    An asbestos free friction material composite for brake linings is synthesized containing fibrous reinforcing constituents, friction imparting and controlling additives, elastomeric additives, fire retarding components and a thermosetting resin. The composite shows exemplary friction characteristics and has great resistance to wear and shows good temperature stability.

  19. Thermally Self-Healing Polymeric Materials : The Next Step to Recycling Thermoset Polymers?

    Zhang, Youchun; Broekhuis, Antonius A.; Picchioni, Francesco


    We developed thermally self-healing polymeric materials on the basis of furan-functionalized, alternating thermosetting polyketones (PK-furan) and bis-maleimide by using the Diels-Alder (DA) and Retro-Diels-Alder (RDA) reaction sequence. PK-furan can be easily obtained under mild conditions by the P

  20. Mathematical modelling of simultaneous solvent evaporation and chemical curing in thermoset coatings: A parameter study

    Kiil, Søren


    A mathematical model, describing the curing behaviour of a two-component, solvent-based, thermoset coating, is used to conduct a parameter study. The model includes curing reactions, solvent intra-film diffusion and evaporation, film gelation, vitrification, and crosslinking. A case study with a ...

  1. Porous epoxy thermosets obtained by a reaction-induced process and their characterizations

    Hao Ai; Kai Xu; Huan Liu; Ming Cai Chen


    A novel reaction-induced method with the aid of solvent for porous thermosetting epoxy was first carried out.Investigations of pore structure using scanning electron microscope (SEM) showed that porous epoxy networks with average pore size ranging from 3 to 20 μm were obtained.The pore structure generated by this method can be tailored by changing the solvent content.


    Comparative studies of the effect of polycyclic aromatic hydrocarbon geometry on the hydrolysis of diol epoxides The interaction of the diol epoxides (DEs) of both planar and non-planar PAHs with water have been examined using quantum mechanical and molecular dynamics. Th...

  3. 40 CFR 721.2625 - Reaction product of alkane-diol and epichlorohydrin.


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of alkane-diol and epichlorohydrin. 721.2625 Section 721.2625 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.2625 Reaction product of alkane-diol and epichlorohydrin. (a)...

  4. Sources and proxy potential of long chain alkyl diols in lacustrine environments.

    Rampen, Sebastiaan W.; Datema, Mariska; Rodrigo-Gámiz, M.; Schouten, Stefan; Reichart, Gert-Jan; Sinninghe Damste, Jaap S.


    Long chain 1,13- and 1,15-alkyl diols form the base of a number of recently proposed proxies used for climate reconstruction. However, the sources of these lipids and environmental controls on their distribution are still poorly constrained. We have analyzed the long chain alkyl diol (LCD) compositi

  5. Sources and proxy potential of long chain alkyl diols in lacustrine environments

    Rampen, S.; Datema, M.; Rodrigo-Gámiz, M.; Schouten, S.; Reichart, G.-J.; Sinninghe Damsté, J.S.


    Long chain 1,13- and 1,15-alkyl diols form the base of a number of recently proposed proxies used for climate reconstruction. However, the sources of these lipids and environmental controls on their distribution are still poorly constrained. We have analyzed the long chain alkyl diol (LCD) compositi

  6. Biosynthesis of R-(+)-octane-1,3-diol. Crucial role of beta-oxidation in the enantioselective generation of 1,3-diols in stored apples.

    Beuerle, T; Schwab, W


    The biosynthesis of R-octane-1,3-diol and R-5(Z)-octene-1,3-diol, two natural antimicrobial agents in apples and pears, was investigated in stored apples after application of [9,10,12,13-3H]linoleic acid, [9,10,12,13,15,16-3H]linolenic acid, [1-14C]linoleic acid, [U-14C]oleic acid, lipoxygenase-derived metabolites of [9,10,12,13-3H]linoleic acid, 13C18-labeled linoleic acid hydroperoxides, and 2H-labeled octanol derivatives. Analysis of the products and quantification of incorporation and labeling pattern were achieved by high-performance liquid chromatography-radiodetection, capillary gas chromatography (GC)-isotope ratio mass spectrometry, and GC-mass spectrometry analysis. Almost all the applied precursors were partly transformed into R-octane-1,3-diol. Linoleic acid derivatives, still containing the 12,13 cis double bond, and octanol derivatives oxy-functionalized at carbon 3 were the most efficient precursors of the 1,3-diol. The data imply that R-octane-1,3-diol is generated in stored apples in the course of the beta-oxidation from R-3-hydroxy-octanoyl-SCoA originating from 2-cis-octenoyl-SCoA by enoyl-CoA hydratase. In an analogous fashion, R-5(Z)-octene-1,3-diol is formed from the unsaturated intermediate.

  7. Isolation of a Pseudomonas aeruginosa strain from soil that can degrade polyurethane diol.

    Mukherjee, Koushik; Tribedi, Prosun; Chowdhury, Arup; Ray, Tanusree; Joardar, Archi; Giri, Subhajit; Sil, Alok Kumar


    Polyurethane diol (PUR-diol), a synthetic polymer, is widely used as a modifier for water-soluble resins and emulsions in wood appliances and auto coatings. Non-biodegradability of polyurethanes (PUR) and PUR-based materials poses a threat to environment that has led scientists to isolate microbes capable of degrading PUR. However, the bio-degradation of PUR-diol has not yet been reported. In this study, we report isolation of a soil bacterium that can survive using PUR-diol as sole carbon source. PUR-diol degradation by the organism was confirmed by thin layer chromatographic analysis of the conditioned medium obtained after the growth wherein a significant reduction of PUR-diol was observed compared to non-inoculated medium. To quantify the PUR-diol degradation, a sensitive assay based on High Performance Thin Layer Chromatography has been developed that showed 32% degradation of PUR-diol by the organism in 10 days. Degradation kinetics showed the maximal depletion of PUR-diol during logarithmic growth of the organism indicating a direct relation between the growth and PUR-diol degradation. Mutagenic study and GC-MS analysis revealed that esterase activity is involved in this degradation event. The ribotyping and metabolic fingerprinting analysis showed that this organism is a strain of Pseudomonous aeruginosa (P. aeruginosa). It has also been observed that this strain is able to degrade Impranil DLN™, a variety of commercially available PUR. Therefore this study identifies a new bacterium from soil that has the potential to reduce PUR-related waste burden and adds a new facet to diverse functional activities of P. aeruginosa.

  8. Thermoset recycling via high-pressure high-temperature sintering: Revisiting the effect of interchange chemistry

    Morin, Jeremy Edward

    In 1844 Charles Goodyear obtained U.S. Patent #3,633 for his "Gum Elastic Composition". In a published circular, which describes his patent for the sulfur vulcanization of gum elastic composition, he stated: "No degree of heat, without blaze, can melt it (rubber)... It resists the most powerful chemical reagents. Aquafortis (nitric acid), sulphuric acid, essential and common oils, turpentine and other solvents... ..." Goodyear's sulfur vulcanization of rubber fueled much of the industrial revolution and made transportation possible, as it exists today. In doing so, Goodyear created one of the most difficult materials to recycle. Rubber will not melt, dissolve, or lend itself to the usual methods of chemical decomposition. Ironically, Goodyear recognized this problem and in 1853 he patented the process of adding ground rubber to virgin material, now currently known as regrind blending. Today, scrap tires represent one of the most serious sources of pollution in the world. Studies estimate that there are roughly 2 billion scrap tires in U.S. landfills and more are being added at a rate of over 273 million tires per year. Current methods of recycling waste tires are crude, ineffective, and use rubber powder as a low cost filler instead of a new rubber. The groundwork for a very simple and effective method of producing high-quality rubber goods using 100% scrap rubber was discovered in 1944 by A. V. Tobolsky et al. This application, however, was not recognized until recently in our laboratory. The process as studied to date represents a method of creating quality, high-value added rubber goods with nothing other than heat and pressure. High pressure is required to obtain a void-free compaction of the rubber particles by forcing all of the free surfaces into intimate contact. High temperature then activates the chemical rearrangement, scission, and reformation of the chemical bonds thus providing new bridges between the once fractured interfaces. This occurs both within

  9. Novel Synthesis of Quinoline-7,8-diol Derivative

    HE,Juan; WANG,Xue-Bin; WAN,Zheng-Kai


    @@ Quinoline 7,8-diol derivatives can be expected to form metal complexes, and are the moiety of marine alkaloid,which exhibits strong cytotoxic activity against several human tumor. Our synthesis of 6 commences from L-dopa (1)(Scheme 1). Esterification of 2 with methanol and treatment of the resulting ester 3 with trichloroethoxycarbonyl (Troc)chloride yielded the N-protected amino acid ester 4. Treatment of 4 with acrolein in 1.3 mol/L methanolic HCl for 4 d at room temperature yielded the quinoline derivative 5, which was dissolved in 25% aq. HBr and the resulting solution was heated at reflux for 6 h to afford compound 6.

  10. 1-(3-Phenylisoxazol-5-ylcyclohexane-1,2-diol

    Luis Astudillo


    Full Text Available In the title compound, C15H17NO3, there are two molecules in the asymmetric unit wherein the isoxazole rings make dihedral angles of 16.16 (15 and 16.79 (13° with the benzene rings, and the cyclohexane rings adopt chair conformations. In both molecules, the hydroxyl groups of the diol fragments are cis oriented, the O—C—C—O torsion angles being 60.76 (12 and −55.86 (11°. The two molecules are linked by a strong O—H...N hydrogen bond and the crystal packing is stabilized by one O—H...N and two O—H...O hydrogen bonds. An intramolecular O—H...O hydrogen bond is observed in one of the molecules.

  11. Utilization of a diol-stationary phase column in ion chromatographic separation of inorganic anions.

    Arai, Kaori; Mori, Masanobu; Kozaki, Daisuke; Nakatani, Nobutake; Itabashi, Hideyuki; Tanaka, Kazuhiko


    We describe the ion chromatographic separation of inorganic anions using a diol-stationary phase column (-CH(OH)CH(2)OH; diol-column) without charged functional groups. Anions were separated using acidic eluent as in typical anion-exchange chromatography. The retention volumes of anions on the diol-column increased with increasing H(+) concentration in the eluent. The anion-exchange capacities of diol-columns in the acidic eluent (pH 2.8) were larger than that of zwitterionic stationary phase column but smaller than that of an anion-exchange column. The separation of anions using the diol-column was strongly affected by the interaction of H(+) ions with the diol-functional groups and by the types of the eluents. In particular, the selection of the eluent was very important for controlling the retention time and resolution. Good separation was obtained using a diol-column (HILIC-10) with 5 mM phthalic acid as eluent. The limits of detection at a signal-to-noise ratio of 3 ranged from 1.2 to 2.7 μM with relative standard deviations (RSD, n=5) of 0.04-0.07% for the retention time and 0.4-2.0% for the peak areas. This method was successfully applied to the determination of H(2)PO(4)(-), Cl(-), and NO(3)(-) in a liquid fertilizer sample.

  12. Absolute Stereochemistry of 1,2-Diols from Lipids of Thermomicrobia.

    Lagutin, Kirill; Wong, Herbert; Vyssotski, Mikhail; MacKenzie, Andrew


    1,2-Diol based phospholipids are a well-known feature of bacteria from the class Thermomicrobia. Since these bacteria contain only lipids with an alkyldiol-1-phosphate backbone instead of sn-glycero-3-phosphate, it is important to elucidate the stereochemistry of the 1,2-diols. We have studied the absolute stereochemistry of long-chain 1,2-diols isolated from Thermorudis pharmacophila (formerly known as Thermomicrobia sp. WKT50.2) by nuclear magnetic resonance (NMR) using α-methoxyphenylacetic acid (MPA). Low-temperature (-60 °C) NMR of bis-(R)-MPA ester showed (R) stereochemistry of the 1,2-diols. This is the first report concerning the stereochemistry of natural 1,2-diols, which replace the glyceride moiety in phospholipids. The (R) stereochemistry of the diols is expected as it is the same configuration as for the common bacterial lipid backbone-sn-glycero-3-phosphate. This is the first application of low-temperature NMR of a single MPA derivative for assignment of stereochemistry of natural 1,2-diols. The results were confirmed by the comparison of NMR data with bis-(R)-MPA ester of (R) and rac-1,2-octanediol.

  13. DFT Study of the Molybdenum-Catalyzed Deoxydehydration of Vicinal Diols

    Lupp, Daniel; Christensen, Niels Johan; Dethlefsen, Johannes Rytter


    The mechanism of the molybdenum-catalyzed deoxydehydration (DODH) of vicinal diols has been investigated using density functional theory. The proposed catalytic cycle involves condensation of the diol with an MoVI oxo complex, oxidative cleavage of the diol resulting in an MoIV complex......, and extrusion of the alkene. We have compared the proposed pathway with several alternatives, and the results have been corroborated by comparison with the molybdenum- catalyzed sulfoxide reduction recently published by Sanz et al. and with experimental observations for the DODH itself. Improved understanding...... of the mechanism should expedite future optimization of molybdenum-catalyzed biomass transformations....

  14. Sensing and Energy Harvesting Novel Polymer Composites

    Zwaag, S. van der; Ende, D.A. van der; Groen, W.A.


    This chapter describes the development and properties of novel functional composite materials consisting of aligned piezo-ceramic particles or fibers in a polymeric matrix, which can be fully integrated in thermoset or thermoplastic products. The materials have a low potential for applications requi

  15. Biological responses of silver-coated thermosets: an in vitro and in vivo study.

    Marsich, E; Travan, A; Donati, I; Turco, G; Kulkova, J; Moritz, N; Aro, H T; Crosera, M; Paoletti, S


    Bisphenol A glycidylmethacrylate (BisGMA)/triethyleneglycol dimethacrylate (TEGDMA) thermosets are biomaterials commonly employed for orthopedic and dental applications; for both these fields, bacterial adhesion to the surface of the implant represents a major issue for the outcome of the surgical procedures. In this study, the antimicrobial properties of a nanocomposite coating formed by polysaccharide 1-deoxylactit-1-yl chitosan (Chitlac) and silver nanoparticles (nAg) on methacrylate thermosets were studied. The Chitlac-nAg system showed good anti-bacterial and anti-biofilm activity although its biocidal properties can be moderately, albeit significantly, inhibited by serum proteins. In vitro studies on the silver release kinetic in physiological conditions showed a steady metal release associated with a gradual loss of antimicrobial activity. However, after 3weeks there was still effective protection against bacterial colonization which could be accounted for by the residual silver. This time-span could be considered adequate to confer short-term protection from early peri-implant infections. Preliminary in vivo tests in a mini-pig animal model showed good biological compatibility of Chitlac-nAg-coated materials when implanted in bony tissue. The comparison was made with implants of titanium Ti6Al4V alloy and with a Chitlac-coated thermoset. Bone healing patterns and biocompatibility parameters observed for nAg-treated material were comparable with those observed for control implants.

  16. Correlation between the state of cure of thermosetting resins and their properties

    Haffane, N.; Benameur, T.; Granger, R.; Vergnaud, J.M. [Faculty of Sciences, University of St Etienne (France)


    Thermosetting resins, in the same way as polymers, are more and more used for coating metal sheets, in order to bring various interesting properties. An important problem arises with the cure of the thermoset, the process of cure being complex with heating conduction and convection and the heat generated by the cure reaction. The kinetics of the heat evolved from the overall cure reaction is determined through calorimetry experiments in scanning mode. The state of cure at time t is expressed by the heat generated by reaction up to time t as a fraction of the total heat generated. A numerical model taking all the facts into account is able to evaluate the profile of the state of cure developed through the thickness of the thermoset. The state of cure which derives from a theoretical point of view is correlated with some properties of interest for the coating, such as the hardness and the resistance to liquids. The resistance to water and ethanol is evaluated by determining the kinetics of absorption which is controlled by diffusion. {copyright} {ital 1996 American Institute of Physics.}

  17. Smart synthesis of high performance thermosets based on ortho-(amide-co-imide functional benzoxazines

    Hatsuo eIshida


    Full Text Available High performance thermosets via amide-imide functional benzoxazine resins as precursors have been synthesized. The structures of synthesized monomers have been confirmed by 1H NMR and FT-IR. Among these two benzoxazine monomers, the ortho-amide-imide functional benzoxazine resin shows powerful features both in the synthesis of benzoxazine monomers and the properties of the corresponding thermosets. For the cross-linked poly(amide-co-imide based on ortho-amide-imide functional benzoxazine, a smart route is adopted to develop a more thermally stable cross-linked poly(benzoxazole-co-imide. Besides, the poly(benzoxazole-co-imide can also undergo a further thermal treatment to form polybenzoxazole. Furthermore, a main-chain type ortho-functional polybenzoxazine with amide-co-imide and benzoxazine groups as repeating units has also been prepared. Both the ortho-amide-imide functional benzoxazine and main-chain type polybenzoxazine resins show the possibility to form high performance thermosets with low cost and easy processability .

  18. Resistance Welding of Thermoplastic Composites: Process and Performance

    Shi, H.


    Compared to thermoset composites, thermoplastic composites are drawing more and more attention by aircraft industries not only due to their excellent material properties but also due to their potentials to reduce cycle time and structure cost by using low-cost manufacturing technologies such as weld

  19. Characterization of Interlaminar Crack Growth in Composites with the Double Cantilever Beam Specimen

    Hunston, D. L.


    A project to examine the double cantilever beam specimen as a quantitative test method to assess the resistance of various composite materials to interlaminar crack growth is discussed. A second objective is to investigate the micromechanics of failure for composites with tough matrix resins from certain generic types of polymeric systems: brittle thermosets, toughened thermosets, and thermoplastics. Emphasis is given to a discussion of preliminary results in two areas: the effects of temperature and loading rate for woven composites, and the effects of matrix toughening in woven and unidirectional composites.

  20. Enantioselective Synthesis of Terminal 1,2-Diols from Acyl Chlorides

    邵攀霖; 申理滔; 叶松


    Optically active terminal 1,2-diols were prepared with high enantiopurity via the TMS-quinidine-catalyzed en- antioselective cyclization of acyl chlorides and oxaziridine, followed by reductive ring-opening of the cycloadducts.

  1. Asymmetric desymmetrization of meso-diols by C2-symmetric chiral 4-pyrrolidinopyridines

    Hartmut Schedel


    Full Text Available In this work we developed C2-symmetric chiral nucleophilic catalysts which possess a pyrrolidinopyridine framework as a catalytic site. Some of these organocatalysts effectively promoted asymmetric desymmetrization of meso-diols via enantioselective acylation.

  2. Mechanochemical investigation of a glassy epoxy-amine thermoset subjected to fatigue

    Foster, Stephen Finley

    Covalent bonds in organic molecules can be produced, altered, and broken through various sources of energy and processes. These include photochemical, thermochemical, chemical, and mechanochemical processes. Polymeric materials derive their physical properties from the time scale of motion, summation of intermolecular forces, and number of chain entanglements and crosslinks. Glassy thermoset polymers experience mechanical fatigue during dynamic stress loading and properties diminish with inevitable material failure at stress levels below the ultimate tensile strength (UTS). Damage modeling has been successful in predicting the number of cycles required to induce failure in a specimen due to stress. However, it does not directly provide an explanation of the origin of fatigue in polymers. It is hypothesized herein that mechanical failure at stress levels below the ultimate strength property is due to the accumulation of mechanically induced homolytic chain scission events throughout the glassy thermoset network. The goal of this research will be to quantify homolytic chain scission events with fatigue cycles with the ultimate goal of correlating mechanical property loss with degradation of covalent network structure. To accomplish this goal, stable free nitroxyl radicals were incorporated into an epoxy-amine matrix to detect homolytic chain scission resulting from fatigue. Chapter II discusses a successful synthesis and characterization of the nitroxyl radical molecule, a product of 4-hydroxy-2,2,5,5-tetramethylpiperdin-1-yl-oxyl (TEMPO) and isophorone diisocyanate designated as BT-IPDI. In Chapter III, the epoxy-amine reaction was determined to be unaffected by incorporation of up to 5 wt% of BT-IPDI. Although 50% UTS fatigue studies produced property degradation and fatigue failure as shown in Chapter IV, analysis of BT-IPDI through EPR did not detect homolytic chain scission. Chapter V reveals that mechano-radicals were produced from cryo-grinding the glassy

  3. Nanostructuration de résines polyester insaturé par des copolymères à blocs : application aux composites SMC et BMC

    Lamy, Yoann


    The aim of this study is to evaluate the potential of PBA-b-P(MMA-co-DMA) and PBA-b-P(BA-co-DMA) block copolymers (BCP) as multifunctional additives nanostructuring the unsaturated polyester thermosetting matrix of SMC and BMC composites. The nanostructuration of the unsaturated polyester resin (UPR) is ensured by the segregation of the poly(butyl acrylate) elastomeric block, and by the miscibility of the second block in the thermoset thanks to the good compatibility of dimethylacrylamide uni...



    Static and fatigue tests under compression load were made on impacted AS4/PEEK and T300/913C graphite/epoxy with [45/90/-45/0]5S stacking sequence. The comparison of the damage tolerance assessment for thermosetting and thermoplastic composites shows that thermoplastics are more damage tolerant under compression. Impacted thermoplastic composites have excellent compression-compression fatigue behavior. The damage growth life is only a few percent of their total fatigue life and no regular damage growth can be found. Some design principles for thermosetting composite structures may still be used.

  5. A Role for the Androgen Metabolite, 5alpha androstane, 3beta, 17beta Diol (3b-DIol in the regulation of the hypothalamo-pituitary-adrenal axis.

    Robert James Handa


    Full Text Available Activation of the hypothalamo-pituitary-adrenal (HPA axis is a basic reaction of animals to environmental perturbations that threaten homeostasis. These responses are ultimately regulated by neurons residing within the paraventricular nucleus of the hypothalamus (PVN. Within the PVN, corticotropin-releasing hormone (CRH, vasopressin (AVP and oxytocin (OT expressing neurons are critical as they can regulate both neuroendocrine and autonomic responses. Estradiol (E2 and testosterone (T are well known reproductive hormones, however, they have also been shown to modulate stress reactivity. In rodent models, evidence shows that under some conditions E2 enhances stress activated ACTH and corticosterone secretion. In contrast, T decreases the gain of the HPA axis. The modulatory role of testosterone was originally thought to be via 5 alpha reduction to the potent androgen, dihydrotestosterone, whereas E2 effects were thought to be mediated by both estrogen receptors alpha (ERα and beta (ERβ. However, DHT has been shown to be metabolized to the ERβ agonist, 5alpha- androstane 3beta,17beta diol (3b-Diol. The actions of 3β-Diol on the HPA axis are mediated by ERbeta which inhibits the PVN response to stressors. In gonadectomized rats, ERbeta agonists reduce CORT and ACTH responses to restraint stress, an effect that is also present in wild-type but not ERbeta knockout mice. The neurobiological mechanisms underlying the actions of ERbeta to alter HPA reactivity are not currently known. CRH, AVP and OT have all been shown to be regulated by estradiol and recent studies indicate an important role of ERbeta in these regulatory processes. Moreover, activation of the CRH and AVP promoters have been shown by 3β-Diol binding to ERbeta and this is thought to be through alternate pathways of gene regulation. Based on available data, a novel and important role for 3beta Diol in the regulation of the HPA axis is suggested.

  6. Association of symmetrical alkane diols with pyridine: DFT/GIAO calculation of (1) H NMR chemical shifts.

    Lomas, John S; Joubert, Laurent; Maurel, François


    Proton nuclear magnetic resonance (NMR) shifts of the free diol and of its 1 : 1 and 1 : 2 hydrogen-bonded complexes with pyridine have been computed for five symmetrical alkane diols on the basis of density functional theory, by applying the gauge-including atomic orbital method to geometry-optimized conformers. For certain conformers, intramolecular OH···OH interactions, evidenced by high NMR OH proton shifts, are further enhanced on going from the free diol to the corresponding 1 : 1 diol/pyridine complex. This is confirmed by atoms-in-molecules and non-covalent interaction plots. The computed OH and CH proton shifts for the diol and the two complexes correlate well with values obtained by analysing data from the NMR titration of the diols in benzene against pyridine. Shift values for the diols in neat pyridine are calculated by weighting the shifts of the various protons in the three forms (free diol, 1 : 1 and 1 : 2 diol/pyridine complexes) according to the experimentally determined association constants. The results are in good agreement with those observed, and after empirical scaling, the root mean square difference is 0.18 ppm. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  7. Toward high performance thermoset/carbon nanotube sheet nanocomposites via resistive heating assisted infiltration and cure.

    Kim, Jae-Woo; Sauti, Godfrey; Siochi, Emilie J; Smith, Joseph G; Wincheski, Russell A; Cano, Roberto J; Connell, John W; Wise, Kristopher E


    Thermoset/carbon nanotube (CNT) sheet nanocomposites were successfully fabricated by resistive heating assisted infiltration and cure (RHAIC) of the polymer matrix resin. Resistive heating takes advantage of the electrical and thermal conductivity of CNTs to rapidly and uniformly introduce heat into the CNT sheet. Heating the CNT sheet reduces the viscosity of the polymer resin due to localized temperature rise in close proximity to the resin, which enhances resin flow, penetration, and wetting of the CNT reinforcement. Once the resin infusion process is complete, the applied power is increased to raise the temperature of the CNT sheet, which rapidly cures the polymer matrix. Tensile tests were used to evaluate the mechanical properties of the processed thermoset/CNT sheet nanocomposites. The improved wetting and adhesion of the polymer resin to the CNT reinforcement yield significant improvement of thermoset/CNT nanocomposite mechanical properties. The highest specific tensile strength of bismaleimide(BMI)/CNT sheet nanocomposites was obtained to date was 684 MPa/(g/cm(3)), using 4 V (2 A) for resin infiltration, followed by precure at 10 V (6 A) for 10 min and post curing at 240 °C for 6 h in an oven. The highest specific Young's modulus of BMI/CNT sheet nanocomposite was 71 GPa/(g/cm(3)) using resistive heating infiltration at 8.3 V (4.7 A) for 3 min followed by resistive heating cure at 12.5 V (7 A) for 30 min. In both cases, the CNT sheets were stretched and held in tension to prevent relaxation of the aligned CNTs during the course of RHAIC.

  8. Variable frequency microwave (VFM) curing, processing of thermoset prepreg laminates. Final report

    Paulauskas, F.L.


    The objective of this work was to investigate the beneficial effect of the variable frequency microwave (VFM) technology to cure thermosetting prepreg laminates. Further, it was to investigate the interrelationship and effect on the curing process of frequency, band width, and curing time with different types of laminates. Previous studies of microwave-assisted curing of neat resins (epoxy) and unidirectional glass and carbon fiber laminates with a fixed frequency of 2.45 GHz, have shown that a substantial reduction in the curing time was obtained. Results of this earlier work indicate that the microwave-assisted curing of multidirectional glass fiber laminates also show a substantial reduction of the required curing time. This may be explained by the penetration of microwave energy directly and throughout the laminate with enhancement of the kinetics of the chemical reaction. The fixed frequency microwave radiation of 2.45 GHz has been demonstrated to be a partially acceptable method to cure unidirectional carbon fiber laminates. Multidirectional carbon fiber/epoxy laminates demonstrate a lack of coupling during the curing process. A direct curing of these laminates was not possible by microwave radiation with the experimental approach used in agreement with previous work. In addition to this short coming, the unidirectional laminate samples cured with the fixed frequency are visually nonuniform. Localized areas of darker colors (burn, hot spots, overheating) are attributed to the formation of standing waves within the microwave cavity. For this reason, the laminates are subject to proper rotation while curing through fixed frequency. The present research indicates that variable frequency microwave technology is a sound and acceptable processing method to effectively cure uni-, bi- or multi-directional thermosetting glass fiber laminates. Also, this methodology will effectively cure unidirectional thermosetting carbon fiber laminates. For all these cases, this

  9. Sustainable epoxy and oxetane thermosets from photo-initiated cationic polymerization

    Ryu, Chang

    A group of sustainable materials are proposed and produced from multifunctional epoxides and oxetanes obtained from renewable sources. Monomers are photopolymerized using diaryliodonium salts designed and synthesized by our group as initiator. A detailed investigation of the network formation of epoxidized linseed oil revealed that crosslinks is markedly dependent to the thickness and viscosity of substrate. Copolymerization studies of difunctional oxetane showed that limonene dioxide was effective in increasing the reaction rates and shorten the inherent induction period, also known as kick-starting effect. Such oxetane thermoset can achieve desirable curing rates and Tg compared to petroleum based epoxy used in applications such as large scale surface coatings.

  10. Epoxy Thermosets: The Detection of Adverse Stoichiometry Using Ultrasonic, Dielectric and NMR Techniques

    Unwin, M. E.; Challis, R. E.


    The relative proportions of hardener and resin (the stoichiometric ratio, SR) in a curing epoxy thermoset strongly influence the engineering properties of the material. We investigate how NMR, dielectric and ultrasonic techniques can be used to track cure and estimate SR in the material. We show that all three methods are sensitive to SR and can give clear and quantitative indications of excess resin. Detection of excess hardener in the finally cured material is more difficult but can be achieved by combined measures of elastic modulus, from the ultrasonic velocity, and loss angle, from ultrasonic attenuation.

  11. Experimental and DFT study of cyclodehydration and acetylation of ferrocenyl diols

    Lapić, Jasmina; Višnjevac, Aleksandar; Cetina, Mario; Djaković, Senka; Vrček, Valerije; Rapić, Vladimir


    Racemic ferrocenyl diols, i.e. ferrocenyl(2-hydroxymethylphenyl)methanol (2), ferrocenyl-2-(2-hydroxymethylphenyl)ethanol (7), and ferrocenyl(2-(2-hydroxyethyl)phenyl)methanol (9) have been prepared by reduction of corresponding ketoesters using NaBH4 in a mixture EtOH and Et2O. In the course of these reactions new cyclic ethers 1-ferrocenyl-2-oxaindane (3), 3-ferrocenylisochromane (8), and 1-ferrocenylisochromane (10) have been isolated as side-products. Intramolecular cyclizations of ferrocenyl diols occur in both acidic and neutral medium. Density functional theory (BP86) calculations were used to explain the mechanism of these cyclodehydrations. Acid catalyzed reaction follows the classical SN1 mechanism, whereas the cyclodehydration in neutral medium is described as an SN2 reaction. X-ray diffraction analysis of new cyclic ether products has been performed. Monoacetates 11, 13 and 15 have been obtained in the reaction of ferrocenyl diols 2, 7, and 9, respectively, and acetic anhydride. Stereoselective acylation of racemic diols by vinyl acetate have been catalyzed by various lipases, and the best stereoselectivity has been observed for the diol 2 in the presence of Penicillium camembertii lipase.

  12. The C32 alkane-1,15-diol as a tracer for riverine input in coastal seas

    Lattaud, Julie; Kim, Jung-Hyun; De Jonge, Cindy; Zell, Claudia; Sinninghe Damsté, Jaap S.; Schouten, Stefan


    Long chain alkyl diols are lipids that occur ubiquitously in marine sediments and are used as a proxy for sea surface temperature (SST), using the Long chain Diol Index (LDI), and for upwelling intensity/high nutrient conditions. The distribution of 1,13- and 1,15-diols has been documented in open marine and lacustrine sediments and suspended particulate matter, but rarely in coastal seas receiving a significant riverine, and thus continental organic matter, input. Here we studied the distribution of diols in four shelf seas with major river outflows: the Gulf of Lion, the Kara Sea, the Amazon shelf and the Berau delta, covering a wide range of climate conditions. The relative abundance of the C32 1,15-diol is consistently higher close to the river mouth and particularly in the suspended particulate matter of the rivers suggesting a terrigenous source. This is supported by statistical analysis which points out a significant positive correlation between the C32 1,15-diol and the Branched and Isoprenoid Tetraether index, a proxy reflecting soil and riverine input in marine environments. However, the C32 1,15-diol was not detected in soils and is unlikely to be derived from vegetation, suggesting that the C32 1,15-diol is mainly produced in rivers. This agrees with the observation that it is a dominant diol in most cultivated freshwater eustigmatophyte algae. We, therefore, suggest that the relative abundance of the C32 1,15-diol can potentially be used as a proxy for riverine organic matter input in shelf seas. Our results also show that long chain alkyl diols delivered by rivers can substantially affect LDI-reconstructed SSTs in coastal regions close to river mouths.

  13. A comparative study on vibrational, conformational and electronic structure of α,α'-diol-o-xylene, α,α'-diol-m-xylene and α,α'-diol-p-xylene.

    Arjunan, V; Saravanan, I; Mythili, C V; Kalaivani, M; Mohan, S


    The Fourier transform infrared (FTIR) and FT-Raman spectra of α,α'-diol-o-xylene (DOLOX), α,α'-diol-m-xylene (DOLMX) and α,α'-diol-p-xylene (DOLPX) of the configuration HOCH(2)-C(6)H(4)-CH(2)OH have been recorded in the range 4000-400 and 4000-100 cm(-1), respectively. The most stable geometry of the compounds was determined by conformational analysis. The complete vibrational assignment and analysis of the fundamental modes of the most stable conformer of the compounds were carried out using the experimental FTIR and FT-Raman data and quantum chemical studies. The observed vibrational frequencies were compared with the wavenumbers derived theoretically for the optimised geometry of the compounds from the DFT-B3LYP gradient calculations employing the standard 6-31G** and high level and 6-311++G** basis sets. The structural parameters and vibrational wavenumbers obtained from the DFT method are in good agreement with the experimental data. The potential energy distributions of the fundamental modes were also calculated by Wilson's FG matrix method. The effect of -CH(2)OH groups on the skeletal vibrations have been discussed. The intra molecular n→σ* and π→π* interactions were discussed with NBO analysis. Copyright © 2012 Elsevier B.V. All rights reserved.




    论述了热固性塑料注射成型的方法、工艺、设备和模具设计方面的问题。%Molding process,equipment and die of thermosetting plastics for injection molding discussed in the paper.

  15. Properties of Thermosets Derived from Chemically Modified Triglycerides and Bio-Based Comonomers

    Evan S. Beach


    Full Text Available A series of materials was prepared by curing acrylated epoxidized soybean oil (AESO and dibutyl itaconate (DBI or ethyl cinnamate (EC comonomers to provide examples of thermosets with a high proportion of bio-based carbon, in accordance with the principles of green chemistry. The comonomers, representative of cellulose-derived (DBI or potentially lignin-derived (EC raw materials, were tested at levels of 25%, 33%, and 50% by mass and the resulting products were characterized by infrared spectroscopy, thermogravimetric analysis, and dynamic mechanical analysis. Both DBI and EC were incorporated into the thermosets to a high extent (>90% at all concentrations tested. The AESO-DBI and AESO-EC blends showed substantial degradation at 390–400 °C, similar to pure AESO. Glass transition temperatures decreased as comonomer content increased; the highest Tg of 41.4 °C was observed for AESO-EC (3:1 and the lowest Tg of 1.4 °C was observed for AESO-DBI (1:1. Accordingly, at 30 °C the storage modulus values were highest for AESO-EC (3:1, 37.0 MPa and lowest for AESO-DBI (1:1, 1.5 MPa.

  16. Improving Mechanical Properties of Thermoset Biocomposites by Fiber Coating or Organic Oil Addition

    Truc T. Ngo


    Full Text Available Two different thermoset biocomposite systems are experimented in this study with the hope to improve their mechanical properties. Fiberglass and hemp, in form of fabrics, are used to reinforce the thermoset polymer matrix, which includes a traditional epoxy resin and a linseed oil-based bioresin (UVL. The fiber/polymer matrix interface is modified using two different approaches: adding a plant-based oil (pine or linseed to the polymer matrix or coating the fibers with 3-(aminopropyltriethoxysilane (APTES prior to integrating them into the polymer matrix. Epoxy resin is cured using an amine-based initiator, whereas UVL resin is cured under ultraviolet light. Results show that hemp fibers with APTES prime coat used in either epoxy or UVL matrix exhibit some potential improvements in the composite’s mechanical properties including tensile strength, modulus of elasticity, and ductility. It is also found that adding oil to the epoxy matrix reinforced with fiberglass mostly improves the material’s modulus of elasticity while maintaining its tensile strength and ductility. However, adding oil to the epoxy matrix reinforced with hemp doubles the material’s ductility while slightly reducing its tensile strength and modulus of elasticity.

  17. Cardanol-based thermoset plastic reinforced by sponge gourd fibers (Luffa cylindrica

    André Leandro da Silva


    Full Text Available Abstract A growing global trend for maximum use of natural resources through new processes and products has enhanced studies and exploration of renewable natural materials. In this study, cardanol, a component of the cashew nut shell liquid (CNSL, was used as a building block for the development of a thermosetting matrix, which was reinforced by raw and modified sponge gourd fibers (Luffa cylindrica. DSC and TG results showed that among biocomposites, the one reinforced by sponge gourd fibers treated with NaOH 10 wt% (BF10 had the highest thermal stability, besides the best performance in the Tensile testing, showing good incorporation, dispersion, and adhesion to polymer matrix, observed by SEM. After 80 days of simulated soil experiments, it has been discovered that the presence of treated fiber allowed better biodegradability behavior to biocomposites. The biobased thermoset plastic and biocomposites showed a good potential to several applications, such as manufacturing of articles for furniture and automotive industries, especially BF10.

  18. Iridium‐Catalyzed Condensation of Amines and Vicinal Diols to Substituted Piperazines

    Lorentz-Petersen, Linda Luise Reeh; Nordstrøm, Lars Ulrik Rubæk; Madsen, Robert


    additives and only produces water as the byproduct. The reaction can be performed between a 1,2‐diamine and a 1,2‐diol or by a double condensation between a primary alkylamine and a 1,2‐diol. At least one substituent is required on the piperazine ring to achieve the cyclization in good yield. The mechanism...... is believed to involve dehydrogenation of the 1,2‐diol to the α‐hydroxy aldehyde, which condenses with the amine to form the α‐hydroxy imine. The latter rearranges to the corresponding α‐amino carbonyl compound, which then reacts with another amine followed by reduction of the resulting imine....

  19. Energy and chemicals from the selective electrooxidation of renewable diols by organometallic fuel cells.

    Bellini, Marco; Bevilacqua, Manuela; Filippi, Jonathan; Lavacchi, Alessandro; Marchionni, Andrea; Miller, Hamish A; Oberhauser, Werner; Vizza, Francesco; Annen, Samuel P; Grützmacher, H


    Organometallic fuel cells catalyze the selective electrooxidation of renewable diols, simultaneously providing high power densities and chemicals of industrial importance. It is shown that the unique organometallic complex [Rh(OTf)(trop2NH)(PPh3)] employed as molecular active site in an anode of an OMFC selectively oxidizes a number of renewable diols, such as ethylene glycol , 1,2-propanediol (1,2-P), 1,3-propanediol (1,3-P), and 1,4-butanediol (1,4-B) to their corresponding mono-carboxylates. The electrochemical performance of this molecular catalyst is discussed, with the aim to achieve cogeneration of electricity and valuable chemicals in a highly selective electrooxidation from diol precursors.

  20. Multiple healing in multi-functional polymer composites

    Lafont, U.L.; Van Zeijl, H.; Van der Zwaag, S.


    In this work, we investigate the formation of self-healing systems that are able to recover more than once more than one (mechanical or other physical) functionality. To this aim composites were created consisting of a polysulfide thermoset rubber matrix having intrinsic self-healing properties fill

  1. Thermoresponsive Polymers and Inverse Opal Hydrogels for the Detection of Diols.

    Couturier, Jean-Philippe; Wischerhoff, Erik; Bernin, Robert; Hettrich, Cornelia; Koetz, Joachim; Sütterlin, Martin; Tiersch, Brigitte; Laschewsky, André


    Responsive inverse opal hydrogels functionalized by boroxole moieties were synthesized and explored as sensor platforms for various low molar mass as well as polymeric diols and polyols, including saccharides, glycopolymers and catechols, by exploiting the diol induced modulation of their structural color. The underlying thermoresponsive water-soluble copolymers and hydrogels exhibit a coil-to-globule or volume phase transition, respectively, of the LCST-type. They were prepared from oligoethylene oxide methacrylate (macro)monomers and functionalized via copolymerization to bear benzoboroxole moieties. The resulting copolymers represent weak polyacids, which can bind specifically to diols within an appropriate pH window. Due to the resulting modulation of the overall hydrophilicity of the systems and the consequent shift of their phase transition temperature, the usefulness of such systems for indicating the presence of catechols, saccharides, and glycopolymers was studied, exploiting the diol/polyol induced shifts of the soluble polymers' cloud point, or the induced changes of the hydrogels' swelling. In particular, the increased acidity of benzoboroxoles compared to standard phenylboronic acids allowed performing the studies in PBS buffer (phosphate buffered saline) at the physiologically relevant pH of 7.4. The inverse opals constructed of these thermo- and analyte-responsive hydrogels enabled following the binding of specific diols by the induced shift of the optical stop band. Their highly porous structure enabled the facile and specific optical detection of not only low molar mass but also of high molar mass diol/polyol analytes such as glycopolymers. Accordingly, such thermoresponsive inverse opal systems functionalized with recognition units represent attractive and promising platforms for the facile sensing of even rather big analytes by simple optical means, or even by the bare eye.

  2. Substituent effects and pH profiles for stability constants of arylboronic acid diol esters.

    Martínez-Aguirre, Mayte A; Villamil-Ramos, Raul; Guerrero-Alvarez, Jorge A; Yatsimirsky, Anatoly K


    Stability constants of boronic acid diol esters in aqueous solution have been determined potentiometrically for a series of meta-, para-substituted phenylboronic acids and diols of variable acidity. The constants β(11-1) for reactions between neutral forms of reactants producing the anionic ester plus proton follow the Hammett equation with ρ depending on pKa of diol and varying from 2.0 for glucose to 1.29 for 4-nitrocatechol. Observed stability constants (K(obs)) measured by UV-vis and fluorometric titrations at variable pH for esters of 4,5-dihydroxy-1,3-benzenedisulfonate (Tiron) generally agree with those expected on the basis of β(11-1) values, but the direct fitting of K(obs) vs pH profiles gives shifted pKa values both for boronic acids and diol as a result of significant interdependence of fitting parameters. The subsituent effects on absorption and fluorescence spectra of Tiron arylboronate esters are characterized. The K(obs) for Tiron determined by (11)B NMR titrations are approximately 1 order of magnitude smaller than those determined by UV-vis titrations under identical conditions. A general equation, which makes possible an estimate of β(11-1) for any pair of boronic acid and diol from their pKa values, is proposed on the basis of established Brönsted-type correlation of Hammett parameters for β(11-1) with acidity of diols. The equation allows one to calculate stability constants expected only on basis of acid-base properties of the components, thus permitting more strict evaluation of contributions of additional factors such as steric or charge effects to the ester stability.

  3. Dielectrophoretically structured piezoelectric composites with high aspect ratio piezoelectric particles inclusions

    Ende, D.A. van den; Kempen, S.E. van; Wu, X.; Groen, W.A.; Randall, C.A.; Zwaag, S. van der


    Piezoelectric composites were prepared by dielectrophoretic alignment of high aspect ratio piezoelectric particles in a thermosetting polymer matrix. A high level of alignment was achieved in the cured composite from a resin containing randomly oriented high aspect ratio particles. Upon application

  4. Synthesis and characterization of yellow water-borne polyurethane using a diol colorant as extender


    A novel and facile method toward a series of yellow water-borne polyurethane was developed by using an intrinsically colored diol in this paper.The yellow aqueous dispersion PCLD-HENA-PU was synthesized based on isophorone diisocyanate(IPDI), polycaprolactonediol(PCLD) and 2,2-dimethylol propionic acid(DMPA) using a yellow diol N,N-bis(2-hydroxyethyl)-4-nitroaniline (HENA) as a chain extender.Due to the complete reaction of OH group in colorant HENA with NCO group in diisocyanate,a series of stable yello...

  5. Synthetic and computational evaluation of regiodivergent epoxide opening for diol and polyol synthesis.

    Gansäuer, Andreas; Karbaum, Peter; Schmauch, David; Einig, Martin; Shi, Lili; Anoop, Anakuthil; Neese, Frank


    In a combined synthetic and computational study, the factors governing the selectivity of the titanocene(III)-catalyzed regiodivergent epoxide opening (REO) with Kagan's complex via electron transfer leading to derivatives of 1,2-, 1,3-, and 1,4-diols were investigated. In this manner, valuable building blocks for the synthesis of 1,3- and 1,4-diols were identified. The computational study provides crucial structural features and energies of the transition states of ring opening that are important for the design of more selective catalysts.

  6. Tandem Olefin Metathesis/Oxidative Cyclization: Synthesis of Tetrahydrofuran Diols from Simple Olefins.

    Dornan, Peter K; Lee, Daniel; Grubbs, Robert H


    A tandem olefin metathesis/oxidative cyclization has been developed to synthesize 2,5-disubstituted tetrahydrofuran (THF) diols in a stereocontrolled fashion from simple olefin precursors. The ruthenium metathesis catalyst is converted into an oxidation catalyst in the second step and is thus responsible for both catalytic steps. The stereochemistry of the 1,5-diene intermediate can be controlled through the choice of catalyst and the type of metathesis conducted. This olefin stereochemistry then controls the THF diol stereochemistry through a highly stereospecific oxidative cyclization.

  7. Regioselective Benzoylation of Diols and Carbohydrates by Catalytic Amounts of Organobase

    Yuchao Lu


    Full Text Available A novel metal-free organobase-catalyzed regioselective benzoylation of diols and carbohydrates has been developed. Treatment of diol and carbohydrate substrates with 1.1 equiv. of 1-benzoylimidazole and 0.2 equiv. of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU in MeCN under mild conditions resulted in highly regioselective benzoylation for the primary hydroxyl group. Importantly, compared to most commonly used protecting bulky groups for primary hydroxyl groups, the benzoyl protective group offers a new protection strategy.

  8. Characterization of clay-modified thermoset polymers under various environmental conditions for the use in high-voltage power pylons

    Kliem, Mathias; Høgsberg, Jan Becker; Wang, Qian


    , the morphology was found to be of exfoliated structure mainly. Static, uniaxial tensile tests showed that the addition of nanoclay to thermoset polymers led to a beneficial effect on the stiffness, whereas the tensile strength and ductility significantly decreased. When exposed to different environmental...

  9. Kinetics of phosphotungstic acid catalyzed oxidation of propan-1,3-diol and butan-1,4-diol by N-chlorosaccharin

    Sanjay Kumar Singh


    Full Text Available The kinetic studies of N-chlorosaccharin (NCSA oxidation of propan-1,3-diol and butan-1,4-diol have been reported in presence of phophotungstic acid and in aqueous acetic acid medium. The reactions follow first-order in NCSA and one to zero order with respect to substrate and phosphotungstic acid. Increase in the concentration of added perchloric acid increases the rate of oxidation. A negative effect on the oxidation rate is observed for solvent whereas the ionic strength does not influence the rate of reaction. Addition of the reaction product, saccharin, exhibited retarding effect. Various activation parameters have been evaluated. The products of the reactions were identified as the corresponding aldehydes. A suitable scheme of mechanism consistent with the experimental results has been proposed.

  10. Influence of prepolymer composition on polyurethane morphology

    Krishnamoorthy, Jayaraman; Jeong, Young Gyu; Hashida, Tomoko; Hsu, Shaw Ling


    Polyurethane chemistry is one of the most studied subjects. Yet many aspects remain unexplained. Polyurethanes are synthesized by the reaction of diisocyanate with diol in the presence of nucleophilic catalysts. Polyurethane prepolymers are obtained by reacting the polyester diol / polyether diol with diisocyanate, with [NCO] / [OH] > 1, resulting in isocyanate-terminated polyester/polyether mixture. Prepolymers thus synthesized can be cured at a later stage to realize various morphologies and structures. Though the initial composition and the final morphology are known, little is known about the intermediate prepolymer mixture. Due to the different reactivity of primary and secondary hydroxyl groups in the polyester and polyether towards isocyanate, prepolymer has a non-random distribution in terms of composition as blends and copolymers. Our aim is to characterize the prepolymer by different techniques and study how the different prepolymer composition, with varying polyester and polyether ratio, affects the morphology and phase separation kinetics of the final product.

  11. On the origins of kinetic resolution of cyclohexane-1,2-diols through stereoselective acylation by chiral tetrapeptides.

    Shinisha, C B; Sunoj, Raghavan B


    The relative energies of cyclohexane-1,2-diols and chiral tetrapeptide (2 (Boc) or 3 (Moc)) complexes calculated using DFT indicate a thermodynamic preference for chiral recognition toward (1R,2R)(e,e)-alpha isomer. The barrier for stereoselective acyl transfer is identified as lower for trans-(1R,2R)-cyclohexane-1,2-diol, leading to the kinetic resolution (KR) of trans-(1S,2S)-cyclohexane-1,2-diol. The prediction is in concert with the reported experiments for trans-diols, while that for hitherto unknown cis-diol demands experimental verification. It is proposed that desymmetrization would enable the resolution of cis-(1R,2S)-2-hydroxycyclohexyl acetate.

  12. Thermal Curing Cycles for Composite Cylinders with Thick Walls and Thermoset Resins


    solved, using the boundary conditions (33,34) and conservation of mass (36), for the normal gap flow . The solutions are d p dpnU = j n V ,- ,x’- + xyf...left side of the ith fiber, due to the local parts of the normal gap flow . The integral (58) with the expressions (8,54,55) is well defined and gives

  13. Nano-Zirconium Tungstate Reinforced Liquid Crystalline Thermosetting Composites with Near Zero Thermal Expansion


    transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). The FTIR spectrum was recorded on a Bruker’s IFS66V FTIR with a...not change much after 154 °C. Nematic LC phase usually displays schlieren texture while smectic LC phase usually shows a fan-shaped focal- conic ...The fan-shaped focal- conic texture for the cure temperatures from 170 °C to 190 °C in the figure is a characteristic of the smectic LC phase. The

  14. Biodegradable polyurethanes for implants. II. In vitro degradation and calcification of materials from poly(epsilon-caprolactone)-poly(ethylene oxide) diols and various chain extenders.

    Gorna, Katarzyna; Gogolewski, Sylwester


    Linear, biodegradable, aliphatic polyurethanes with various degrees of hydrophilicity were synthesized in bulk at 50-100 degrees C. The ratios between the hydrophilic and hydrophobic segments were 0:100, 30:70, 40:60, 50:50, and 70:30, respectively. The hydrophilic segment consisted of poly(ethylene oxide) (PEO) diol (molecular weight = 600 or 2000) or the poly(ethylene-propylene-ethylene oxide) (PEO-PPO-PEO) diol Pluronic F-68 (molecular weight = 8000). The hydrophobic segment was made of poly(epsilon-caprolactone) diol (molecular weight = 530, 1250, or 2000). The chain extenders were 1,4-butane diol and 2-amino-1-butanol. The diisocyanate was aliphatic hexamethylene diisocyanate. The polymers absorbed water in an amount that increased with the increasing content of the PEO segment in the polymer chain. The total amount of absorbed water did not exceed 2% for the poly(ester urethane)s and was as high as 212% for some poly(ester ether urethane)s that behaved in water like hydrogels. The polymers were subjected to in vitro degradation at 37 +/- 0.1 degrees C in phosphate buffer solutions for up to 76 weeks. The poly(ester urethane)s showed 1-2% mass loss at 48 weeks and 1.1-3.8% mass loss at 76 weeks. The poly(ester ether urethane)s manifested 1.6-76% mass loss at 48 weeks and 1.6-96% mass loss at 76 weeks. The increasing content and molecular weight of the PEO segment enhanced the rate of mass loss. Similar relations were also observed for polyurethanes from PEO-PPO-PEO (Pluronic) diols. Materials obtained with 2-amino-1-butanol as the chain extender degraded at a slower rate than similar materials synthesized with 1,4-butane diol. All the materials already manifested a progressive decrease in the molecular weight in the first month of in vitro aging. The rate of molecular weight loss was higher for poly(ester ether urethane)s than for poly(ester urethane)s. For poly(ester ether urethane)s, the rate of molecular weight loss was higher for materials containing

  15. Alloys and composites of polybenzoxazines properties and applications

    Rimdusit, Sarawut; Tiptipakorn, Sunan


    This book provides an introduction to the unique and fascinating properties of alloys and composites from novel commercialized thermosetting resins based on polybenzoxazines. Their outstanding properties such as processability, thermal, mechanical, electrical properties as well as ballistic impact properties of polybenzoxazine alloys and composites make them attractive for various applications in electronic packaging encapsulation, light weight ballistic armour composites and bipolar plate in fuel cells.

  16. Microbial Stereoselective One-Step Conversion of Diols to Chiral Lactones in Yeast Cultures

    Filip Boratyński


    Full Text Available It has been shown that whole cells of different strains of yeast catalyze stereoselective oxidation of meso diols to the corresponding chiral lactones. Among screening-scale experiments, Candida pelliculosa ZP22 was selected as the most effective biocatalyst for the oxidation of monocyclic diols 3a–b with respect to the ratio of high conversion to stereoselectivity. This strain was used in the preparative oxidation, affording enantiomerically-enriched isomers of lactones: (+-(3aR,7aS-cis-hexahydro-1(3H -isobenzofuranone (2a and (+-(3aS,4,7,7aR-cis-tetrahydro-1(3H-isobenzofuranone (2b. Scaling up the culture growth, as well as biotransformation conditions has been successfully accomplished. Among more bulky substrates, bicyclic diol 3d was totally converted into enantiomerically-pure exo-bridged (+-(3aR,4S,7R,7aS-cis-tetrahydro-4,7-methanoisobenzofuran -1(3H-one (2d by Yarrovia lipolytica AR71. Microbial oxidation of diol 3f by Candida sake AM908 and Rhodotorula rubra AM4 afforded optically-pure cis-3-butylhexahydro-1(3H -isobenzofuranone (2f, however with low conversion.

  17. Chemical consequences of long-range orbital interaction in perhydronaphtalene-1,4 diol monosulfonate esters.

    Orru, R.V.A.


    In this thesis the base-induced reactions of perhydronaphthalene-1,4-diol monosulfonate esters are described. These compounds undergo smoothly, typical carbocationic processes upon treatment with sodium tert -amylate in refluxing benzene. The product outcome, product ratio, and (relative) rate of th

  18. Efficient hydrogenation of biomass-derived cyclic di-esters to 1,2-diols.

    Balaraman, Ekambaram; Fogler, Eran; Milstein, David


    The unprecedented homogeneous hydrogenation of cyclic di-esters, in particular biomass-derived glycolide and lactide, to the corresponding 1,2-diols is catalyzed by Ru(II) PNN (1) and Ru(II) CNN (2) pincer complexes under mild hydrogen pressure and (in the case of 1) neutral conditions. No racemization was observed when a chiral di-ester was used.

  19. Potential biological sources of long chain alkyl diols in a lacustrine system

    Villanueva, Laura; Besseling, Marc; Rodrigo-Gámiz, Marta; Rampen, Sebastiaan W.; Verschuren, Dirk; Sinninghe Damsté, Jaap S.


    Long chain alkyl diols (LCDs) have been detected in a range of marine and lacustrine environments, as well as in several algal cultures. However, the identity of the producers, their preferred ecological niche and seasonality are uncertain. We applied a gene-based approach to determine the identity

  20. Lipase-catalyzed synthesis of oligoesters of 2,5-furandicarboxylic acid with aliphatic diols

    Cruz-Izquierdo, Álvaro; Broek, van den Lambertus A.M.; Serra, Juan L.; Llama, María J.; Boeriu, Carmen G.


    2,5-Furandicarboxylic acid is a platform chemical for the production of biobased polymers and materials. This study reports the synthesis of furan oligoesters via polytransesterification of dimethyl furan-2,5-dicarboxylate and linear α, ω-aliphatic diols with chain length ranging from C2 to C12,

  1. Binary phase diagram of monolayers of simple 1,2-diol derivatives

    Wolf, C. De; Bringezu, F.; Brezesinski, G.;


    The miscibility properties of monolayers of two 1,2-diol derivatives, 1-palmitoylglycerol (1) and 1-hexadecylglycerol (2), have been studied at the air-water interface using grazing incidence X-ray diffraction (GIXD). While, at all pressures investigated, compound (I) exhibits only a NN...

  2. Lipase-catalyzed synthesis of oligoesters of 2,5-furandicarboxylic acid with aliphatic diols

    Cruz-Izquierdo, Álvaro; Broek, van den Lambertus A.M.; Serra, Juan L.; Llama, María J.; Boeriu, Carmen G.


    2,5-Furandicarboxylic acid is a platform chemical for the production of biobased polymers and materials. This study reports the synthesis of furan oligoesters via polytransesterification of dimethyl furan-2,5-dicarboxylate and linear α, ω-aliphatic diols with chain length ranging from C2 to C12,

  3. An efficient hydrophilic interaction liquid chromatography separation of 7 phospholipid classes based on a diol column

    Zhu, C.; Dane, A.; Spijksma, G.; Wang, M.; Greef, J. van der; Luo, G.; Hankemeier, T.; Vreeken, R.J.


    A hydrophilic interaction liquid chromatography (HILIC) - ion trap mass spectrometry method was developed for separation of a wide range of phospholipids. A diol column which is often used with normal phase chromatography was adapted to separate different phospholipid classes in HILIC mode using a m

  4. Probing the interactions between boronic acids and cis-diol-containing biomolecules by affinity capillary electrophoresis.

    Lü, Chenchen; Li, Hengye; Wang, Heye; Liu, Zhen


    The affinity of boronic acids to cis-diol-containing biomolecules has found wide applications in many fields, such as sensing, separation, drug delivery, and functional materials. A sound understanding of the binding interactions will greatly facilitate exquisite applications of this chemistry. Although a few analytical tools have been available for the characterization of the interactions, these techniques are associated with some apparent drawbacks, so they are only applicable to a limited range of boronic acids and cis-diol-containing biomolecules. Therefore, a widely applicable method is still greatly needed. In this work, an affinity capillary electrophoresis (ACE) method was established and validated to probe the interactions between boronic acids and cis-diol-containing biomolecules. The method was proven to be applicable to almost all types of cis-diol-containing biomolecules and boronic acids. Based on this method, a quantitative, comparative study on the interactions between 14 boronic acids that have important potentials for application with 5 typical monosaccharides of biological importance was carried out. The findings provided new insights into boronate affinity interactions, particularly the relationship between the binding strength with the molecular structures of the binding species. Besides, effects of pH and temperature on the binding strength were also investigated. This method exhibited several significant advantages, including (1) possibility of simultaneous study of multiple interactions, (2) low requirement on the purity of the binding species, (3) wide applicability, and (4) high accuracy and precision.

  5. Mechanochemical modification of lignin and application of the modified lignin for thermoplastics and thermosets

    Guo, Xiaojie; Zhang, Jinwen; Xin, Junna

    In this work, mechanochemical modification of lignin and use of the modified lignin in thermoplastics and thermosets were studied. Oleated lignin was successfully prepared by transesterification between lignin and methyl, and the oleation reaction was performed in a solvent-free and room temperature ball milling process with a relatively short time. PLA/lignin blends were prepared through melt extrusion. Compared with the PLA/lignin blends, the PLA/oleated lignin blends exhibited finer dispersion of lignin in the blends, increased glass transition temperature and higher tensile properties, suggesting improved compatibility between lignin and PLA. Carboxylic and anhydride groups were also introduced into the structure of lignin via mechanochemical modification, and the resulting lignin derivatives were used as curing agents for epoxies. The dynamic mechanical properties and thermal stability of the cured epoxy resins were studied using dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA).

  6. Residual internal stress optimization for EPON 828/DEA thermoset resin using fiber Bragg grating sensors

    Rohr, Garth D.; Rasberry, Roger D.; Kaczmarowski, Amy K.; Stavig, Mark E.; Gibson, Cory S.; Udd, Eric; Roach, Allen R.; Nation, Brendan


    Internal residual stresses and overall mechanical properties of thermoset resins are largely dictated by the curing process. It is well understood that fiber Bragg grating (FBG) sensors can be used to evaluate temperature and cure induced strain while embedded during curing. Herein, is an extension of this work whereby we use FBGs as a probe for minimizing the internal residual stress of an unfilled and filled Epon 828/DEA resin. Variables affecting stress including cure cycle, mold (release), and adhesion promoting additives will be discussed and stress measurements from a strain gauge pop-off test will be used as comparison. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  7. Liquid Crystalline Thermosets from Ester, Ester-imide, and Ester-amide Oligomers

    Dingemans, Theodorus J. (Inventor); Weiser, Erik S. (Inventor); St. Clair, Terry L. (Inventor)


    Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,000 grams per mole. The end-capped liquid crystaloligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oli-gomers are stable forup to an hour in the melt phase. They are highly processable by a variety of melt process shape forming and blending techniques. Once processed and shaped, the end-capped liquid crystal oigomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures.

  8. Application of bioethanol derived lignin for improving physico-mechanical properties of thermoset biocomposites.

    Bajwa, Dilpreet S; Wang, Xinnan; Sitz, Evan; Loll, Tyler; Bhattacharjee, Sujal


    Lignin is the most abundant of renewable polymers next to cellulose with a global annual production of 70million tons, largely produced from pulping and second generation biofuel industries. Low value of industrial lignin makes it an attractive biomaterial for wide range of applications. The study investigated the application of wheat straw and corn stover based lignin derived from ethanol production for use in thermoset biocomposites. The biocomposite matrix constituted a two component low viscosity Araldite(®)LY 8601/Aradur(®) 8602 epoxy resin system and the lignin content varied from 0 to 25% by weight fraction. The analysis of the physical and mechanical properties of the biocomposites show bioethanol derived lignin can improve selective properties such as impact strength, and thermal stability without compromising the modulus and strength attributes. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. A biodegradable thermoset polymer made by esterification of citric acid and glycerol.

    Halpern, Jeffrey M; Urbanski, Richard; Weinstock, Allison K; Iwig, David F; Mathers, Robert T; von Recum, Horst A


    A new biomaterial, a degradable thermoset polymer, was made from simple, economical, biocompatable monomers without the need for a catalyst. Glycerol and citric acid, nontoxic and renewable reagents, were crosslinked by a melt polymerization reaction at temperatures from 90 to 150°C. Consistent with a condensation reaction, water was determined to be the primary byproduct. The amount of crosslinking was controlled by the reaction conditions, including temperature, reaction time, and ratio between glycerol and citric acid. Also, the amount of crosslinking was inversely proportional to the rate of degradation. As a proof-of-principle for drug delivery applications, gentamicin, an antibiotic, was incorporated into the polymer with preliminary evaluations of antimicrobial activity. The polymers incorporating gentamicin had significantly better bacteria clearing of Staphylococcus aureus compared to non-gentamicin gels for up to 9 days.

  10. Iterative tandem catalysis of secondary diols and diesters to chiral polyesters.

    van As, Bart A C; van Buijtenen, Jeroen; Mes, Tristan; Palmans, Anja R A; Meijer, E W


    The well-known dynamic kinetic resolution of secondary alcohols and esters was extended to secondary diols and diesters to afford chiral polyesters. This process is an example of iterative tandem catalysis (ITC), a polymerization method where the concurrent action of two fundamentally different catalysts is required to achieve chain growth. In order to procure chiral polyesters of high enantiomeric excess value (ee) and good molecular weight, the catalysts employed need to be complementary and compatible during the polymerization reaction. We here show that Shvo's catalyst and Novozym 435 fulfil these requirements. The optimal polymerization conditions of 1,1'-(1,3-phenylene) diethanol (1,3-diol) and diisopropyl adipate required 2 mol% Shvo's catalyst and 12 mg Novozym 435 per mmol alcohol group in the presence of 0.5 M 2,4-dimethyl-3-pentanol as the hydrogen donor. With these conditions, chiral polyesters were obtained with peak molecular weights up to 15 kDa, an ee value up to 99% and with 1-3 % ketone end groups. Also with the structural isomer, 1,4-diol, a chiral polyester was obtained, albeit with lower molecular weight (8.3 kDa) and slightly lower ee (94%). Aliphatic secondary diols also resulted in enantio-enriched polymers but at most an ee of 46 % was obtained with molecular weights in the range of 3.3-3.7 kDa. This low ee originates from the intrinsic low enantioselectivity of Novozym 435 for this type of secondary aliphatic diols. The results presented here show that ITC can be applied to procure chiral polyesters with good molecular weight and high ee from optically inactive AA-BB type monomers.

  11. Interaction of model aryl- and alkyl-boronic acids and 1,2-diols in aqueous solution.

    Marinaro, William A; Prankerd, Richard; Kinnari, Kaisa; Stella, Valentino J


    The goal of this work was to quantitate ester formation between alkyl and aryl boronic acids and vicinal-diols or 1,2-diols in aqueous solution. As used here, 1,2-diols includes polyols with one or more 1,2-diol pairs. Multiple techniques were used including apparent pKa shifts of the boronic acids using UV spectrophotometry (for aryl acids) and titration (for aryl and alkyl acids). Isothermal microcalorimetry was also used, with all reactions being enthalpically favored. For all the acids and 1,2-diols and the conditions studied, evidence only supported 1:1 ester formation. All the esters formed were found to be significantly more acidic, as Lewis acids, by 3-3.5 pKa units than the corresponding nonesterified boronic acid. The equilibrium constants for ester formation increased with increasing number of 1,2-diol pairs but stereochemistry may also play a role as sorbitol with five possible 1,2-diol pairs and five isomers (taking into account the stereochemistry of the alcohol groups) was twice as efficient at ester formation compared with mannitol, also with five possible 1,2-diol pairs but only three isomers. Alkyl boronic acids formed esters to a greater extent than aryl acids. Although some quantitative differences were seen between the various techniques used, rank ordering of the structure/reactivity was consistent. Formulation implications of ester formation between boronic acids and 1,2-diols are discussed. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

  12. Thermosetting resin modified by hyperbranched polymer%超支化聚合物改性热固性树脂

    王思明; 王晓洁; 刘锋; 李建


    介绍了超支化聚合物(HBP)的结构和特性,综述了其在改性热固性树脂[如环氧树脂(EP)、不饱和聚酯树脂、乙烯基树脂及酚醛树脂(PF)等]方面的应用。最后对HBP改性热固性树脂的发展方向进行了展望。%The structure and character of hyperbranched polymer(HBP)were introduced,the its applications were summarized in modified thermosetting resin[such as epoxy resin(EP),unsaturated polyester resin,vinyl resin and phenolic resin(PF)]. Finally,the development direction of HBP modified thermosetting resin was expected.

  13. 液晶热固体的合成与性能%Preparation and Properties of Liquid Crystalline Thermosets

    刘伟昌; 申胜军; 刘德山


      综述了液晶热固体的新进展,主要包括合成液晶热固体的基本条件、液晶热固体的力学及电学性能和独特的自增强结构,并依交联点类型对液晶热固体进行了分类,着重介绍了相应的合成方法及特点。%  The progresses of liquid crystalline thermosets (LCTs) are reviewed in this paper. The basic conditions of LCTs synthesis and the mechanical and electronic properties,as well as the special self-strengthen structure are introduced. The liquid crystalline thermosets are classified by the crosslinking sites and the corresponding preparation methods are described.

  14. 5alpha-Androstane-3beta,17beta-diol (3beta-diol), an estrogenic metabolite of 5alpha-dihydrotestosterone, is a potent modulator of estrogen receptor ERbeta expression in the ventral prostrate of adult rats.

    Oliveira, André G; Coelho, Polyanna H; Guedes, Fernanda D; Mahecha, Germán A B; Hess, Rex A; Oliveira, Cleida A


    Prostate is one of the major targets for dihydrotestosterone (DHT), however this gland is also recognized as a nonclassical target for estrogen as it expresses both types of estrogen receptors (ER), especially ERbeta. Nevertheless, the concentrations of aromatase and estradiol in the prostate are low, indicating that estradiol may not be the only estrogenic molecule to play a role in the prostate. It is known that DHT can be metabolized to 5alpha-androstane-3beta,17beta-diol (3beta-diol), a hormone that binds to ERbeta but not to AR. The concentration of 3beta-diol in prostate is much higher than that of estradiol. Based on the high concentration of 3beta-diol and since this metabolite is a physiological ERbeta ligand, we hypothesized that 3beta-diol would be involved in the regulation of ERbeta expression. To test this hypothesis, adult male rats were submitted to castration followed by estradiol, DHT or 3beta-diol replacement. ERbeta and AR protein levels in the prostate were investigated by immunohistochemistry and Western blotting assays. The results showed that after castration, the structure of the prostate was dramatically changed and ERbeta and AR protein levels were decreased. Estradiol had just minor effects on the parameters analyzed. DHT-induced partial recovery of ERbeta while it was the most effective inductor of AR expression. Replacement with 3beta-diol-induced the highest levels of ERbeta, but was comparatively less effective in recovering the AR expression and the gland structure. These results offer evidence that one functional role of 3beta-diol in the prostate may be autoregulation of its natural receptor, ERbeta.

  15. Molecular Modeling of Thermosetting Polymers: Effects of Degree of Curing and Chain Length on Thermo-Mechanical Properties


    the mechanical properties of one particular thermosetting polymer, DGEBA /DETDA epoxy system using atomistic molecular dynamics simulations. A series...response of the DGEBA /DETDA epoxy system, the atomistic simulation part described below will only consider a DGEBA monomer as the resin...on the reaction of the DGEBA (diglycidyl ether of bisphenol A) monomers with curing agent EPI-Cure-W (diethylenetoluenediamine, DETDA) (Figure 2

  16. Ruthenium-catalysed synthesis of 2- and 3-substituted quinolines from anilines and 1,3-diols

    Monrad, Rune Nygaard; Madsen, Robert


    A straightforward synthesis of substituted quinolines is described by cyclocondensation of anilines with 1,3-diols. The reaction proceeds in mesitylene solution with catalytic amounts of RuCl3·xH 2O, PBu3 and MgBr2·OEt2. The transformation does not require any stoichiometric additives and only...... produces water and dihydrogen as byproducts. Anilines containing methyl, methoxy and chloro substituents as well as naphthylamines were shown to participate in the heterocyclisation. In the 1,3-diol a substituent was allowed in the 1- or the 2-position giving rise to 2- and 3-substituted quinolines......, respectively. The best results were obtained with 2-alkyl substituted 1,3-diols to afford 3-alkylquinolines. The mechanism is believed to involve dehydrogenation of the 1,3-diol to the 3-hydroxyaldehyde which eliminates water to the corresponding α,β-unsaturated aldehyde. The latter then reacts with anilines...

  17. Characterization of the binding strengths between boronic acids and cis-diol-containing biomolecules by affinity capillary electrophoresis.

    Lü, Chenchen; Liu, Zhen


    The affinity of boronic acids toward cis-diol-containing biomolecules has found wide applications in many fields, such as sensing, separation, drug delivery, and functional materials. A sound understanding of the binding interactions will greatly facilitate exquisite applications of this chemistry. Traditional techniques are associated with some apparent drawbacks, so they are only applicable to a limited range of boronic acids and cis-diol-containing biomolecules. This chapter describes an affinity capillary electrophoresis (ACE) method for the characterization of the binding strengths between boronic acids and cis-diol-containing biomolecules. As compared with existing approaches, such as (11)B NMR, the ACE method exhibits several significant advantages: (1) possibility of simultaneous study of multiple interactions, (2) low requirement on the purity of the binding species, (3) widely applicable to almost all types of cis-diol-containing compounds and boronic acids, and (4) high accuracy and precision.

  18. Kinetic studies of chemical shrinkage and residual stress formation in thermoset epoxy adhesives under confined curing conditions

    Schumann, M.; Geiß, P. L.


    Faultless processing of thermoset polymers in demanding applications requires a profound mastering of the curing kinetics considering both the physico-chemical changes in the transition from the liquid to the solid state and the consolidation of the polymers network in the diffusion controlled curing regime past the gel point. Especially in adhesive joints shrinkage stress occurring at an early state of the curing process under confined conditions is likely to cause defects due to local debonding and thus reduce their strength and durability1. Rheometry is considered the method of choice to investigate the change of elastic and viscous properties in the progress of curing. Drawbacks however relate to experimental challenges in accessing the full range of kinetic parameters of thermoset resins with low initial viscosity from the very beginning of the curing reaction to the post-cure consolidation of the polymer due to the formation of secondary chemical bonds. Therefore the scope of this study was to interrelate rheological data with results from in-situ measurements of the shrinkage stress formation in adhesive joints and with the change of refractive index in the progress of curing. This combination of different methods has shown to be valuable in gaining advanced insight into the kinetics of the curing reaction. The experimental results are based on a multi component thermoset epoxy-amine adhesive.

  19. Liquid crystal alignment in electro-responsive nanostructured thermosetting materials based on block copolymer dispersed liquid crystal

    Tercjak, A; Garcia, I; Mondragon, I [Materials-Technologies Group, Departamento IngenierIa Quimica y M Ambiente, Escuela Politecnica, Universidad PaIs Vasco/Euskal Herriko Unibertsitatea, Plaza Europa 1, E-20018 Donostia-San Sebastian (Spain)], E-mail:, E-mail:


    Novel well-defined nanostructured thermosetting systems were prepared by modification of a diglicydylether of bisphenol-A epoxy resin (DGEBA) with 10 or 15 wt% amphiphilic poly(styrene-b-ethylene oxide) block copolymer (PSEO) and 30 or 40 wt% low molecular weight liquid crystal 4'-(hexyl)-4-biphenyl-carbonitrile (HBC) using m-xylylenediamine (MXDA) as a curing agent. The competition between well-defined nanostructured materials and the ability for alignment of the liquid crystal phase in the materials obtained has been studied by atomic and electrostatic force microscopy, AFM and EFM, respectively. Based on our knowledge, this is the first time that addition of an adequate amount (10 wt%) of a block copolymer to 40 wt% HBC-(DGEBA/MXDA) leads to a well-organized nanostructured thermosetting system (between a hexagonal and worm-like ordered structure), which is also electro-responsive with high rate contrast. This behavior was confirmed using electrostatic force microscopy (EFM), by means of the response of the HBC liquid crystal phase to the voltage applied to the EFM tip. In contrast, though materials containing 15 wt% PSEO and 30 wt% HBC also form a well-defined nanostructured thermosetting system, they do not show such a high contrast between the uncharged and charged surface.

  20. Liquid crystal alignment in electro-responsive nanostructured thermosetting materials based on block copolymer dispersed liquid crystal

    Tercjak, A.; Garcia, I.; Mondragon, I.


    Novel well-defined nanostructured thermosetting systems were prepared by modification of a diglicydylether of bisphenol-A epoxy resin (DGEBA) with 10 or 15 wt% amphiphilic poly(styrene-b-ethylene oxide) block copolymer (PSEO) and 30 or 40 wt% low molecular weight liquid crystal 4'-(hexyl)-4-biphenyl-carbonitrile (HBC) using m-xylylenediamine (MXDA) as a curing agent. The competition between well-defined nanostructured materials and the ability for alignment of the liquid crystal phase in the materials obtained has been studied by atomic and electrostatic force microscopy, AFM and EFM, respectively. Based on our knowledge, this is the first time that addition of an adequate amount (10 wt%) of a block copolymer to 40 wt% HBC-(DGEBA/MXDA) leads to a well-organized nanostructured thermosetting system (between a hexagonal and worm-like ordered structure), which is also electro-responsive with high rate contrast. This behavior was confirmed using electrostatic force microscopy (EFM), by means of the response of the HBC liquid crystal phase to the voltage applied to the EFM tip. In contrast, though materials containing 15 wt% PSEO and 30 wt% HBC also form a well-defined nanostructured thermosetting system, they do not show such a high contrast between the uncharged and charged surface.

  1. 4 Birds 1 Stone to Inhibit 5androstane-3alpha,17beta-diol Conversion to DHT


    Award Number: W81XWH-15-1-0409 TITLE: 4 Birds 1 Stone to Inhibit 5androstane-3alpha,17beta-diol Conversion to DHT PRINCIPAL INVESTIGATOR...SUBTITLE 5a. CONTRACT NUMBER 5b. GRANT NUMBER W81XWH-15-1-04094 Birds 1 Stone to Inhibit 5androstane-3alpha,17beta-diol Conversion to DHT 5c...testicular androgens, testosterone or dihydrotestosterone ( DHT ). Men diagnosed with advanced prostate cancer or failure potentially curative therapy are

  2. Synthesis of cyclic imides from nitriles and diols using hydrogen transfer as a substrate-activating strategy.

    Kim, Jaewoon; Hong, Soon Hyeok


    An atom-economical and versatile method for the synthesis of cyclic imides from nitriles and diols was developed. The method utilizes a Ru-catalyzed transfer-hydrogenation reaction in which the substrates, diols, and nitriles are simultaneously activated into lactones and amines in a redox-neutral manner to afford the corresponding cyclic imides with evolution of H2 gas as the sole byproduct. This operationally simple and catalytic synthetic method provides a sustainable and easily accessible route to cyclic imides.

  3. Asymmetric reduction of α-hydroxy aromatic ketones to chiral aryl vicinal diols using carrot enzymes system

    Xiang Liu; Yi Wang; Hai Yan Gao; Jian He Xu


    Asymmetric reduction of α-hydroxy aromatic ketones was carried out by using carrot enzymes system,yielding corresponding chiral vicinal diols with special functional groups.The optimum reaction conditions were obtained after investigation of various influencing factors.Chiral aryl vicinal diols were produced with good yields and excellent enantiomeric excesses under appropriate conditions,Meanwhile,the steric factors and electronic effects of the substituents on the aromatic ring were shown to have an interesting influence on both yield and enantioselectivity.

  4. Binding of B(a)P diol epoxide to chromosomal histone proteins

    Kootstra, A.; Cronen, M. C.; Slaga, T. J.


    In order to understand how a chemical such as benzo(a)pyrene (B(a)P) exerts its carcinogenic effect, a fundamental knowledge is required concerning the interaction of metabolites of B(a)P with the macromolecules of the eukaryotic cell and the consequences of such interaction at the molecular level. Since current evidence suggests that the DNA is an important target of the ultimate carcinogenic form of B(a)P, the B(a)P diol epoxide, we have studied the binding of B(a)P diol epoxide (anti) to chromatin in vitro, in order to obtain some information about the interaction of this carcinogen with the various components of chromatin.

  5. Voltammetric response of ferroceneboronic acid to diol and phenolic compounds as possible pollutants

    Shigehiro Takahashi; Naoyuki Abiko; Nobuhiro Haraguchi; Hiroyuki Fujita; Eriko Seki; Tetsuya Ono; Kentaro Yoshida; Jun-ichi Anzai


    A voltametric determination of possible organic pollutants such as diol and phenolic compounds in water was studied using ferroceneboronic acid (FBA) as a redox-active marker.A cyclic voltammogram of FBA exhibited a pair of oxidation and reduction peaks at 230 and 170 mV at pH 7.0, respectively, while another pair of redox peaks was observed in the presence of diol or phenolic compounds tested.The results were rationalized based on the formation of boronate esters of FBA with the added compounds.The changes in the redox peak currents were dependent on the concentration of the additives, suggesting a usefulness of FBA in the electrochemical determination of these compounds in water.

  6. Multiple healing in multi-functional polymer composites

    Lafont, U.L.; Van Zeijl, H.; van der Zwaag, S.


    In this work, we investigate the formation of self-healing systems that are able to recover more than once more than one (mechanical or other physical) functionality. To this aim composites were created consisting of a polysulfide thermoset rubber matrix having intrinsic self-healing properties filled with thermally/electrically conductive particles. The cohesion, adhesion and thermal/electrical conduction recovery of these composites are investigated, monitored and quantified as function of ...

  7. Resistance Welding of Thermoplastic Composites: Process and Performance

    Shi, H.


    Compared to thermoset composites, thermoplastic composites are drawing more and more attention by aircraft industries not only due to their excellent material properties but also due to their potentials to reduce cycle time and structure cost by using low-cost manufacturing technologies such as welding. Resistance welding has been regarded as one of the most promising welding techniques owing to the low energy consumption, simplicity of welding operation and capability for scaling up. Previou...

  8. Damage tolerance of continuous fibre composites: material and environmental effects

    Bibo, G.A.; Hogg, P.J. [Queen Mary and Westfield Coll., London (United Kingdom). Dept. of Materials


    Aerospace design philosophies are used to discuss critically, the suitability of composite materials to primary structural applications. The principal issues limiting the use of composites, compression after impact performance and high cost, are examined in terms of material/manufacturing form and environmental conditioning. The material types investigated consist of thermoset and thermoplastic matrix reinforced unidirectional prepreg tape and textile manufactured architectures. (orig.) 141 refs.

  9. Preparation for Supramolecular Complexes of Chiral Diols BDPDD, DMBDPD and BINOL with Some Prochiral Compounds


    Interaction between chiral diols BDPDD, DMBDPD and BINOL with prochiral compounds was examined and some new supramolecular complexes were prepared. It was found that these chiral hosts could include prochiral guests,α,β-unsaturated compounds or piper- azinedione derivatives to give inclusion crystals in different molar ratio. Formations of these supramolecular complexes were characterized by the data of IR and 1H NMR spectra.

  10. One step synthesis of 6-oxo-cholestan-3β,5α-diol

    Voisin, Maud; Silvente-Poirot, Sandrine; Poirot, Marc, E-mail:


    Highlights: • Cholesterol-5,6-epoxides are metabolized into cholestane-3β,5α,6β-triol (CT) in cancer cells. • 6-Oxo-cholestan-3β,5α-diol (OCDO) is a putative metabolite of CT. • The one step syntheses of CT and OCDO from cholesterol are reported. • The one step syntheses of labelled CT and OCDO are reported. - Abstract: Cholesterol metabolism has been recently linked to cancer, highlighting the importance of the characterization of new metabolic pathways in the sterol series. One of these pathways is centered on cholesterol-5,6-epoxides (5,6-ECs). 5,6-ECs can either generate dendrogenin A, a tumor suppressor present in healthy mammalian tissues, or the carcinogenic cholestane-3β,5α,6β-triol (CT) and its putative metabolite 6-oxo-cholestan-3β,5α-diol (OCDO) in tumor cells. We are currently investigating the identification of the enzyme involved in OCDO biosynthesis, which would be highly facilitated by the use of commercially unavailable [{sup 14}C]-cholestane-3β,5α,6β-triol and [{sup 14}C]-6-oxo-cholestan-3β,5α-diol. In the present study we report the one-step synthesis of [{sup 14}C]-cholestane-3β,5α,6β-triol and [{sup 14}C]-6-oxo-cholestan-3β,5α-diol by oxidation of [{sup 14}C]-cholesterol with iodide metaperiodate (HIO{sub 4})

  11. Synthesis and characterization of biodegradable materials: PDLLA-(MAh-Diol)n-PDLLA copolymer

    Jia Chen; Yuan Liang Wang; Mei Na Huang


    The novel biodegradable copolymer PDLLA-(MAH-Diol)n-PDLLA with unsaturated bond was synthesized by copolymerizing lactide and prepolymer, which was prepared by the polycondensation of maleic anhydride and poly(ethylene glycol), using ptoluene sulphonic acid as catalyst. The new copolymer has improved hydrophilicity and flexibility. The structure and properties of the novel polymers were studied by FTIR, NMR, GPC-MALLS and DSC.

  12. Zirconium-doped magnetic microspheres for the selective enrichment of cis-diol-containing ribonucleosides.

    Fan, Hua; Chen, Peihong; Wang, Chaozhan; Wei, Yinmao


    Zirconium-doped magnetic microspheres (Zr-Fe3O4) for the selective enrichment of cis-diol-containing biomolecules were easily synthesized via a one-step hydrothermal method. Characterization of the microspheres revealed that zirconium was successfully doped into the lattice of Fe3O4 at a doping level of 4.0 at%. Zr-Fe3O4 possessed good magnetic properties and high specificity towards cis-diol molecules, as shown using 28 compounds. For ribonucleosides, the adsorbent not only has favorable anti-interferential abilities but also has a high adsorption capacity up to 159.4μmol/g. As an example of a real application, four ribonucleosides in urine were efficiently enriched and detected via magnetic solid-phase extraction coupled with high-performance liquid chromatography. Under the optimized extraction conditions, the detection limits were determined to be between 0.005 and 0.017μg/mL, and the linearities ranged from 0.02 to 5.00μg/mL (R≥0.996) for these analytes. The accuracy of the analytical method was examined by studying the relative recoveries of the analytes in real urine samples, with recoveries varying from 77.8% to 119.6% (RSDs<10.6%, n=6). The results indicate that Zr-Fe3O4 is a suitable adsorbent for the analysis of cis-diol-containing biomolecules in practical applications.

  13. Functional thermoplastics from linear diols and diisocyanates produced entirely from renewable lipid sources.

    Hojabri, Leila; Kong, Xiaohua; Narine, Suresh S


    An unsaturated terminal diol, 1,18-octadec-9-endiol (ODEDO), and a saturated terminal diol, 1,9-nonanediol (NDO), were synthesized from oleic acid. The feasibility of utilizing these new diols for the production of thermoplastic polyurethanes (TPUs) was demonstrated by reacting them with a fatty acid-derived diisocyanate, 1,7-heptamethylene diisocyanate (HPMDI), and a commercially available petroleum-derived diisocyanate, 1,6-hexamethylene diisocyanate (HDI). One type of phase structure was obtained for both TPUs in this study, owing to the similarity between the ODEDO and NDO molecular structure. In addition, double yielding behavior (observed for the first time in polyurethanes) was observed in the stress-strain curves for both TPU systems. Compared to the TPUs prepared from HDI, the totally biobased TPUs (ODEDO-NDO-HPDMI) demonstrated comparable properties within acceptable tolerances, considering the impacts on physical properties due to the odd-even effect introduced by the HPDMI. This work is the first that establishes the production of linear thermoplastic polyurethanes entirely from lipid feedstock.


    Gamper, Howard B.; Yokota, Hisao A.; Bartholomew, James C.


    SV40 minichromosomes were reacted with (+)7{beta},8{alpha}-dihydroxy-9{alpha},10{alpha}-epoxy- 7,8,9,10-tetrahydrobenzo[a]pyrene (BaP diol epoxide). Low levels of modification (< 5 DNA adducts/minichromosome) did not detectably alter the structure of the minichromosomes but high levels (> 200 DNA adducts/minichromosome) led to extensive fragmentation. Relative to naked SV40 DNA BaP diol epoxide induced alkylation and strand scission of minichromosomal DNA was reduced or enhanced by factors of 1.5 and 2.0, respectively. The reduction in covalent binding was attributed to the presence of histones, which competed with DNA for the hydrocarbon and reduced the probability of BaP diol epoxide intercalation by tightening the helix. The enhancement of strand scission was probably due to the catalytic effect of histones on the rate of S-elimination at apurinic sites, although an altered adduct profile or the presence of a repair endonuclease were not excluded. Staphylococcal nuclease digestion indicated that BaP dial epoxide randomly alkylated the minichromosomal DNA. This is in contrast to studies with cellular chromatin where internucleosomal DNA was preferentially modified. Differences in the minichromosomal protein complement were responsible for this altered susceptibility.

  15. Multiple welding of long fiber epoxy vitrimer composites.

    Chabert, Erwan; Vial, Jérôme; Cauchois, Jean-Pierre; Mihaluta, Marius; Tournilhac, François


    Vitrimers appear as a new class of polymers that exhibit mechanical strength and are insoluble even at high temperatures, like thermosets, and yet, like thermoplastics, they are heat processable, recyclable and weldable. The question arises whether this welding property is maintained in composite materials made of more than 50 vol% of reinforcing fibers. In this paper, we quantitatively analyze the bond strength of epoxy vitrimer-based composite plates made by resin transfer molding and compare them to their non-vitrimer counterparts made of a standard thermoset epoxy. It is demonstrated that only epoxy vitrimer samples show substantial bond strength and the ability to be repeatedly welded thanks to the exchange reactions, which promote improved surface conformity and chemical bonding between the adherands at the joint interface. This opens the way towards joining composite parts without adhesives nor mechanical fasteners.

  16. Composite Structures and Materials Research at NASA Langley Research Center

    Starnes, James H., Jr.; Dexter, H. Benson; Johnston, Norman J.; Ambur, Damodar R.; Cano, roberto J.


    A summary of recent composite structures and materials research at NASA Langley Research Center is presented. Fabrication research to develop low-cost automated robotic fabrication procedures for thermosetting and thermoplastic composite materials, and low-cost liquid molding processes for preformed textile materials is described. Robotic fabrication procedures discussed include ply-by-ply, cure-on-the-fly heated placement head and out-of-autoclave electron-beam cure methods for tow and tape thermosetting and thermoplastic materials. Liquid molding fabrication processes described include Resin Film Infusion (RFI), Resin Transfer Molding (RTM) and Vacuum-Assisted Resin Transfer Molding (VARTM). Results for a full-scale composite wing box are summarized to identify the performance of materials and structures fabricated with these low-cost fabrication methods.

  17. Thermosetting polymer for dynamic nuclear polarization: Solidification of an epoxy resin mixture including TEMPO

    Noda, Yohei, E-mail: [Quantum Beam Science Centre, Sector of Nuclear Science Research, Japan Atomic Energy Agency, Shirakata-Shirane, Tokai, Ibaraki 319-1195 (Japan); Kumada, Takayuki [Quantum Beam Science Centre, Sector of Nuclear Science Research, Kansai Photon Science Institute, Japan Atomic Energy Agency, Kizugawa, Kyoto 619-0215 (Japan); Yamaguchi, Daisuke; Shamoto, Shin-ichi [Quantum Beam Science Centre, Sector of Nuclear Science Research, Japan Atomic Energy Agency, Shirakata-Shirane, Tokai, Ibaraki 319-1195 (Japan)


    We investigated the dynamic nuclear polarization (DNP) of typical thermosetting polymers (two-component type epoxy resins; Araldite{sup ®} Standard or Araldite{sup ®} Rapid) doped with a (2,2,6,6-tetramethylpiperidine-1-yl)oxy (TEMPO) radical. The doping process was developed by carefully considering the decomposition of TEMPO during the solidification of the epoxy resin. The TEMPO electron spin in each two-component paste decayed slowly, which was favorable for our study. Furthermore, despite the dissolved TEMPO, the mixture of the two-component paste successfully solidified. With the resulting TEMPO-doped epoxy-resin samples, DNP experiments at 1.2 K and 3.35 T indicated a magnitude of a proton-spin polarization up to 39%. This polarization is similar to that (35%) obtained for TEMPO-doped polystyrene (PS), which is often used as a standard sample for DNP. To combine this solidification of TEMPO-including mixture with a resin-casting technique enables a creation of polymeric target materials with a precise and complex structure.

  18. Tannic Acid as a Bio-Based Modifier of Epoxy/Anhydride Thermosets

    Xiaoma Fei


    Full Text Available Toughening an epoxy resin by bio-based modifiers without trade-offs in its modulus, mechanical strength, and other properties is still a big challenge. This paper presents an approach to modify epoxy resin with tannic acid (TA as a bio-based feedstock. Carboxylic acid-modified tannic acid (TA–COOH was first prepared through a simple esterification between TA and methylhexahydrophthalic anhydride, and then used as a modifier for the epoxy/anhydride curing system. Owing to the chemical modification, TA–COOH could easily disperse in epoxy resin and showed adequate interface interaction between TA–COOH and epoxy matrix, in avoid of phase separation. The use of TA–COOH in different proportions as modifier of epoxy/anhydride thermosets was studied. The results showed that TA–COOH could significantly improve the toughness with a great increase in impact strength under a low loading amount. Moreover, the addition of TA–COOH also simultaneously improved the tensile strength, elongation at break and glass transition temperature. The toughening and reinforcing mechanism was studied by scanning electron microscopy (SEM, dynamic mechanical analysis (DMA and thermal mechanical analysis (TMA, which should be owned to the synergistic effect of good interface interaction, aromatic structure, decreasing of cross linking density and increasing of free volume. This approach allows us to utilize the renewable tannic acid as an effective modifier for epoxy resin with good mechanical and thermal properties.

  19. Thermoset nanocomposites from two-component waterborne polyurethanes and cellulose whiskers.

    Wu, Guo-min; Chen, Jian; Huo, Shu-ping; Liu, Gui-feng; Kong, Zhen-wu


    We prepared thermoset nancomposites from biomass-based two-component waterborne polyurethane (2K-WPU) and cellulose namowhiskers (CNWs). Due to the formation of hydrogen bonds, the viscosity of 2K-WPU dispersion was found to be increased with the addition of CNWs. SEM images showed "sea-island structure" corresponding to the microphase separation between CNWs nano-filler and the 2K-WPU matrix. The α-relaxation temperature (Tα) and glass transition temperature (Tg) increased with the increase of CNWs content, which was due to the formation of a rigid CNWs nano-phase acting as crosslinking points in the 2K-WPU matrix. Mechanical properties from tensile test showed Young's modulus and tensile strength of 2K-WPU/CNWs nanocomposites were reinforced by the addition of CNWs. Thermo-stability of 2K-WPU/CNWs nanocomposites decreased slightly with the increase of CNWs content, which could be attributed to the increased thermal conductivity of the material after adding CNWs. Copyright © 2014 Elsevier Ltd. All rights reserved.

  20. Isothermal recovery response and constitutive model of thermoset shape memory polymers

    Tan, Huifeng; Zhou, Tao; Liu, Yuyan; Lan, Lan


    Deformation recovery capability is one of the important indexes to examination shape memory effect of the shape memory polymers (SMPs). And the shape memory characteristic of SMPs is closely related to different phase states and mechanical properties above and below the glass transition temperature (Tg). In this paper, we investigated the strain recovery response of a thermoset shape memory epoxy resin modified by polyurethane (PU) through uniaxial compression experiments under various isothermal conditions and strain rates and developed a "three-phase" constitutive model based on phase transition concept, which including stationary phase, active phase and frozen phase. This model established the mutual transformation relationships between frozen phase and active phase of SMPs by introducing temperature switch function, which presents the stain storage and release process of SMPs under loading and changing temperature environment. Besides, the proposed model represents the SMPs deformation process of viscous hysteresis response by employing the rheological elements description of the three phases. The numerical results agree very well with experiment results of stress-strain response curve of isothermal compression/unloading test, which validated this model can predict the finite deformation behavior of SMPs.

  1. Thermoset nanocomposites from waterborne bio-based epoxy resin and cellulose nanowhiskers.

    Wu, Guo-min; Liu, Di; Liu, Gui-feng; Chen, Jian; Huo, Shu-ping; Kong, Zhen-wu


    Thermoset nanocomposites were prepared from a waterborne terpene-maleic ester type epoxy resin (WTME) and cellulose nanowhiskers (CNWs). The curing behaviors of WTME/CNWs nanocomposites were measured with rotational rheometer. The results show that the storage modulus (G') of WTME/CNWs nanocomposites increased with the increase of CNWs content. Observations by scanning electron microscopy (SEM) demonstrate that the incorporation of CNWs in WTME matrix caused microphase separation and destroyed the compactness of the matrix. This effect leads to the glass transition temperatures (Tg) of WTME/CNWs nanocomposites slightly decrease with the increase of CNWs content, which were confirmed by both DSC and DMA tests. The mechanical properties of WTME/CNWs nanocomposites were investigated by tensile testing. The Yong's modulus (E) and tensile strength (σb) of the nanocomposites were significantly reinforced by the addition of CNWs. These results indicate that CNWs exhibit excellent reinforcement effect on WTME matrix, due to the formation and increase of interfacial interaction by hydrogen bonds between CNWs nano-filler and the WTME matrix.

  2. Viscoelastic and Mechanical Properties of Thermoset PMR-type Polyimide-Clay Nanocomposites

    Abdalla, Mohamed O.; Dean, Derrick; Campbell, Sandi


    High temperature thermoset polyimide-clay nanocomposites were prepared by blending 2.5 and 5 wt% of an unmodified Na(+-) montmorillonite (PGV) and two organically modified FGV (PGVCl0COOH, PGVC12) with a methanol solution of PMR-15 precursor. The methanol facilitated the dispersal of the unmodified clay. Dynamic mechanical analysis results showed a significant increase in the thermomechanical properties (E' and E") of 2.5 wt% clay loaded nanocomposites in comparison with the neat polyimide. Higher glass transition temperatures were observed for 2.5 wt% nanocomposites compared to the neat polyimide. Flexural properties measurements for the 2.5 wt% nanocomposites showed a significant improvement in the modulus and strength, with no loss in elongation. This trend was not observed for the 5 wt% nanocomposites. An improvement in the CTE was observed for the PGV/PMR-15 nanocomposites, while a decrease was observed for the organically modified samples. This was attributed to potential variations in the interface caused by modifier degradation.

  3. In vitro metabolism of benzo[a]pyrene-7,8-dihydrodiol and dibenzo[def,p]chrysene-11,12 diol in rodent and human hepatic microsomes

    Smith, Jordan N.; Mehinagic, Denis; Nag, Subhasree; Crowell, Susan R.; Corley, Richard A.


    Polycyclic aromatic hydrocarbons (PAHs) are contaminants that are ubiquitously found in the environment, produced through combustion of organic matter or petrochemicals, and many of which are procarcinogens. The prototypic PAH, benzo[a]pyrene (B[a]P) and the highly carcinogenic dibenzo[def,p]chrysene (DBC) are metabolically activated by isoforms of the P450 enzyme superfamily producing benzo[a]pyrene-7,8-dihydrodiol (B[a]P diol), dibenzo[def,p]chrysene-11,12 diol (DBC diol). Each of these diols can be further metabolized by cytochrome P450 enzymes to highly reactive diol-epoxide metabolites that readily react with DNA or by phase II conjugation facilitating excretion. To complement prior in vitro metabolism studies with parent B[a]P and DBC, both phase I metabolism and phase II glucuronidation of B[a]P diol and DBC diol were measured in hepatic microsomes from female B6129SF1/J mice, male Sprague-Dawley rats, and female humans. Metabolic parameters, including intrinsic clearance and Michaelis-Menten kinetics were calculated from substrate depletion data. Mice and rats demonstrated similar B[a]P diol phase I metabolic rates. Compared to rodents, human phase I metabolism of B[a]P diol demonstrated lower overall metabolic capacity, lower intrinsic clearance at higher substrate concentrations (>0.14 µM), and higher intrinsic clearance at lower substrate concentrations (<0.07 µM). Rates of DBC diol metabolism did not saturate in mice or humans and were highest overall in mice. Higher affinity constants and lower capacities were observed for DBC diol glucuronidation compared to B[a]P diol glucuronidation; however, intrinsic clearance values for these compounds were consistent within each species. Kinetic parameters reported here will be used to extend physiologically based pharmacokinetic (PBPK) models to include the disposition of B[a]P and DBC metabolites in animal models and humans to support future human health risk assessments.

  4. Failure Plane Orientations for Fiber Composites

    Christensen, R.M.; DeTeresa, S.J.


    Using a recently developed failure theory for transversely isotropic fiber composites, it is shown how the orientation of the failure surface can be determined for transverse tension and compression. Experimental data on failure surface orientations have been obtained for four carbon fiber composite systems based on both thermoplastic and thermosetting matrix materials. Average compression failure planes for the different composite materials were measured to range from 31{sup o} to 38{sup o} from the load axis. Reasonable agreement was obtained between these measured angles and those predicted from application of the new failure theory.

  5. Composition


    Memory Pieces are open compositions to be realised solo by an improvising musicians. See more about my composition practise in the entry "Composition - General Introduction". Caution: streaming the sound files will in some cases only provide a few minutes' sample. Please DOWNLOAD them to hear them...

  6. Composition

    Bergstrøm-Nielsen, Carl


    New Year is an open composition to be realised by improvising musicians. It is included in "From the Danish Seasons" (see under this title). See more about my composition practise in the entry "Composition - General Introduction". This work is licensed under a Creative Commons "by-nc" License. You...

  7. Composition

    Bergstrøm-Nielsen, Carl


    Strategies are open compositions to be realised by improvising musicians. See more about my composition practise in the entry "Composition - General Introduction". Caution: streaming the sound files will in some cases only provide a few minutes' sample. Please DOWNLOAD them to hear them in full...

  8. Biological responses of human gingival fibroblasts (HGFs in an innovative co-culture model with Streptococcus mitis to thermosets coated with a silver polysaccharide antimicrobial system.

    Silvia Sancilio

    Full Text Available This study sought to evaluate the in vitro biological response of human gingival fibroblasts (HGFs co-coltured with Streptococcus mitis to bisphenol A glycidylmethacrylate/triethylene glycol dimethacrylate (BisGMA/TEGDMA thermosets coated with Chitlac-nAg, a nanocomposite system with antimicrobial properties. To avoid bacterial adhesion to dental devices and to reduce cytotoxicity against eukaryotic cells, we coated BisGMA/TEGDMA methacrylic thermosets with a new material, Chitlac-nAg, formed by stabilizing silver nanoparticles, which have well-known antimicrobial properties, with a polyelectrolyte solution containing Chitlac. Cytotoxicity, cell morphology, cell migration and inflammatory interleukine-6 (IL-6 and prostaglandin E2 (PGE2 secretion were evaluated. Our results showed that the cytotoxicity exerted on HGFs by our nanocomposite material was absent in our co-culture model, where fibroblasts are able to adhere and migrate. After 24 h thermosets coated with Chitlac as well as those coated with Chitlac-nAg exerted a minimal cytotoxic effect on HGFs, while after 48 h LDH release rises up 20%. Moreover the presence of S. mitis reduced this release in a greater amount with Chitlac-nAg coated thermosets. The secretion of IL-6 was significant in both Chitlac and Chitlac-nAg coated thermosets, but PGE2 production was minimal, suggesting that the IL-6 production was not related to an inflammatory response. Co-culture and the addiction of saliva did not influence IL-6 and PGE2 secretion. Data obtained in the present work suggest that Chitlac n-Ag coated thermosets could significantly improve the success rates of restorative dentistry, since they limit bacterial adhesion and are not toxic to HGFs.

  9. Solubility and thermodynamic behavior of vanillin in propane-1,2-diol+water cosolvent mixtures at different temperatures.

    Shakeel, Faiyaz; Haq, Nazrul; Siddiqui, Nasir A; Alanazi, Fars K; Alsarra, Ibrahim A


    The solubilities of bioactive compound vanillin were measured in various propane-1,2-diol+water cosolvent mixtures at T=(298-318)K and p=0.1 MPa. The experimental solubility of crystalline vanillin was determined and correlated with calculated solubility. The results showed good correlation of experimental solubilities of crystalline vanillin with calculated ones. The mole fraction solubility of crystalline vanillin was recorded highest in pure propane-1,2-diol (7.06×10(-2) at 298 K) and lowest in pure water (1.25×10(-3) at 298 K) over the entire temperature range investigated. Thermodynamic behavior of vanillin in various propane-1,2-diol+water cosolvent mixtures was evaluated by Van't Hoff and Krug analysis. The results showed an endothermic, spontaneous and an entropy-driven dissolution of crystalline vanillin in all propane-1,2-diol+water cosolvent mixtures. Based on solubility data of this work, vanillin has been considered as soluble in water and freely soluble in propane-1,2-diol.

  10. Impact of large aggregated uricases and PEG diol on accelerated blood clearance of PEGylated canine uricase.

    Chun Zhang

    Full Text Available BACKGROUND: Uricase has proven therapeutic value in treating hyperuricemia but sufficient reduction of its immunogenicity may be the largest obstacle to its chronic use. In this study, canine uricase was modified with 5 kDa mPEG-SPA and the impact of large aggregated uricases and cross-linked conjugates induced by difunctional PEG diol on immunogenicity was investigated. METHODS AND FINDINGS: Recombinant canine uricase was first expressed and purified to homogeneity. Source 15Q anion-exchange chromatography was used to separate tetrameric and aggregated uricase prior to pegylation, while DEAE anion-exchange chromatography was used to remove Di-acid PEG (precursor of PEG diol from unfractionated 5 kDa mPEG-propionic acid. Tetrameric and aggregated uricases were separately modified with the purified mPEG-SPA. In addition, tetrameric uricases was modified with unfractionated mPEG-SPA, resulting in three types of 5 kDa mPEG-SPA modified uricase. The conjugate size was evaluated by dynamic light scattering and transmission electron microscope. The influence of differently PEGylated uricases on pharmacokinetics and immunogenicity were evaluated in vivo. The accelerated blood clearance (ABC phenomenon previously identified for PEGylated liposomes occurred in rats injected with PEGylated uricase aggregates. Anti-PEG IgM antibodies, rather than neutralizing antibodies, were found to mediate the ABC. CONCLUSIONS: The size of conjugates is important for triggering such phenomena and we speculate that 40-60 nm is the lower size limit that can trigger ABC. Removal of the uricase aggregates and the PEG diol contaminant and modifying with small PEG reagents enabled ABC to be successfully avoided and sufficient reduction in the immunogenicity of 5 kDa mPEG-modified tetrameric canine uricase.

  11. Improvement of thermal properties and flame retardancy of epoxy-amine thermosets by introducing bisphenol containing azomethine moiety


    Full Text Available A novel bisphenol 1, 4'-bis{4-[(4-hydroxy phenyliminomethylidene] phenoxy} benzene (BHPB, which contains azomethine moiety and flexible aromatic ether linkage, was synthesized and introduced into the curing system composed of diglycidyl ether of bisphenol A (DGEBA and diamine. The curing behavior of DGEBA/diamine changed dramatically due to the introduction of BHPB. The resultant epoxy thermosets containing BHPB had high Tgs (127-160 °C, high Td, 5% (>=330°C and high integral procedure decomposition temperature (IPDT values (662-1230°C and good flame retardancy for their high Limited Oxygen Index (LOI values (above 29.5.


    Sticker, Drago; Rothbauer, Mario; Ehgartner, Josef


    The precise control of the oxygen concentration in a cellular environment allows the study of cells under physiologically relevant conditions. This work reports on a novel method for the generation of reduced dissolved oxygen concentrations in microfluidic chambers for cell- and organ......-on-chip applications. Using a thermoset polymeric material (OSTEMERTM), which effectively scavenges dissolved oxygen (DO), microfluidic devices have been fabricated where oxygen was rapidly depleted from the microfluidic chamber. It is shown that hypoxic and anaerobic conditions can be generated through the inherent...

  13. Synthesis of cyclic carbonates from diols and CO2 catalyzed by carbenes.

    Bobbink, Felix D; Gruszka, Weronika; Hulla, Martin; Das, Shoubhik; Dyson, Paul J


    The synthesis of cyclic carbonates from epoxides and CO2 is a well-established reaction, whereas the synthesis of cyclic carbonates from diols and CO2 is considerably more challenging, and few efficient catalysts are available. Here, we describe heterocyclic carbene catalysts, including one derived from a cheap and efficient thiazolium salt, for this latter reaction. The reaction proceeds at atmospheric pressure in the presence of an alkyl halide and Cs2CO3. Reaction mechanisms for the transformations involved are also proposed.

  14. 2-[(5-Chloro-2-oxidobenzylideneazaniumyl]-2-methylpropane-1,3-diol

    Dong-Yue Wang


    Full Text Available The title compound, C11H14ClNO3, was prepared by the condensation of equimolar quantities of 5-chlorosalicylaldehyde and 2-amino-2-methylpropane-1,3-diol in methanol. In the crystal, it exists in the zwitterionic form, with nominal proton transfer from the phenol group to the imine N atom. This results in the formation of an intramolecular N—H...O hydrogen bond, which generates an S(6 ring. Intermolecular O—H...O hydrogen bonds arise from the hydroxy groups, forming (001 sheets.

  15. Ultrasonicated Synthesis of N-Benzyl-2,3-substituted Morpholines, via the Mitsunobu Diol Cyclisation

    B. Jayachandra Reddy


    Full Text Available A facile five step synthesis of N-benzyl-2,3-substituted morpholines (i-iii was performed. The key steps were microwave assisted Friedel-crafts acylation and diol cyclization carried out via an ultra sonication of Mitsunobu reaction using DEAD (diethylazodicarboxylate, TPP in THF for 1 h. The morpholine products were generated as diasteriomers (ii andiii which has been separated by the column chromatography to good yield. The structure of compounds (i-iii has been characterized by the spectral and chemical studies.

  16. A Facile and Efficient Synthesis of (15R)-Latanoprost from Chiral Precursor Corey Lactone Diol

    K Vijendhar; B Srinivas; Sathyanarayana Boodida


    An efficient asymmetric synthetic route for the synthesis of anti-glaucoma agent, (15R)-latanoprost using Corey lactone diol as chiral substrate under Swern oxidation, allylic reduction and Wittig reaction conditions has been developed. In this method, reduction of keto and alkene functional groups has been achieved in a single step using low cost catalyst NiCl2/NaBH4 in methanol. This new synthetic protocol is a good alternative for the synthesis of latanoprost with high stereo selectivity and improved yield.

  17. Exploiting Acid Phosphatases in the Synthesis of Phosphorylated Monoalcohols and Diols

    Tasnádi, Gábor; Lukesch, Michael; Zechner, Michaela; Jud, Wolfgang; Hall, Mélanie; Ditrich, Klaus; Baldenius, Kai; Hartog, Aloysius F.; Wever, Ron


    Abstract A set of phosphatases was evaluated for their potential to catalyze the regio‐ and stereoselective phosphorylation of alcohols using a high‐energy inorganic phosphate donor, such as di‐, tri‐ and polyphosphate. Parameters such as type and amount of phosphate donor and pH of the reaction were investigated in order to minimize the thermodynamically favored hydrolysis of the phosphate donor and the formed phosphate ester. Diols were monophosphorylated with high selectivities. This biocatalytic phosphorylation method provides selectively activated and/or protected synthetic intermediates for further chemical and/or enzymatic transformations and is applicable to a large scale (6.86 g) in a flow setup with immobilized phosphatase.

  18. Preparation of Rh[16aneS4-diol](211)At and Ir[16aneS4-diol](211)At complexes as potential precursors for astatine radiopharmaceuticals. Part I: Synthesis.

    Pruszyński, Marek; Bilewicz, Aleksander; Zalutsky, Michael R


    The goal of this study was to evaluate a new approach that can be applied for labeling biomolecules with (211)At. Many astatine compounds that have been synthesized are unstable in vivo, providing motivation for seeking different (211)At labeling strategies. The approach evaluated in this study was to attach astatide anions to soft metal cations, which are also complexed by a bifunctional ligand. Ultimately, this complex could in principle be subsequently conjugated to a biomolecule with the proper selection of ligand functionality. We report here the attachment of (211)At(-) and *I(-) (*I = (131)I or (125)I) anions to the soft metal cations Rh(III) and Ir(III), which are complexed by the 1,5,9,13-tetrathiacyclohexadecane-3,11-diol (16aneS4-diol) ligand. Radioactive *I(-) anions were used for preliminary studies directed at the optimization of reaction conditions and to provide a baseline for comparison of results with (211)At. Four complexes Rh[16aneS4-diol]*I/(211)At and Ir[16aneS4-diol]*I/(211)At were synthesized in high yield in a one-step procedure, and the products were characterized mainly by paper electrophoresis and reversed-phase HPLC. The influences of time and temperature of heating and concentrations of metal cations and sulfur ligand 16aneS4-diol, as well as pH on the reaction yields were determined. Yields of about 80% were obtained when the quantities of Rh(III) or Ir(III) cations and 16aneS4-diol ligand in the solutions were 62.5 nmol and 250 nmol, respectively, and the pH ranged 3.0-4.0. Syntheses required heating for 1-1.5 h at 75-80 degrees C. The influence of microwave heating on the time and completeness of the complexation reaction was evaluated and compared with the conventional method of heating in an oil bath. Microwave synthesis accelerates reactions significantly. With microwave heating, yields of about 75% for Rh[16aneS4-diol](131)I and Ir[16aneS4-diol](131)I complexes were obtained after only 20 min exposure of the reaction mixtures to

  19. Correlation analysis of reactivity in the oxidation of some organic diols by tripropylammonium fluorochromate in non-aqueous media

    S. Sheik Mansoor


    Full Text Available The kinetics of oxidation of some organic diols by tripropylammonium fluorochromate (TriPAFC have been studied in dimethylsulfoxide (DMSO. The main product of oxidation is the corresponding hydroxy aldehydes. The reaction is first order with respect to TriPAFC and exhibited Michaelis-Menten type kinetics with respect to organic diols. The reaction is catalyzed by hydrogen ions. The hydrogen ion dependence has the form: kobs = a + b[H+]. Various thermodynamic parameters for the oxidation have been reported and discussed along with the validity of isokinetic relationship. Oxidation of diols was studied in 18 different organic solvents. The rate data are showing satisfactory correlation with Kamlet–Taft solvotochromic parameters (α, β and π∗. A suitable mechanism of oxidation has been proposed.

  20. An asymmetric route to 2,3-epoxy-syn-1,4-cyclohexane diol derivatives using ring closing metathesis (RCM)

    Soumitra Maity; Subrata Ghosh


    An asymmetric route for the synthesis of highly functionalized 2,3-epoxy-syn-1,4-cyclohexane diol derivatives present in some polyketide natural products has been developed. The key step involves RCM of an appropriately constructed 1,7-dienol derived from D-mannitol to cyclohexane-1,4-diol followed by its stereoselective epoxidation.

  1. Methylene acetal formation from 1,2- and 1,3-diols using an O,S-acetal, 1,3-dibromo-5,5-dimethylhydantoin, and BHT.

    Maegawa, Tomohiro; Koutani, Yasuyuki; Otake, Kazuki; Fujioka, Hiromichi


    A mild and efficient method for formation of methylene acetals from 1,2- and 1,3-diols using methoxymethylphenylsulfide, 1,3-dibromo-5,5-dimethylhydantoin (DBDMH), and dibutylhydroxytoluene (BHT) is described. The use of BHT in this process suppresses side reactions and enables high-yielding formation of methylene acetals of various diols, including carbohydrate-type substrates.

  2. Synthesis of Hydroxylated Sterols(Ⅱ)--Synthesis of 24-Methylenecholest-4-en-3β,6α-diol


    @@ In our study on the soft coral,Alcyonium patagonicum,a new hydroxylated sterol,24-methylenecholest-4-en-3β,6α-diol(1) exhibiting a potent activity to murine leukemia cells(IC50=1 μg/mL) has been isolated[1] and synthesized[2,3].As a part of our studies on the relationship between the chemical structure and the biological activity of the hydroxylated sterols,the synthesis of 24-methylenecholest-4-en-3β,6α-diol(2) is reported here.

  3. 6-Methyl-1,3,5-triazine-2,4-diamine butane-1,4-diol monosolvate

    Rajni M. Bhardwaj


    Full Text Available The title co-crystal, C4H7N5·C4H10O2, crystallizes with one molecule of 6-methyl-1,3,5-triazine-2,4-diamine (DMT and one molecule of butane-1,4-diol in the asymmetric unit. The DMT molecules form ribbons involving centrosymmetric R22(8 dimer motifs between DMT molecules along the c-axis direction. These ribbons are further hydrogen bonded to each other through butane-1,4-diol, forming sheets parallel to (121.

  4. Fluorinated Boronic Acid-Appended Bipyridinium Salts for Diol Recognition and Discrimination via (19)F NMR Barcodes.

    Axthelm, Jörg; Görls, Helmar; Schubert, Ulrich S; Schiller, Alexander


    Fluorinated boronic acid-appended benzyl bipyridinium salts, derived from 4,4'-, 3,4'-, and 3,3'-bipyridines, were synthesized and used to detect and differentiate diol-containing analytes at physiological conditions via (19)F NMR spectroscopy. An array of three water-soluble boronic acid receptors in combination with (19)F NMR spectroscopy discriminates nine diol-containing bioanalytes--catechol, dopamine, fructose, glucose, glucose-1-phosphate, glucose-6-phosphate, galactose, lactose, and sucrose--at low mM concentrations. Characteristic (19)F NMR fingerprints are interpreted as two-dimensional barcodes without the need of multivariate analysis techniques.

  5. The glass transition in cured epoxy thermosets: A comparative molecular dynamics study in coarse-grained and atomistic resolution

    Langeloth, Michael; Böhm, Michael C.; Müller-Plathe, Florian [Eduard-Zintl-Institut für Anorganische und Physikalische Chemie and Center of Smart Interfaces, Technische Universität Darmstadt, Alarich Weiss Straße 4, D-64287 Darmstadt (Germany); Sugii, Taisuke, E-mail: [Center for Technology Innovation – Mechanical Engineering, Research & Development Group, Hitachi, Ltd., 832-2, Horiguchi, Hitachinaka, Ibaraki 312-0034 (Japan)


    We investigate the volumetric glass transition temperature T{sub g} in epoxy thermosets by means of molecular dynamics simulations. The epoxy thermosets consist of the resin bisphenol A diglycidyl ether and the hardener diethylenetriamine. A structure based coarse-grained (CG) force field has been derived using iterative Boltzmann inversion in order to facilitate simulations of larger length scales. We observe that T{sub g} increases clearly with the degree of cross-linking for all-atomistic (AA) and CG simulations. The transition T{sub g} in CG simulations of uncured mixtures is much lower than in AA-simulations due to the soft nature of the CG potentials, but increases all the more with the formation of rigid cross-links. Additional simulations of the CG mixtures in contact with a surface show the existence of an interphase region of about 3 nm thickness in which the network properties deviate significantly from the bulk. In accordance to experimental studies, we observe that T{sub g} is reduced in this interphase region and gradually increases to its bulk value with distance from the surface. The present study shows that the glass transition is a local phenomenon that depends on the network structure in the immediate environment.

  6. Instrumented thick-walled tube method for measuring thermal pressure in fluids and isotropic stresses in thermosetting resins

    Merzlyakov, Mikhail; Simon, Sindee L.; McKenna, Gregory B.


    We have developed a method for measuring the thermal pressure coefficient and cure-induced and thermally induced stresses based on an instrumented thick-walled tube vessel. The device has been demonstrated at pressures up to 330 MPa and temperatures to 300 °C. The method uses a sealed stainless steel thick-walled tube to impose three-dimensional isotropic constraints. The tube is instrumented with strain gauges in hoop and in axial directions and can be used in open or closed configurations. By making measurements of the isotropic stresses as a function of temperature, the method allows determination of the thermal pressure coefficient in both the glassy and rubbery (or liquid) states. The method also can be used to measure isotropic stress development in thermosetting resins during cure and subsequent thermal cycling. Experimental results are presented for sucrose benzoate, di-2-ethylhexylsebacate, and an epoxy resin. The current report shows that the method provides reliable estimates for the thermal pressure coefficient. The thermal pressure coefficient is determined with resolution on the order of 10kPa/K. Among advantages of the method is that the tubes are reusable, even when measurements are made for cure response of thermosetting resins.

  7. Composition

    Bergstrøm-Nielsen, Carl


    Cue Rondo is an open composition to be realised by improvising musicians. See more about my composition practise in the entry "Composition - General Introduction". Caution: streaming the sound/video files will in some cases only provide a few minutes' sample, or the visuals will not appear at all....... Please DOWNLOAD them to see/hear them in full length! This work is licensed under a Creative Commons "by-nc" License. You may for non-commercial purposes use and distribute it, performance instructions as well as specially designated recordings, as long as the author is mentioned. Please see http...

  8. Nickel coated graphite fiber conductive composites

    Evans, R.E.; Hall, D.E.; Luxon, B.A.


    Nickel coated graphite (NCG) fiber, consisting of a thin continuous plating of high purity nickel over an aerospace-grade graphite core, offers performance added features by combining the lightweight and high structural reinforcement of graphite fiber with the thermal and electrical conductivity of nickel. These NCG filaments, which are composite constructions in their own right, can be processed and impregnated with thermosetting or thermoplastic resins in the same manner that graphite fiber tows are processed and impregnated to produce roving, tape or fabric prepreg. Therefore, NCG fibers can be readily integrated into structural laminate assemblies using established composites-manufacturing practices.

  9. Carbon fiber reinforced thermoplastic composites for future automotive applications

    Friedrich, K.


    After a brief introduction to polymer composite properties and markets, the state of the art activities in the field of manufacturing of advanced composites for automotive applications are elucidated. These include (a) long fiber reinforced thermoplastics (LFT) for secondary automotive components, and (b) continuous carbon fiber reinforced thermosetting composites for car body applications. It is followed by future possibilities of carbon fiber reinforced thermoplastic composites for e.g. (i) crash elements, (ii) racing car seats, and (iii) production and recycling of automotive fenders.

  10. In vitro metabolism of benzo[a]pyrene-7,8-dihydrodiol and dibenzo[def,p]chrysene-11,12 diol in rodent and human hepatic microsomes.

    Smith, Jordan N; Mehinagic, Denis; Nag, Subhasree; Crowell, Susan R; Corley, Richard A


    Polycyclic aromatic hydrocarbons (PAHs) are contaminants that are ubiquitously found in the environment, produced through combustion of organic matter or petrochemicals, and many of which are procarcinogens. The prototypic PAH, benzo[a]pyrene (B[a]P) and the highly carcinogenic dibenzo[def,p]chrysene (DBC) are metabolically activated by isoforms of the P450 enzyme superfamily producing benzo[a]pyrene-7,8-dihydrodiol (B[a]P diol), dibenzo[def,p]chrysene-11,12 diol (DBC diol). Each of these diols can be further metabolized by cytochrome P450 enzymes to highly reactive diol-epoxide metabolites that readily react with DNA or by phase II conjugation facilitating excretion. To complement prior in vitro metabolism studies with parent B[a]P and DBC, both phase I metabolism and phase II glucuronidation of B[a]P diol and DBC diol were measured in hepatic microsomes from female B6129SF1/J mice, male Sprague-Dawley rats, and female humans. Metabolic parameters, including intrinsic clearance and Michaelis-Menten kinetics were calculated from substrate depletion data. Mice and rats demonstrated similar B[a]P diol phase I metabolic rates. Compared to rodents, human phase I metabolism of B[a]P diol demonstrated lower overall metabolic capacity, lower intrinsic clearance at higher substrate concentrations (>0.14μM), and higher intrinsic clearance at lower substrate concentrations (P diol glucuronidation; however, intrinsic clearance values for these compounds were consistent within each species. Kinetic parameters reported here will be used to extend physiologically based pharmacokinetic (PBPK) models to include the disposition of B[a]P and DBC metabolites in animal models and humans to support future human health risk assessments.

  11. Repairable Woven Carbon Fiber Composites with Full Recyclability Enabled by Malleable Polyimine Networks.

    Taynton, Philip; Ni, Huagang; Zhu, Chengpu; Yu, Kai; Loob, Samuel; Jin, Yinghua; Qi, H Jerry; Zhang, Wei


    Carbon-fiber reinforced composites are prepared using catalyst-free malleable polyimine networks as binders. An energy neutral closed-loop recycling process has been developed, enabling recovery of 100% of the imine components and carbon fibers in their original form. Polyimine films made using >21% recycled content exhibit no loss of mechanical performance, therefore indicating all of the thermoset composite material can be recycled and reused for the same purpose.

  12. Analysis of Natural Graphite, Synthetic Graphite, and Thermosetting Resin Candidates for Use in Fuel Compact Matrix

    Trammell, Michael P [ORNL; Pappano, Peter J [ORNL


    The AGR-1 and AGR-2 compacting process involved overcoating TRISO particles and compacting them in a steel die. The overcoating step is the process of applying matrix to the OPyC layer of TRISO particles in a rotating drum in order to build up an overcoat layer of desired thickness. The matrix used in overcoating is a mixture of natural graphite, synthetic graphite, and thermosetting resin in the ratio, by weight, of 64:16:20. A wet mixing process was used for AGR-1 and AGR-2, in that the graphites and resin were mixed in the presence of ethyl alcohol. The goal of the wet mixing process was to 'resinate' the graphite particles, or coat each individual graphite particle with a thin layer of resin. This matrix production process was similar to the German, Chinese, Japanese, and South African methods, which also use various amount of solvent during mixing. See Appendix 1 for information on these countries matrix production techniques. The resin used for AGR-1 and AGR-2 was provided by Hexion, specifically Hexion grade Durite SC1008. Durite SC1008 is a solvated (liquid) resole phenolic resin. A resole resin does not typically have a hardening agent added. The major constituent of SC1008 is phenol, with minor amounts of formaldehyde. Durite SC1008 is high viscosity, so additional ethyl alcohol was added during matrix production in order to reduce its viscosity and enhance graphite particle resination. The current compacting scale up plan departs from a wet mixing process. The matrix production method specified in the scale up plan is a co-grinding jet mill process where powdered phenolic resin and graphite are all fed into a jet mill at the same time. Because of the change in matrix production style, SC1008 cannot be used in the jet milling process because it is a liquid. The jet milling/mixing process requires that a suite of solid or powdered resins be investigated. The synthetic graphite used in AGR-1 and AGR-2 was provided by SGL Carbon, grade KRB2000. KRB

  13. Improved Mechanical Performance Fracture Properties and Reliability of Radical-Cured Thermosets.

    Redline, Erica Marie; Bolintineanu, Dan; Lane, J. Matthew; Stevens, Mark J.; Alam, Todd M.; Celina, Mathias C.


    The aim of this study was to alter polymerization chemistry to improve network homogeneity in free-radical crosslinked systems. It was hypothesized that a reduction in heterogeneity of the network would lead to improved mechanical performance. Experiments and simulations were carried out to investigate the connection between polymerization chemistry, network structure and mechanical properties. Experiments were conducted on two different monomer systems - the first is a single monomer system, urethane dimethacrylate (UDMA), and the second is a two-monomer system consisting of bisphenol A glycidyl dimethacrylate (BisGMA) and triethylene glycol dimethacrylate (TEGDMA) in a ratio of 70/30 BisGMA/TEGDMA by weight. The methacrylate systems were crosslinked using traditional radical polymeriza- tion (TRP) with azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO) as an initiator; TRP systems were used as the control. The monomers were also cross-linked using activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) as a type of controlled radical polymerization (CRP). FTIR and DSC were used to monitor reac- tion kinetics of the systems. The networks were analyzed using NMR, DSC, X-ray diffraction (XRD), atomic force microscopy (AFM), and small angle X-ray scattering (SAXS). These techniques were employed in an attempt to quantify differences between the traditional and controlled radical polymerizations. While a quantitative methodology for characterizing net- work morphology was not established, SAXS and AFM have shown some promising initial results. Additionally, differences in mechanical behavior were observed between traditional and controlled radical polymerized thermosets in the BisGMA/TEGDMA system but not in the UDMA materials; this finding may be the result of network ductility variations between the two materials. Coarse-grained molecular dynamics simulations employing a novel model of the CRP reaction were carried out for

  14. Further characterization of benzo[a]pyrene diol-epoxide (BPDE)-induced comet assay effects.

    Bausinger, Julia; Schütz, Petra; Piberger, Ann Liza; Speit, Günter


    The present study aims to further characterize benzo[a]pyrene diol-epoxide (BPDE)-induced comet assay effects. Therefore, we measured DNA effects by the comet assay and adduct levels by high-performance liquid chromatography (HPLC) in human lymphocytes and A549 cells exposed to (±)-anti-benzo[a]pyrene-7,8-diol 9,10-epoxide [(±)-anti-BPDE] or (+)-anti-benzo[a]pyrene-7,8-diol 9,10-epoxide [(+)-anti-BPDE]. Both, the racemic form and (+)-anti-BPDE, which is the most relevant metabolite with regard to mutagenicity and carcinogenicity, induced DNA migration in cultured lymphocytes in the same range of concentrations to a similar extent in the alkaline comet assay after exposure for 2h. Nevertheless, (+)-anti-BPDE induced significantly enhanced DNA migration after 16 and 18h post-cultivation which was not seen in response to (±)-anti-BPDE. Combination of the comet assay with the Fpg (formamidopyrimidine-DNA glycosylase) protein did not enhance BPDE-induced effects and thus indicated the absence of Fpg-sensitive sites (oxidized purines, N7-guanine adducts, AP-sites). The aphidicolin (APC)-modified comet assay suggested significant excision repair activity of cultured lymphocytes during the first 18h of culture after a 2 h-exposure to BPDE. In contrast to these repair-related effects measured by the comet assay, HPLC analysis of stable adducts did not reveal any significant removal of (+)-anti-BPDE-induced adducts from lymphocytes during the first 22h of culture. On the other hand, HPLC measurements indicated that A549 cells repaired about 70% of (+)-anti-BPDE-induced DNA-adducts within 22h of release. However, various experiments with the APC-modified comet assay did not indicate significant repair activity during this period in A549 cells. The conflicting results obtained with the comet assay and the HPLC-based adduct analysis question the real cause for BPDE-induced DNA migration in the comet assay and the reliability of the APC-modified comet assay for the

  15. Enantioselective Synthesis of Vicinal (R,R)-Diols by Saccharomyces cerevisiae Butanediol Dehydrogenase

    Calam, Eduard; González-Roca, Eva; Fernández, M. Rosario; Dequin, Sylvie; Parés, Xavier; Virgili, Albert


    Butanediol dehydrogenase (Bdh1p) from Saccharomyces cerevisiae belongs to the superfamily of the medium-chain dehydrogenases and reductases and converts reversibly R-acetoin and S-acetoin to (2R,3R)-2,3-butanediol and meso-2,3-butanediol, respectively. It is specific for NAD(H) as a coenzyme, and it is the main enzyme involved in the last metabolic step leading to (2R,3R)-2,3-butanediol in yeast. In this study, we have used the activity of Bdh1p in different forms—purified enzyme, yeast extracts, permeabilized yeast cells, and as a fusion protein (with yeast formate dehydrogenase, Fdh1p)—to transform several vicinal diketones to the corresponding diols. We have also developed a new variant of the delitto perfetto methodology to place BDH1 under the control of the GAL1 promoter, resulting in a yeast strain that overexpresses butanediol dehydrogenase and formate dehydrogenase activities in the presence of galactose and regenerates NADH in the presence of formate. While the use of purified Bdh1p allows the synthesis of enantiopure (2R,3R)-2,3-butanediol, (2R,3R)-2,3-pentanediol, (2R,3R)-2,3-hexanediol, and (3R,4R)-3,4-hexanediol, the use of the engineered strain (as an extract or as permeabilized cells) yields mixtures of the diols. The production of pure diol stereoisomers has also been achieved by means of a chimeric fusion protein combining Fdh1p and Bdh1p. Finally, we have determined the selectivity of Bdh1p toward the oxidation/reduction of the hydroxyl/ketone groups from (2R,3R)-2,3-pentanediol/2,3-pentanedione and (2R,3R)-2,3-hexanediol/2,3-hexanedione. In conclusion, Bdh1p is an enzyme with biotechnological interest that can be used to synthesize chiral building blocks. A scheme of the favored pathway with the corresponding intermediates is proposed for the Bdh1p reaction. PMID:26729717


    The use of supercritical carbon dioxide as a reaction medium for polyester synthesis is hindered by the low solubility of diols in CO2. However, it has been previously demonstrated that fluorinated compounds can exhibit greater miscibility with carbon dioxide than t...

  17. Size-exclusion chromatography based on silica-diol for the analysis of the proinsulin fusion protein.

    Gusarova, V; Vorobjeva, T; Gusarov, D; Lasman, V; Bayramashvili, D


    Size-exclusion chromatography based on silica-diol sorbent was employed to analyze the recombinant proinsulin fusion protein obtained during the process of refolding and the following ion-exchange purification. The assay was qualified as a control method estimating its accuracy, precision, linearity, limit of detection, limits of quantitation, specificity, and robustness. The results show the reliability for the intended use.

  18. Standard practice for infrared flash thermography of composite panels and repair patches used in aerospace applications

    American Society for Testing and Materials. Philadelphia


    1.1 This practice describes a procedure for detecting subsurface flaws in composite panels and repair patches using Flash Thermography (FT), in which an infrared (IR) camera is used to detect anomalous cooling behavior of a sample surface after it has been heated with a spatially uniform light pulse from a flash lamp array. 1.2 This practice describes established FT test methods that are currently used by industry, and have demonstrated utility in quality assurance of composite structures during post-manufacturing and in-service examinations. 1.3 This practice has utility for testing of polymer composite panels and repair patches containing, but not limited to, bismaleimide, epoxy, phenolic, poly(amide imide), polybenzimidazole, polyester (thermosetting and thermoplastic), poly(ether ether ketone), poly(ether imide), polyimide (thermosetting and thermoplastic), poly(phenylene sulfide), or polysulfone matrices; and alumina, aramid, boron, carbon, glass, quartz, or silicon carbide fibers. Typical as-fabricate...


    Pearlman, A.L.; Navsky, B.N.; Bartholomew, J.C


    A cell cycle synchronization system is described for the analysis of the perturbation of cell cycle kinetics and the cycle-phase specificity of chemicals and other agents. We used the system to study the effects of ({+-})r-7, t-8-dihydroxy-t-9, 10-oxy-7,8,9,10-tetrahydrobenzo[a]pyrene (BaP diol epoxide) upon the cell cycle of mouse liver epithelial cells(NMuLi). BaP diol epoxide(0.6 uM) was added to replated cultures of NMuLi cells that had been synchronized in various stages of the cell cycle by centrifugal elutriation. DNA histograms were obtained by flow cytometry as a function of time after replating. The data were analyzed by a computer modeling routine and reduced to a few graphs illustrating the 'net effects' of the BaP diol epoxide relative to controls. BaP diol epoxide slowed S-phase traversal in all samples relative to their respective control. Traversal through G{sub 2}M was also slowed by at least 50%. BaP diol epoxide had no apparent effect upon G{sub 1} traversal by cycling cells, but delayed the recruitment of quiescent G{sub 0} cells by about 2 hrs. The methods described constitute a powerful new approach for probing the cell cycle effects of a wide variety of agents. The present system appears to be extremely sensitive and capable of characterizing the action of agents on each phase of the cell cycle. The methods are automatable and would allow for the assay and possible differential characterization of mutagens and carcinogens.

  20. Normal-phase high performance liquid chromatography of estradiol derivatives on amino- and diol- columns



    Full Text Available The retention behaviour of estradiol derivatives was studied by HPLC on chemically bonded polar stationary phases: commercially available amino- and diol- columns, as a function of the heptane-propan-1-ol as the mobile phase, when the volume fraction of propan-1-ol in the binary mobile phase was low, even less than 5 %. The relationship between the logarithm of the retention constant (log k and the logarithm of the volume fraction of propan-1-ol (–log j in the eluent was linear for all solutes studied. The results are discussed in terms of the solute and stationary phase properties and compared with the results of the same derivatives obtained in earlier investigations.

  1. Isolation and Crystal Structure of 1′,4′-Trans-diol of Abscisic Acid

    WANG Tian-Shan; ZHOU Jin-Yan; TAN Hong


    1 ′,4′-Trans-diol of abscisic acid was isolated from botrytis cinerea as a colorless crystal. The molecular and crystal structures have been determined by X-ray diffraction analysis. It crystallizes in orthorhombic system, space group P212121 with a = 6.724(3), b = 17.559(6), c =12.265(2) (A), a = β = y = 90°, V = 1448.1(8) (A)3, Z = 4, Dx = 1.222 g/cm3, F(000) = 576 and μ(MoKa) = 0.087 mm-1. The final R = 0.0628 and wR = 0.1604 for 2501 independent reflections with Rint = 0.0160 and 1679 observed reflections with I >2σ(Ⅰ). There are three intermolecular hydrogen bonds in a unit cell.


    REN Qisheng; HUANG Wenqiang; ZHAO Fengzhi; Ho Binglin


    A novel polymer- bound 1,2 - diol, 3 - polystyrylsulfonyl- 1,2 - propanediol (6) had ben prepared by the reaction of sodium polystyrylsulfinate with allyl bromide, followed by oxidation and. hydrolysis or directly with 3 - chloro - 1,2 - propanediol in the presence of a phase transfer catalyst ,n - tetrabutylammonium iodide. The capacity of resin 6 for terephthaldehyde reached 1.43 mmol/g. The aldehydic groups attached to polymer 6 reacted with hydroxylamine hydrochloride or reduced by sodium borohydride giving p-formylbenzaldoxime (yield:89%)and p-formyl -benzalcohol (yield:73 A % ), respectively. The high yields of these polymer-supported reactions showed that the polymer 6 possessed the effective isolation of its reactive sites.

  3. [BMIM][PF(6)] promotes the synthesis of halohydrin esters from diols using potassium halides.

    Oromí-Farrús, Mireia; Eras, Jordi; Villorbina, Gemma; Torres, Mercè; Llopis-Mestre, Veronica; Welton, Tom; Canela, Ramon


    Haloesterification of diverse diols with various carboxylic acids was achieved using potassium halides (KX) as the only halide source in ionic liquids. The best yield was obtained in [BMIM][PF(6)] when 1,2-octanediol, palmitic acid and KBr were used. This yield was 85% and the regioisomer with the bromine in primary position was present in a 75:25 ratio. The regioisomeric ratio could be improved using either KCl or some phenylcarboxylic acids. [BMIM][PF(6)] acts as both reaction media and catalyst of the reaction. To the best of our knowledge, this type of combined reaction using an ionic liquid is unprecedented. The other solvents tested did not lead either to the same yield or to the same regioisomeric ratio.

  4. Thermoforming of thermoplastic matrix composites. Part I

    Harper, R.C.


    Long-fiber-reinforced polymer matrix composites find widespread use in a variety of commercial applications requiring properties that cannot be provided by unreinforced plastics or other common materials of construction. However, thermosetting matrix resins have long been plagued by production processes that are slow and difficult to automate. This has limited the use of long-fiber-reinforced composites to relatively low productivity applications in which higher production costs can be justified. Unreinforced thermoplastics, by their very nature, can easily be made into sheet form and processed into a variety of formed shapes by various pressure assisted thermoforming means. It is possible to incorporate various types of fiber reinforcement to suit the end use of the thermoformed shape. Recently developed thermoplastic resins can also sometimes correct physical property deficiencies in a thermoset matrix composite. Many forms of thermoplastic composite material now exist that meet all the requirements of present day automotive and aerospace parts. Some of these are presently in production, while others are still in the development stage. This opens the possibility that long-fiber-reinforced thermoplastics might break the barrier that has long limited the applications for fiber-reinforced composites. 37 refs., 8 figs., 5 tabs.

  5. The waterborne polyurethane dispersions based on polycarbonate diol: Effect of ionic content

    Cakić, Suzana M., E-mail: [University of Niš, Faculty of Technology, Bulevar oslobodjenja 124, 16000 Leskovac (Serbia); Špírková, Milena [Institute of Macromolecular Chemistry AS CR v.v.i., Heyrovskeho Nam. 2, 16206 Prague (Czech Republic); Ristić, Ivan S.; B-Simendić, Jaroslava K. [University of Novi Sad, Faculty of Technology, Bulevar cara Lazara 1, 21000 Novi Sad (Serbia); M-Cincović, Milena [University of Belgrade, Vinča Institute of Nuclear Science, P.O. Box 522, 11001 Belgrade (Serbia); Poręba, Rafał [Institute of Macromolecular Chemistry AS CR v.v.i., Heyrovskeho Nam. 2, 16206 Prague (Czech Republic)


    Three water-based polyurethane dispersions (PUD) were synthesized by modified dispersing procedure using polycarbonate diol (PCD), isophorone diisocyanate (IPDI), dimethylolpropionic acid (DMPA), triethylamine (TEA) and ethylenediamine (EDA). The ionic group content in the polyurethane-ionomer structure was varied by changing the amount of the internal emulsifier, DMPA (4.5, 7.5 and 10 wt.% to the prepolymer weight). The expected structures of obtained materials were confirmed by FTIR spectroscopy. The effect of the DMPA content on the thermal properties of polyurethane films was measured by TGA, DTA, DSC and DMTA methods. Increased DMPA amounts result in the higher hard segment contents and in the increase of the weight loss corresponding to the degradation of the hard segments. The reduction of hard segment content led to the elevated temperature of decomposition and to the decrease of the glass transition temperature and thermoplasticity. The atomic force microscopy (AFM), results indicated that phase separation between hard and soft segment of PUD with higher DMPA content is more significant than of PUD with lower DMPA content. The physico-mechanical properties, such as hardness, adhesion test and gloss of the dried films were also determined considering the effect of DMPA content on coating properties. Highlights: ► Polyurethane dispersions (PUD) were synthesized from polycarbonate diol. ► The effect of the DMPA content on the thermal properties of PUD films was measured. ► The thermal stability of PUD was increased by decreasing the DMPA content. ► T{sub g} values of PUD were increased by increasing ionic content. ► The PUD with the highest content of DMPA showed more significant phase separation confirmed by AFM results.

  6. Polymer damage mitigation---predictive lifetime models of polymer insulation degradation and biorenewable thermosets through cationic polymerization for self-healing applications

    Hondred, Peter Raymond

    Over the past 50 years, the industrial development and applications for polymers and polymer composites has become expansive. However, as with any young technology, the techniques for predicting material damage and resolving material failure are in need of continued development and refinement. This thesis work takes two approaches to polymer damage mitigation---material lifetime prediction and spontaneous damage repair through self-healing while incorporating bio-renewable feedstock. First, material lifetime prediction offers the benefit of identifying and isolating material failures before the effects of damage results in catastrophic failure. Second, self-healing provides a systematic approach to repairing damaged polymer composites, specifically in applications where a hands-on approach or removing the part from service are not feasible. With regard to lifetime prediction, we investigated three specific polymeric materials---polytetrafluoroethylene (PTFE), poly(ethylene-alt-tetrafluoroethylene) (ETFE), and Kapton. All three have been utilized extensively in the aerospace field as a wire insulation coating. Because of the vast amount of electrical wiring used in aerospace constructions and the potential for electrical and thermal failure, this work develops mathematical models for both the thermal degradation kinetics as well as a lifetime prediction model for electrothermal breakdown. Isoconversional kinetic methods, which plot activation energy as a function of the extent of degradation, present insight into the development each kinetic model. The models for PTFE, ETFE, and Kapton are one step, consecutive three-step, and competitive and consecutive five-step respectively. Statistical analysis shows that an nth order autocatalytic reaction best defined the reaction kinetics for each polymer's degradation. Self-healing polymers arrest crack propagation through the use of an imbedded adhesive that reacts when cracks form. This form of damage mitigation focuses on

  7. Manufacturing Aspects of Advanced Polymer Composites for Automotive Applications

    Friedrich, Klaus; Almajid, Abdulhakim A.


    Composite materials, in most cases fiber reinforced polymers, are nowadays used in many applications in which light weight and high specific modulus and strength are critical issues. The constituents of these materials and their special advantages relative to traditional materials are described in this paper. Further details are outlined regarding the present markets of polymer composites in Europe, and their special application in the automotive industry. In particular, the manufacturing of parts from thermoplastic as well as thermosetting, short and continuous fiber reinforced composites is emphasized.

  8. Influence of end groups in hyperbranched polyesters used as modifiers in the characteristics of epoxy thermosets cured by adipic dihydrazide

    A. Serra


    Full Text Available Mixtures of diglycidylether of bisphenol A (DGEBA resin and different ratios of aliphatic-aromatic hyperbranched polyester (HBP were cured by a latent curing agent, adipic dihydrazide (AH. The HBPs prepared have hydroxyl groups or 10-undecenoyl or allyl groups as chain ends. The curing mixtures were investigated by differential scanning calorimetry (DSC to study the curing process and to evaluate the kinetic parameters of the different formulations. These studies suggest that HBPs decrease the curing rate of epoxy/AH in the case of vinyl terminated HPB, whereas OH terminated HBP accelerates the first stages and delays the lasts. The thermosets obtained showed an improvement in microhardness and impact strength without any reduction of the Tg and thermal parameters. Microparticle phase separation was observed with the undecenoyl HBP derivatives or when a 10% of allyl HBP derivative was in the formulation.

  9. The base-free chemoselective ring opening of epoxides with carboxylic acids using [bmim]Br: a rapid entry into 1,2-diol mono-esters synthesis.

    Rad, Mohammad Navid Soltani; Behrouz, Somayeh


    A facile and highly convenient base-free protocol for the chemoselective preparation of 1,2-diol mono-esters is described. In this method, the regioselective ring opening of epoxides with carboxylic acids in the presence of [bmim]Br furnishes the corresponding 1,2-diol mono-esters in excellent yields. This method is efficient for various structurally diverse epoxides and carboxylic acids and it can be efficiently applied for the scale up synthesis of 1,2-diol mono-esters in reasonable to good yields. [bmim]Br remarkably influences the reaction progress and acts as both solvent and catalyst in this protocol.

  10. Resin Matrix/Fiber Reinforced Composite Material,Ⅲ:Simulating Results

    Li Chensha(李辰砂); Jiao Caishan; Liu Ying; Wang Zhengping; Wang Hongjie; Cao Maosheng


    According to the mathematical model which describes the curing process of composites constructed from continuous fiber-reinforced, thermosetting resin matrix prepreg materials, and the consolidation of the composite, the computer code calculates the data of the process variables of the flat-plate composites cured by a specified cure cycle, provides the variation of temperature distribution, the cure degree process, the resin variation and fibers stress inside the composite, the void variation and the residual stress distribution. The mechanism of curing process is illustrated and the cure cycle of composite material is optimized.

  11. Composites

    Chmielewski, M.; Nosewicz, S.; Pietrzak, K.; Rojek, J.; Strojny-Nędza, A.; Mackiewicz, S.; Dutkiewicz, J.


    It is commonly known that the properties of sintered materials are strongly related to technological conditions of the densification process. This paper shows the sintering behavior of a NiAl-Al2O3 composite, and its individual components sintered separately. Each kind of material was processed via the powder metallurgy route (hot pressing). The progress of sintering at different stages of the process was tested. Changes in the microstructure were examined using scanning and transmission electron microscopy. Metal-ceramics interface was clean and no additional phases were detected. Correlation between the microstructure, density, and mechanical properties of the sintered materials was analyzed. The values of elastic constants of NiAl/Al2O3 were close to intermetallic ones due to the volume content of the NiAl phase particularly at low densities, where small alumina particles had no impact on the composite's stiffness. The influence of the external pressure of 30 MPa seemed crucial for obtaining satisfactory stiffness for three kinds of the studied materials which were characterized by a high dense microstructure with a low number of isolated spherical pores.

  12. The Cost of Automotive Polymer Composites: A Review and Assessment of DOE's Lightweight Materials Composites Research

    Das, S.


    Polymer composite materials have been a part of the automotive industry for several decades, with early application in the 1953 Corvette. These materials have been used for applications with low production volumes, because of their shortened lead times and lower investment costs relative to conventional steel fabrication. Important drivers of the growth of polymer composites have been the reduced weight and parts consolidation opportunities the material offers, as well as design flexibility, corrosion resistance, material anisotropy, and mechanical properties. Although these benefits are well recognized by the industry, polymer composite use has been dampened by high material costs, slow production rates, and to a lesser extent, concerns about recyclability. Also impeding large scale automotive applications is a curious mixture of concerns about material issues such as crash energy absorption, recycling challenges, competitive and cost pressures, the industry's general lack of experience and comfort with the material, and industry concerns about its own capabilities (Flynn and Belzowski 1995). Polymer composite materials are generally made of two or more material components--fibers, either glass or carbon, reinforced in the matrix of thermoset or thermoplastic polymer materials. The glass-reinforced thermoset composites are the most commonly used composite in automotive applications today, but thermoplastic composites and carbon fiber-reinforced thermosets also hold potential. It has been estimated that significant use of glass-reinforced polymers as structural components could yield a 20-35% reduction in vehicle weight. More importantly, the use of carbon fiber-reinforced materials could yield a 40-65% reduction in weight.

  13. Biobased Carbon Fibers and Thermosetting Resins for Use in DOD Composites Applications: SERDP WP 1758 Final Report


    normalized weight as a function of time for styrene, PM, MG, and ME at 30 °C. See inset for the PM, MG, and ME behavior. The maximum standard deviation...per gram of SKL, 15 min of mixing time , and 25 washing cycles were established as standard protocol for each batch of SKL purification. After...problem is further complicated by the automotive companies ’ desire to enhance fuel efficiency (50 mpg by 2025) by changing from a metal to a

  14. The separation and synthesis of lipidic 1,2- and 1,3-diols from natural phenolic lipids for the complexation and recovery of boron.

    Tyman, John H P; Mehet, Satinderjit K


    A study has been made of the semi-synthesis of 1,3-diols (anacardic alcohols) from natural phenolic lipid resources from Anacardium occidentale and Anacardium giganteum which have given C15 and C11 derivatives, respectively. An isomeric 1,3-diol (isoanacardic alcohol) has been obtained from cardanol separated from technical cashew nut-shell liquid. Homologous 1,3-diols have been synthesised from a range of synthetic 2-alkyl-, 3-alkyl- and 4-alkylphenols and from 6-alkylsalicylic acids. The natural 1,2-diol, urushiol, from Rhus vernicifera has been purified. All these lipidic compounds have been studied for their complexation and the potential recovery of boron as boric acid.

  15. Preparation and characterization of fluorophenylboronic acid-functionalized affinity monolithic columns for the selective enrichment of cis-diol-containing biomolecules.

    Li, Qianjin; Liu, Zhen


    Boronate affinity monolithic columns have been developed into an important means for the selective recognition and capture of cis-diol-containing biomolecules, such as glycoproteins, nucleosides and saccharides. The ligands of boronic acids are playing an important role in boronate affinity monolithic columns. Although several boronate affinity monoliths with high affinity toward cis-diol-containing biomolecules have been reported, only few publications are focused on their detailed procedures for preparation and characterization. This chapter describes in detail the preparation and characterization of a boronate affinity monolithic column applying 2,4-difluoro-3-formyl-phenylboronic acid (DFFPBA) as a ligand. The DFFPBA-functionalized monolithic column not only exhibited an ultrahigh boronate affinity toward cis-diol-containing biomolecules, but also showed great potential for the selective enrichment of cis-diol-containing biomolecules in real samples.

  16. Long chain diol index (LDI) as an organic-based sea surface temperature proxy in the Korean East Sea (NW Pacific)

    Gal, Jong-Ku; Kim, Jung-Hyun; Kang, Su-Jin; Lee, Dong-Hun; Shin, Kyung-Hoon


    Long chain diol index (LDI) was introduced as an organic-based sea surface temperature (SST) proxy. LDI is expressed as the C30 1,15-diol abundance relative to those of C28 1,13-, C30 1,13- and C30 1,15-diols. There were a few studies which accessed the potential of LDI based on the culture, core top sediments, suspended particulate organic matters, and down-core sediments. However it is still unknown about the source of the diols and robustness as the SST proxy in the various marine environments. In the current study, we examined the applicability of the LDI in the East Sea of Korea where productivity and thus sedimentation rates are high. We will compare the LDI data with those of alkenone-based UK'37 by analyzing two multicores covering the last 100 year.

  17. Microfibrillated Lignocellulose Enables the Suspension-Polymerisation of Unsaturated Polyester Resin for Novel Composite Applications

    Yutao Yan


    Full Text Available A new route towards embedding fibrillated cellulose in a non-polar thermoset matrix without any use of organic solvent or chemical surface modification is presented. It is shown that microfibrillated lignocellulose made from cellulose with high residual lignin content is capable of stabilising an emulsion of unsaturated polyester resin in water due to its amphiphilic surface-chemical character. Upon polymerisation of the resin, thermoset microspheres embedded in a microfibrillated cellulose network are formed. The porous network structure persists after conventional drying in an oven, yielding a mechanically stable porous material. In an application experiment, the porous material was milled into a fine powder and added to the polyester matrix of a glass fibre-reinforced composite. This resulted in a significant improvement in fracture toughness of the composite, whereas a reduction of bending strength and stiffness was observed in parallel.

  18. Mutagenicity and tumorigenicity of the four enantiopure bay-region 3,4-diol-1,2-epoxide isomers of dibenz[a,h]anthracene.

    Chang, Richard L; Wood, Alexander W; Huang, Mou Tuan; Xie, Jian Guo; Cui, Xiao Xing; Reuhl, Kenneth R; Boyd, D R; Lin, Yong; Shih, Weichung Joe; Balani, Suresh K; Yagi, Haruhiko; Jerina, Donald M; Conney, Allan H


    Each enantiomer of the diastereomeric pair of bay-region dibenz[a,h]anthracene 3,4-diol-1,2-epoxides in which the benzylic 4-hydroxyl group and epoxide oxygen are either cis (isomer 1) or trans (isomer 2) were evaluated for mutagenic activity. In strains TA 98 and TA 100 of Salmonella typhimurium, the diol epoxide with (1S,2R,3S,4R) absolute configuration [(-)-diol epoxide-1] had the highest mutagenic activity. In Chinese hamster V-79 cells, the diol epoxide with (1R,2S,3S,4R) absolute configuration [(+)-diol epoxide-2] had the highest mutagenic activity. The (1R,2S,3R,4S) diol epoxide [(+)-diol epoxide-1] also had appreciable activity, whereas the other two bay-region diol epoxide enantiomers had very low activity. In tumor studies, the (1R,2S,3S,4R) enantiomer was the only diol epoxide isomer tested that had strong activity as a tumor initiator on mouse skin and in causing lung and liver tumors when injected into newborn mice. This stereoisomer was about one-third as active as the parent hydrocarbon, dibenz[a,h]anthracene as a tumor initiator on mouse skin; it was several-fold more active than dibenz[a,h]anthracene as a lung and liver carcinogen when injected into newborn mice. (-)-(3R,4R)-3β,4α-dihydroxy-3,4-dihydro-dibenz[a,h]anthracene [(-)-3,4-dihydrodiol] was slightly more active than dibenz[a,h]anthracene as a tumor initiator on mouse skin, whereas (+)-(3S,4S)-3α,4β-dihydroxy-3,4-dihydro-dibenz[a,h]anthracene [(+)-3,4-dihydrodiol] had only very weak activity. The present investigation and previous studies with the corresponding four possible enantiopure bay-region diol epoxide enantiomers/diastereomers of benzo[a]pyrene, benz[a]anthracene, chrysene, benzo[c]phenanthrene, dibenz[c,h]acridine, dibenz[a,h]acridine and dibenz[a,h]anthracene indicate that the bay-region diol epoxide enantiomer with [R,S,S,R] absolute stereochemistry has high tumorigenic activity on mouse skin and in newborn mice.

  19. Simultaneous monitoring of curing shrinkage and degree of cure of thermosets by attenuated total reflection Fourier transform infrared (ATR FT-IR) spectroscopy.

    Fernàndez-Francos, Xavier; Kazarian, Sergei G; Ramis, Xavier; Serra, Àngels


    We present a novel methodology to simultaneously monitor of the degree of cure and curing shrinkage of thermosetting formulations. This methodology is based on the observation of changes in the infrared absorption of reactive functional groups and the groups used as a standard reference for normalization. While the optical path length is exact and controlled in transmission infrared spectroscopy, in attenuated total reflection Fourier transform infrared (ATR FT-IR), the exact determination of volume changes requires the measurement of the refractive indices of the studied system throughout the curing process or at least an indirect parallel measurement of this property. The methodology presented here allows one to achieve quantitative measurements of the degree of cure and shrinkage for thermosets using in situ ATR FT-IR spectroscopy.

  20. Biocatalytic Synthesis of Epoxy Resins from Fatty Acids as a Versatile Route for the Formation of Polymer Thermosets with Tunable Properties.

    Torron, Susana; Semlitsch, Stefan; Martinelle, Mats; Johansson, Mats


    The work herein presented describes the synthesis and polymerization of series of bio-based epoxy resins prepared through lipase catalyzed transesterification. The epoxy-functional polyester resins with various architectures (linear, tri-branched, and tetra-branched) were synthesized through condensation of fatty acids derived from epoxidized soybean oil and linseed oil with three different hydroxyl cores under bulk conditions. The selectivity of the lipases toward esterification/transesterification reactions allowed the formation of macromers with up to 12 epoxides in the backbone. The high degree of functionality of the resins resulted in polymer thermosets with Tg values ranging from -25 to over 100 °C prepared through cationic polymerization. The determining parameters of the synthesis and the mechanism for the formation of the species were determined through kinetic studies by (1)H NMR, SEC, and molecular modeling studies. The correlation between macromer structure and thermoset properties was studied through real-time FTIR measurements, DSC, and DMA.

  1. Application of waste bulk moulded composite (BMC) as a filler for isotactic polypropylene composites.

    Barczewski, Mateusz; Matykiewicz, Danuta; Andrzejewski, Jacek; Skórczewska, Katarzyna


    The aim of this study was to produce isotactic polypropylene based composites filled with waste thermosetting bulk moulded composite (BMC). The influence of BMC waste addition (5, 10, 20 wt%) on composites structure and properties was investigated. Moreover, additional studies of chemical treatment of the filler were prepared. Modification of BMC waste by calcium stearate (CaSt) powder allows to assess the possibility of the production of composites with better dispersion of the filler and more uniform properties. The mechanical, processing, and thermal properties, as well as structural investigations were examined by means of static tensile test, Dynstat impact strength test, differential scanning calorimetry (DSC), wide angle X-ray scattering (WAXS), melt flow index (MFI) and scanning electron microscopy (SEM). Developed composites with different amounts of non-reactive filler exhibited satisfactory thermal and mechanical properties. Moreover, application of the low cost modifier (CaSt) allows to obtain composites with better dispersion of the filler and improved processability.

  2. Crystallization features and spontaneous resolution of 3-(2,6-dimethoxyphenoxy)propane-1,2-diol: The case of stable conglomerate and metastable solid solution

    Bredikhin, Alexander A.; Bredikhina, Zemfira A.; Antonovich, Olga A.; Zakharychev, Dmitry V.; Krivolapov, Dmitry B.


    Phase behavior of 3-(2,6-dimethoxyphenoxy)propane-1,2-diol 1 was investigated by IR spectroscopy, X-ray diffraction, and DSC methods. Racemic diol 1 prone to spontaneous resolution and has been resolved into (S)- and (R)-enantiomers by a preferential crystallization procedure. Separation takes place, but it gives crystalline precipitates with moderate (60-70%) enantiomeric excess values. The plausible reason is the formation of metastable phase of solid solution during the crystallization.

  3. Cs2CO3-promoted polycondensation of CO2with diols and dihalides for the synthesis of miscellaneous polycarbonates

    Chen, Zuliang


    A one-pot protocol for the direct synthesis of polycarbonates through polycondensation of diols, dihalides and CO2 in the presence of Cs2CO3 is described. The conditions were optimized by studying the polycondensation of CO2 with 1,4-phenylenedimethanol and 1,4-dibromobutane as model monomers. Then, diols and dihalides with different spacers between the reactive groups including aliphatic, aromatic and poly(ethylene glycol) were tested under optimal conditions. Miscellaneous polycarbonates exhibiting molar masses in the range of 43 000 g mol-1 (GPC) and conversion higher than 96% could be obtained. The proposed mechanism rules out the possibility of ether linkage formation during polycondensation and accounts for the creation of carbonate linkages in two different ways. The thermal properties of the synthesized polycarbonates were unveiled by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). © 2016 The Royal Society of Chemistry.

  4. Regioselective, borinic acid-catalyzed monoacylation, sulfonylation and alkylation of diols and carbohydrates: expansion of substrate scope and mechanistic studies.

    Lee, Doris; Williamson, Caitlin L; Chan, Lina; Taylor, Mark S


    Synthetic and mechanistic aspects of the diarylborinic acid-catalyzed regioselective monofunctionalization of 1,2- and 1,3-diols are presented. Diarylborinic acid catalysis is shown to be an efficient and general method for monotosylation of pyranoside derivatives bearing three secondary hydroxyl groups (7 examples, 88% average yield). In addition, the scope of the selective acylation, sulfonylation, and alkylation is extended to 1,2- and 1,3-diols not derived from carbohydrates (28 examples); the efficiency, generality, and operational simplicity of this method are competitive with those of state-of-the-art protocols including the broadly applied organotin-catalyzed or -mediated reactions. Mechanistic details of the organoboron-catalyzed processes are explored using competition experiments, kinetics, and catalyst structure-activity relationships. These experiments are consistent with a mechanism in which a tetracoordinate borinate complex reacts with the electrophilic species in the turnover-limiting step of the catalytic cycle.

  5. Efficient Pd@MIL-101(Cr) hetero-catalysts for 2-butyne-1,4-diol hydrogenation exhibiting high selectivity

    Yin, Dongdong


    Pd@MIL-101(Cr) hetero-catalysts have been successfully prepared using the metal-organic chemical vapour deposition (MOCVD) approach, by choosing [Pd(η-CH)(η-CH)] as a volatile precursor, and the hydrothermally stable metal-organic framework, MIL-101(Cr) as a support. The prepared Pd@MIL-101(Cr) hetero-catalysts characterized with various analytical techniques, exhibited highly monodispersed immobilized Pd nanoparticles in the MIL-101(Cr) cavities, while retaining the pristine crystallinity and porosity. The intact hybrid Pd@MIL-101(Cr) has been demonstrated to be an efficient catalyst for 2-butyne-1,4-diol hydrogenation with excellent activity, stability and selectivity (2-butene-1,4-diol (>94%)).

  6. Sustainable Pathways to Pyrroles through Iron-Catalyzed N-Heterocyclization from Unsaturated Diols and Primary Amines.

    Yan, Tao; Barta, Katalin


    Pyrroles are prominent scaffolds in pharmaceutically active compounds and play an important role in medicinal chemistry. Therefore, the development of new, atom-economic, and sustainable catalytic strategies to obtain these moieties is highly desired. Direct catalytic pathways that utilize readily available alcohol substrates have been recently established; however, these approaches rely on the use of noble metals such as ruthenium or iridium. Here, we report on the direct synthesis of pyrroles using a catalyst based on the earth-abundant and inexpensive iron. The method uses 2-butyne-1,4-diol or 2-butene-1,4-diol that can be directly coupled with anilines, benzyl amines, and aliphatic amines to obtain a variety of N-substituted pyrroles in moderate-to-excellent isolated yields.

  7. Benzo(a)pyrene diol epoxides as intermediates in nucleic acid binding in vivo and in vitro

    Weinstein, I.B.; Jeffrey, A.M.; Jennette, K.W.


    Evidence has been obtained that a specific isomer of a diol epoxide derivative of benzo(a)pyrene, (+/-)-7 beta,8alpha-dihydroxy-9alpha, 10alpha-epoxy-7,8,9,10-tetrahydrobenzo(a)pyrene, is an intermediate in the binding of benzo(a)pyrene to RNA in cultured bovine bronchial mucosa. An adduct is for...... is formed between position 10 of this derivative and the 2-amino group of guanine.......Evidence has been obtained that a specific isomer of a diol epoxide derivative of benzo(a)pyrene, (+/-)-7 beta,8alpha-dihydroxy-9alpha, 10alpha-epoxy-7,8,9,10-tetrahydrobenzo(a)pyrene, is an intermediate in the binding of benzo(a)pyrene to RNA in cultured bovine bronchial mucosa. An adduct...

  8. Fluorinated porphyrin tweezer: a powerful reporter of absolute configuration for erythro and threo diols, amino alcohols, and diamines.

    Li, Xiaoyong; Tanasova, Marina; Vasileiou, Chrysoula; Borhan, Babak


    A general and sensitive nonempirical protocol to determine the absolute configurations of erythro and threo diols, amino alcohols, and diamines is reported. Binding of diols to the porphyrin tweezer system is greatly enhanced by increasing the Lewis acidity of the metalloporphyrin. Supramolecular complexes formed between the porphyrin tweezer host and chiral substrates exhibited exciton-coupled bisignate CD spectra with predictable signs based on the substituents on the chiral center. The working model suggests that the observed helicity of the porphyrin tweezer is dictated via steric differentiation experienced by the porphyrin ring bound to each chiral center. A variety of erythro and threo substrates were investigated to verify this chiroptical method. Their absolute configurations were unequivocally determined, and thus a general mnemonic is provided for the assignment of chirality.

  9. Lipase-catalyzed synthesis of aliphatic polyesters via copolymerization of lactone, dialkyl diester, and diol.

    Jiang, Zhaozhong


    Candida antarctica lipase (CALB) has been successfully used as catalyst for copolymerization of dialkyl diester with diol and lactone to form aliphatic polyesters. The polymerization reactions were performed using a two stage process: first stage oligomerization under low vacuum followed by second stage polymerization under high vacuum. Use of the two-stage process is required to obtain products with high molecular weights at high yields for the following reasons: (i) the first stage reaction ensures that the monomer loss via evaporation is minimized to maintain 1:1 diester to diol stoichiometric ratio, and the monomers are converted to nonvolatile oligomers; (ii) use of high vacuum during the second stage accelerates equilibrium transesterification reactions to transform the oligomers to high molecular weight polymers. Thus, terpolymers of omega-pentadecalactone (PDL), diethyl succinate (DES), and 1,4-butanediol (BD) with a M w of whole product (nonfractionated) up to 77000 and M w/ M n between 1.7 and 4.0 were synthesized in high yields (e.g., 95% isolated yield). A desirable reaction temperature for the copolymerizations was found to be around 95 degrees C. At 1:1:1 PDL/DES/BD monomer molar ratio, the resultant terpolymers contained equal moles of PDL, succinate, and butylene repeat units in the polymer chains. (1)H and (13)C NMR analyses were used to determine the polyester microstructures. The synthesized PDL-DES-BD terpolymers possessed near random structures with all possible combinations of PDL, succinate, and butylene units via ester linkages in the polymer backbone. Furthermore, thermal stability and crystallinity of a pure PDL-DES-BD terpolymer with 1:1:1 PDL to succinate to butylene unit ratio and M w of 85400 were studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The copolyester was found to be a semicrystalline material with a T g of -34 degrees C and a T m of 64 degrees C, which degrades in a single weight loss

  10. 可固化高陶瓷产率聚碳硅烷的合成与性能研究%Synthesis and Properties of a High Ceramic Yield Thermosetting Polycarbosilane

    袁钦; 宋永才; 李永强


    Thermosetting polycarbosilane (PVCS) was prepared from polycarbosilane (PCS) and 2,4,6, 8-Tetravinyl-2,4,6,8-tetramethylcyclotrasiloxane (Dvi4). The chemical composition, structure and curing abil-ity and pyrolysis properties were investigated by GPC, DSC, PT-IR, TG, XRD and other analytical tools. The results showed that PVCS contained Si-H and C C=C reactive groups could cure at 200 ~ 350℃, and the re-sidual weight was 96. 6% at 350℃. The ceramic yield of PVCS at 1000℃ in N2 atmosphere was 80. 0 wt% , β-SiC crystallite appeared in the ceramics product at 1200℃.%以聚碳硅烷(PCS)和四甲基四乙烯基环四硅氧烷(DVi4)为原料,合成了新型含乙烯基聚碳硅烷(PVCS).利用FT- IR、GPC、DSC、TG、XRD等分析手段对PVCS的结构、固化特性及裂解特性进行表征.结果表明:PVCS中含有Si-H及C=C基,可在200~ 350℃固化,350℃固化质量保留率为96.6%,1 000℃陶瓷产率为80.0%,1 200℃陶瓷产物出现β- SiC微晶.

  11. Computational and DNMR investigation of the isomerism and stereodynamics of the 2,2'-binaphthalene-1,1'-diol scaffold.

    Mazzanti, Andrea; Chiarucci, Michel; Bentley, Keith W; Wolf, Christian


    The relative stabilities of three conformational isomers of 2,2'-binaphthalene-1,1'-diol diisobutyrate and the energy barriers to rotation about the pivotal aryl-aryl bond and the two aryl-oxygen bonds were investigated by variable-temperature NMR spectroscopy in conjunction with DFT computations. The experimental and calculated data were found to be in very good agreement and provide new insights into the dynamic stereochemistry of BINOL-derived tropos ligands.

  12. Boronate-Phenolic Network Capsules with Dual Response to Acidic pH and cis-Diols.

    Guo, Junling; Sun, Huanli; Alt, Karen; Tardy, Blaise L; Richardson, Joseph J; Suma, Tomoya; Ejima, Hirotaka; Cui, Jiwei; Hagemeyer, Christoph E; Caruso, Frank


    Dual-responsive boronate-phenolic network (BPN) capsules are fabricated by the complexation of phenylborate and phenolic materials. The BPN capsules are stable in the presence of competing carbohydrates, but dissociate at acidic pH or in the presence of competing cis-diols at physiological pH. This engineered capsule system provides a platform for a wide range of biological and biomedical applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Iridium- and ruthenium-catalysed synthesis of 2,3-disubstituted indoles from anilines and vicinal diols

    Tursky, Matyas; Lorentz-Petersen, Linda Luise Reeh; Olsen, L. B.;


    A straightforward and atom-economical method is described for the synthesis of 2,3-disubstituted indoles. Anilines and 1,2-diols are condensed under neat conditions with catalytic amounts of either [Cp*IrCl2](2)/MsOH or RuCl3 center dot xH(2)O/phosphine (phosphine = PPh3 or xantphos). The reaction...

  14. Stereoselective synthesis of 1,3-anti diols by an Ipc-mediated domino aldol-coupling/reduction sequence.

    Dieckmann, Michael; Menche, Dirk


    A novel domino process for 1,3-anti diol synthesis by the union of a methyl ketone with an aldehyde is described. The operationally simple procedure is based on an Ipc-boron-aldol coupling and subsequent Ipc-mediated reduction of the intermediate β-hydroxy-ketone. The sequence proceeds with excellent anti-selectivities and enables the rapid construction of complex polyketide fragments.

  15. Theoretical investigations of the reaction between 1,4-dithiane-2,5-diol and azomethine imines: mechanisms and diastereoselectivity.

    Zheng, Linjie; Qiao, Yan; Lu, Mengxue; Chang, Junbiao


    In the present study, mechanistic insights into the domino reaction between 1,4-dithiane-2,5-diol and azomethine imines were derived from the computational study with B3LYP and M06-2X functionals. On the whole, the domino process comprises two consecutive reactions: cleavage of 1,4-dithiane-2,5-diol leading to mercaptoacetaldehyde and [3 + 3] cycloaddition of mercaptoacetaldehyde with azomethine imines. The cleavage of 1,4-dithiane-2,5-diol can take place via multiple possible pathways (1A-1E), and pathway 1E in which double-methanol molecules mediate the proton transfer process is the most energetically favorable, with an energy barrier of 19.9 kcal mol(-1). For the [3 + 3] cycloaddition, three possible pathways (2F-2H) were explored. The calculated energy profiles reveal that pathway 2H with activation energies ranging from 6.9 to 10.2 kcal mol(-1) is more energetically favorable than pathways 2F and 2G. Specifically, pathway 2H comprises three reaction steps: deprotonation of mercaptoacetaldehyde by DABCO allows for the formation of the thiol anion, which subsequently launches a nucleophilic attack on azomethine imines followed by intramolecular cyclization resulting in the final products. The calculated results are in agreement with the experimental observations that the reaction can proceed most efficiently in the presence of both DABCO and methanol. Furthermore, the hydrogen bonding interaction is identified to be the main factor determining the observed diastereoselectivity The current systematic theoretical study gives a full scenario of the reaction between 1,4-dithiane-2,5-diol and azomethine imines catalyzed by DABCO, and thus provides some valuable clues for further investigation and development of this kind of important reaction.

  16. Rheological behavior of composites based on carbon fibers recycled from aircraft waste

    Marcaníková, Lucie; Hausnerová, Berenika; KITANO, Takeshi


    Rheological investigation of composite materials prepared from the recycled aircraft waste materials based on thermoset (epoxy/resin) matrix and long carbon fibers (CF) is presented with the aim of their utilization in consumer industry applications. The carbon fibers recovered via thermal process of pyrolysis were cut into about 150 pm length and melt mixed with thermoplastic matrices based on polypropylene (PP) and polyamide 6 (PA) and various modifiers - ethylene-ethyl acrylate-maleic anhy...

  17. Studies on Carbon-Fly Ash Composites with Chopped PANOX Fibers

    Patel,Rakesh V; Manocha, S.


    Chemical analysis and morphological studies of fly ash reveals the complex chemical constituents present as spherical particles with diameter of less than 25 μm. The constituents of fly ash are silica, alumina, iron oxide, titanium dioxide, calcium and magnesium oxide, and other trace elements. The use of thermosetting as well thermoplastic polymer matrix has been made by several workers to develop polymer matrix fly ash particulate composites by using the hard and abrasive properties of fly ...

  18. Rheological behavior of composites based on carbon fibers recycled from aircraft waste

    Marcaníková, Lucie; Hausnerová, Berenika; Kitano, Takeshi


    Rheological investigation of composite materials prepared from the recycled aircraft waste materials based on thermoset (epoxy/resin) matrix and long carbon fibers (CF) is presented with the aim of their utilization in consumer industry applications. The carbon fibers recovered via thermal process of pyrolysis were cut into about 150 pm length and melt mixed with thermoplastic matrices based on polypropylene (PP) and polyamide 6 (PA) and various modifiers - ethylene-ethyl acrylate-maleic anhy...

  19. Identification and characterization of dimeric oxidation products of p-cymene-2,3-diol isolated from Thymus vulgaris L.

    Rainis, Guido; Ternes, Waldemar


    The aim of this study was to investigate the oxidation products of p-cymene-2,3-diol, a major antioxidative constituent of thyme (Thymus vulgaris L.). Although a dimeric form of p-cymene-2,3-diol and some derivative substances exhibiting valuable food technological and health-promoting properties have been reported in earlier publications, no obvious correlation has been shown between these substances. A modified HPLC-ESI-MS method made it possible to prove that two dimers, 3,4,3',4'-tetrahydroxy-5,5'-diisopropyl-2,2'-dimethylbiphenyl (1) and the newly identified 3',4'-dihydroxy-5,5'-diisopropyl-2,2'-dimethylbiphenyl-3,4-dione (2), are oxidation products of p-cymene-2,3-diol. 2 was characterized by the fragmentation pattern determined by multiple mass spectrometry, (1)H NMR, (13)C NMR, H-H COSY, HSQC, and HMBC. Both biphenyls were also quantitated in freeze-dried thyme as well as in a food matrix spiked with thyme extract. Model experiments using raw and cooked minced pork meat as matrix and sodium nitrite as oxidizing and reduction agent with and without ascorbic acid as protective reagent showed the correlation between food processing and dimer generation.

  20. Synthesis, characterization and cytocompatibility of a poly(diol-tricarballylate) visible light photo-cross-linked biodegradable elastomer.

    Shaker, Mohamed A; Doré, Jules J E; Younes, Husam M


    The synthesis, characterization and in vitro cytocompatibility of a new family of photo-cross-linked amorphous poly(diol-tricarballylate) (PDT) biodegradable elastomeric polyesters are reported. The synthesis was based on the polycondensation reaction between tricarballylic acid and alkylene diols, followed by acrylation. The prepared and acrylated poly(diol-tricarballylate) (APDT) was characterized by means of FT-IR, (1)H-NMR, GPC and DSC. Liquid-to-solid photo-curing was carried out by exposing the APDT to visible light in the presence of camphorquinone as a photoinitiator. The thermal properties, mechanical characteristics, sol content, long-term in vitro degradation and cytocompatibility of the prepared PDT elastomers were also reported. The mechanical and degradation properties of this new photocurable elastomer can be precisely controlled by varying the density of acrylate moieties in the matrix of the polymer, and through changes in the pre-polymer chain length. The use of visible light cross-linking, possibility of solventless drug loading, controllable mechanical properties and cytocompatibility of these new elastomers make them excellent candidates for use in controlled implantable drug-delivery systems of protein drugs and other biomedical applications.

  1. Toxicological assessment of 3-chloropropane-1,2-diol and glycidol fatty acid esters in food.

    Bakhiya, Nadiya; Abraham, Klaus; Gürtler, Rainer; Appel, Klaus Erich; Lampen, Alfonso


    Fatty acid esters of 3-chloropropane-1,2-diol (3-MCPD) and glycidol are a newly identified class of food process contaminants. They are widespread in refined vegetable oils and fats and have been detected in vegetable fat-containing products, including infant formulas. There are no toxicological data available yet on the 3-MCPD and glycidol esters, and the primary toxicological concern is based on the potential release of 3-MCPD or glycidol from the parent esters by lipase-catalyzed hydrolysis in the gastrointestinal tract. Although 3-MCPD is assessed as a nongenotoxic carcinogen with a tolerable daily intake (TDI) of 2 μg/kg body weight (bw), glycidol is a known genotoxic carcinogen, which induces tumors in numerous organs of rodents. The initial exposure estimates, conducted by Federal Institute for Risk Assessment (BfR) under the assumption that 100% of the 3-MPCD and glycidol are released from their esters, revealed especially that infants being fed commercial infant formula could ingest harmful amounts of 3-MCPD and glycidol. However, the real oral bioavailability may be lower. As this gives rise for toxicological concern, the currently available toxicological data of 3-MCPD and glycidol and their esters are summarized in this review and discussed with regard to data gaps and further research needs.

  2. Influence of dough ingredients on 3-chloropropane-1,2-diol (3-MCPD) formation in toast.

    Breitling-Utzmann, C M; Hrenn, H; Haase, N U; Unbehend, G M


    The influence of different dough ingredients such as fat, salt, sourdough, emulsifiers, and sugar on the formation of 3-chloropropane-1,2-diol (3-MCPD) during toast preparation under domestic conditions was investigated. In comparison with a fat-free recipe, addition of 1% peanut fat considerably increased 3-MCPD formation, but varying the fat (2-5%) or salt (1.6-2.4%) contents within technological acceptable limits did not show any significant differences. A baking agent, which is usually commercially applied by many toast bakers or industrial toast manufacturers, increased 3-MCPD formation in toasted bread slices. Considerable evidence was found that the baking agent's main component sucrose had the major part in increasing 3-MCPD levels. Emulsifiers containing monoacylglycerols moderately increased 3-MCPD levels, but the addition of lecithin did not have any significant influence. 3-MCPD levels showed a good correlation with the lightness (L* value) of the bread slices; their 3-MCPD content increased exponentially towards dark coloured toasts. The relation between 3-MCPD and 2-MCPD was an average of 3:1 in all samples. Dichloropropanols such as, for example, 1,3-dichloropropanol could not be detected.

  3. Understanding the mechanism of B(12)-dependent diol dehydratase: a synergistic retro-push--pull proposal.

    Smith, D M; Golding, B T; Radom, L


    Ab initio molecular orbital theory is used to investigate the coenzyme B(12)-dependent reactions catalyzed by diol dehydratase. The key step in such reactions is believed to be a 1,2-hydroxyl migration, which occurs within free-radical intermediates. The barrier for this migration, if unassisted, is calculated to be too high to be consistent with the observed reaction rate. However, we find that "pushing" the migrating hydroxyl, through interaction with a suitable acid, is able to provide significant catalysis. This is denoted retro-push catalysis, the retro prefix signifying that the motion of the migrating group is in the direction opposite to the electron motion. Similarly, the "pulling" of the migrating group, through interaction of the spectator hydroxyl with an appropriate base, is found to substantially reduce the rearrangement barrier. Importantly, the combination of these two effects results in a barrier reduction that is notably greater than additive. This synergistic interplay of the push and the pull provides an attractive means of catalysis. Our proposed retro-push--pull mechanism leads to results that are consistent with isotope-labeling experiments, with experimental rate data, and with the crystal structure of the enzyme.

  4. Semi-aromatic polyesters based on a carbohydrate-derived rigid diol for engineering plastics.

    Wu, Jing; Eduard, Pieter; Thiyagarajan, Shanmugam; Noordover, Bart A J; van Es, Daan S; Koning, Cor E


    New carbohydrate-based polyesters were prepared from isoidide-2,5-dimethanol (extended isoidide, XII) through melt polymerization with dimethyl esters of terephthalic acid (TA) and furan-2,5-dicarboxylic acid (FDCA), yielding semi-crystalline prepolymers. Subsequent solid-state post-condensation (SSPC) gave high molecular weight (Mn =30 kg mol(-1) for FDCA) materials, the first examples of high Mn , semi-aromatic homopolyesters containing isohexide derivatives obtained via industrially relevant procedures. NMR spectroscopy showed that the stereo-configuration of XII was preserved under the applied conditions. The polyesters are thermally stable up to 380 °C. The TA- and FDCA-based polyesters have high Tg (105 °C and 94 °C, resp.) and Tm (284 °C and 250 °C, resp.) values. Its reactivity, stability, and ability to afford high Tg and Tm polyesters make XII a promising diol for the synthesis of engineering polymers.

  5. Antioxidants Inhibit Formation of 3-Monochloropropane-1,2-diol Esters in Model Reactions.

    Li, Chang; Jia, Hanbing; Shen, Mingyue; Wang, Yuting; Nie, Shaoping; Chen, Yi; Zhou, Yongqiang; Wang, Yuanxing; Xie, Mingyong


    The capacities of six antioxidants to inhibit the formation of 3-monochloropropane-1,2 diol (3-MCPD) esters were examined in this study. Inhibitory capacities of the antioxidants were investigated both in chemical models containing the precursors (tripalmitoyl glycerol, 1,2-dipalmitoyl-sn-glycerol, monopalmitoyl glycerol, and sodium chloride) of 3-MCPD esters and in oil models (rapeseed oil and sodium chloride). Six antioxidants, butylated hydroxytoluene (BHT), butylated hydroxy anisole (BHA), tert-butyl hydroquinone (TBHQ), propyl gallate (PG), L-ascorbyl palmitate (AP), and α-tocopherol (VE), were found to exhibit inhibiting capacities on 3-MCPD ester formation both in chemical models and in oil models. TBHQ provided the highest inhibitory capacity both in chemical models and in oil models; 44% of 3-MCPD ester formation was inhibited in the presence of TBHQ (66 mg/kg of oil) after heating of rapeseed oil at 230 °C for 30 min, followed by PG and AP. BHT, BHA, and VE appeared to have weaker inhibitory abilities in both models. VE exhibited the lowest inhibition rate; 22% of 3-MCPD esters were inhibited in the presence of VE (172 mg/kg of oil) after heating of rapeseed oil at 230 °C for 30 min. In addition, the inhibition rates of PG and VE decreased dramatically with an increase in temperature or heating time. The results suggested that some antioxidants, such as TBHQ, PG, and AP, could be the potential inhibitors of 3-MCPD esters in practice.

  6. Fatty acid esters of 3-chloropropane-1,2-diol in edible oils.

    Zelinková, Z; Svejkovská, B; Velísek, J; Dolezal, M


    A series of 25 virgin and refined edible oils, obtained from retailers, was analyzed for levels of free 3-chloropropane-1,2-diol (3-MCPD) and 3-MCPD released from esters with higher fatty acids (bound 3-MCPD). Oils containing free 3-MCPD ranging from 280 degrees C, and heating at 230 degrees C (260 degrees C) for up to 8 h, led to an increase in bound 3-MCPD levels. On the other hand, heating of olive oil resulted in a decrease in bound 3-MCPD levels. For comparison, fat isolated from salami was analyzed for intact fatty acid esters of 3-MCPD. This fat contained bound 3-MCPD at a level of 1670 microg kg-1 and the fatty acid esters of 3-MCPD mainly consisted of 3-MCPD diesters; monoesters of 3-MCPD were present in smaller amounts. The major types of 3-MCPD diesters (about 85%) were mixed diesters of palmitic acid with C18 fatty acids (stearic, oleic, linoleic acids). These diesters were followed by 3-MCPD distearate (11%) and 3-MCPD dipalmitate (4%). Generally, very little 3-MCPD existed as the free compound (31 microg kg-1).

  7. Selective hydrodeoxygenation of cyclic vicinal diols to cyclic alcohols over tungsten oxide-palladium catalysts.

    Amada, Yasushi; Ota, Nobuhiko; Tamura, Masazumi; Nakagawa, Yoshinao; Tomishige, Keiichi


    Hydrodeoxygenation of cyclic vicinal diols such as 1,4-anhydroerythritol was conducted over catalysts containing both a noble metal and a group 5-7 transition-metal oxide. The combination of Pd and WOx allowed the removal of one of the two OH groups selectively. 3-Hydroxytetrahydrofuran was obtained from 1,4-anhydroerythritol in 72 and 74% yield over WOx -Pd/C and WOx -Pd/ZrO2 , respectively. The WOx -Pd/ZrO2 catalyst was reusable without significant loss of activity if the catalyst was calcined as a method of regeneration. Characterization of WOx -Pd/C with temperature-programmed reduction, X-ray diffraction, and transmission electron microscopy/energy-dispersive X-ray spectroscopy suggested that Pd metal particles approximately 9 nm in size were formed on amorphous tungsten oxide particles. A reaction mechanism was proposed on the basis of kinetics, reaction results with tungsten oxides under an atmosphere of Ar, and density functional theory calculations. A tetravalent tungsten center (W(IV) ) was formed by reduction of WO3 with the Pd catalyst and H2 , and this center served as the reductant for partial hydrodeoxygenation.

  8. Preparation and properties of gluten/calcium carbonate composites

    Min Zuo; Zheng Zheng Lai; Yi Hu Song; Qiang Zheng


    Environment friendly thermosetting composites were prepared by blending wheat gluten (WG) as matrix, calcium carbonate (CaCO3) as filler and glycerol as plasticizer followed by compression molding the mixture at 120 ℃ to crosslink the WG matrix. Morphology observation showed that the CaCO3 particles were finely dispersed in matrix. Incorporation of CaCO3 up to 10 wt% into the composites caused Young's modulus and tensile strength to increase markedly. On the other hand, the moisture absorption and elongation at break decreased slightly.

  9. Resin Matrix/Fiber Reinforced Composite Material, Ⅱ: Method of Solution and Computer Code

    Li Chensha(李辰砂); Jiao Caishan; Liu Ying; Wang Zhengping; Wang Hongjie; Cao Maosheng


    According to a mathematical model which describes the curing process of composites constructed from continuous fiber-reinforced, thermosetting resin matrix prepreg materials, and the consolidation of the composites, the solution method to the model is made and a computer code is developed, which for flat-plate composites cured by a specified cure cycle, provides the variation of temperature distribution, the cure reaction process in the resin, the resin flow and fibers stress inside the composite, the void variation and the residual stress distribution.

  10. Calibrating Long-chain Diols for Quantitative Temperature Reconstructions in the High Elevation, Lacustrine Environments of the Sierra Nevada, Spain

    Toney, J. L.; García-Alix, A.; Jimenez-Moreno, G.; Anderson, R. S.; Perez-Martinez, C.; Jimenez, L.


    High-alpine, oligotrophic lakes in the Sierra Nevada are sensitive archives of paleoclimate and paleoecology. In this study we present the first quantitative calibration of lacustrine long-chain diols to instrumental temperature anamoly data. The data suggest that the long-chain diol index (LDI) is linearly correlated with the regional temperature anomaly data (TA = 8.8997 x LDI - 2.1113, r2 = 0.65) over the past 165-years and that this correlation can accurately be applied downcore to reconstructure temperature change over the course of the Holocene. This study compares the newly generated diol-inferred temperature dataset with existing multiproxy records to show that the mid-Holocene transition that shows a step change in vegetation and humidity toward aridification was likely driven by an increased and sustained temperature anomaly of +1.5°C from 6.4 to 5.8ka. Major changes occurred with respect to biogeography and vegetation communities in the Sierra Nevada at this time, but until now, the drivers of change have been unclear. In addition to the diol-inferred temperature anomaly data, compound-specific stable H-isotopes of terrestrial and aquatic plant waxes indicate that this warm event was directly preceded by a brief cold excursion at Laguna de Rio Seco that likely reduced terrestrial plant development and enhanced input of meltwater - suggested by low lake-water H-isotope values. The diol-inferred temperatures suggest that meltwater lowered the lake water temperature with a -1.2°C anomaly from 6.6 to 6.4ka. This suggests that the subsequent warming over the next 600-years likely caused a local, extreme shift to higher temperatures due to the lack of buffering by meltwater once the year-on-year snowpack was depleted. Briefer warm anomalies occur at 5.5, 3.2, and 1.5ka, which correspond to know periods of reduced precipitation in the Mediterranean region (e.g., see discussion in Martin-Puertas et al. 2010, doi:10.5194/cpd-6-1655-2010). A similar, but more

  11. Optimization of the Thermosetting Pultrusion Process by Using Hybrid and Mixed Integer Genetic Algorithms

    Baran, Ismet; Tutum, Cem Celal; Hattel, Jesper Henri


    In this paper thermo-chemical simulation of the pultrusion process of a composite rod is first used as a validation case to ensure that the utilized numerical scheme is stable and converges to results given in literature. Following this validation case, a cylindrical die block with heaters is added...... to the pultrusion domain of a composite part and thermal contact resistance (TCR) regions at the die-part interface are defined. Two optimization case studies are performed on this new configuration. In the first one, optimal die radius and TCR values are found by using a hybrid genetic algorithm based......) such that the total number of heaters is minimized while satisfying the constraints for the maximum composite temperature, the mean of the cure degree at the die exit and the pulling speed....

  12. Smart, Sustainable, and Ecofriendly Chemical Design of Fully Bio-Based Thermally Stable Thermosets Based on Benzoxazine Chemistry.

    Froimowicz, Pablo; R Arza, Carlos; Han, Lu; Ishida, Hatsuo


    A smart synthetic chemical design incorporating furfurylamine, a natural renewable amine, into a partially bio-based coumarin-containing benzoxazine is presented. The versatility of the synthetic approach is shown to be flexible and robust enough to be successful under more ecofriendly reaction conditions by replacing toluene with ethanol as the reaction solvent and even under solventless conditions. The chemical structure of this coumarin-furfurylamine-containing benzoxazine is characterized by FTIR, (1) H NMR spectroscopy and two-dimensional (1) H-(1) H nuclear Overhauser effect spectroscopy (2D (1) H-(1) H NOESY). The thermal properties of the resin toward polymerization are characterized by differential scanning calorimetry (DSC) and the thermal stability of the resulting polymers by thermogravimetric analysis (TGA). The results reveal that the furanic moiety induces a co-operative activating effect, thus lowering the polymerization temperature and also contributes to a better thermal stability of the resulting polymers. These results, in addition to those of natural renewable benzoxazine resins reviewed herein, highlight the positive and beneficial implication of designing novel bio-based polybenzoxazine and possibly other thermosets with desirable and competitive properties. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Instrumented sphere method for measuring thermal pressure in fluids and isotropic stresses and reaction kinetics in thermosetting resins

    Merzlyakov, Mikhail; Meng, Yan; Simon, Sindee L.; McKenna, Gregory B.


    A novel technique is described for measuring thermal pressure in fluids and for measuring isotropic stress development and reaction kinetics in thermosetting resins during cure and thermal cycling. The method uses a 12.7-mm-diam sealed stainless steel spherical pressure vessel to impose three-dimensional isotropic constraints. The vessel is instrumented with strain gauges and thermocouples. Both isotropic stresses and reaction kinetics during cure at cure temperatures as high as 300 °C can be measured. In addition, measurement of the isotropic stress as a function of temperature yields the thermal pressure coefficient in both the glassy and rubbery (or liquid) states. Experimental results are presented for sucrose benzoate, a pressure-transmitting oil di-2-ethylhexylsebacate and an epoxy resin. The method provides reproducible estimates for the thermal pressure coefficient and the stresses are highly isotropic. A suggestion for improved versions of the device is: thicker walled vessels can be used to increase the upper stress limit (currently at 30 MPa). Also if a lower temperature range is to be studied, then aluminum can be used as a vessel material. Since epoxy resins have better adhesion to aluminum than to stainless steel, there may be an advantage to this.

  14. The effect of thermal contact resistance on the thermosetting pultrusion process

    Baran, Ismet; Tutum, Cem C.; Hattel, Jesper H.


    In the present study the control volume based finite difference (CV/FD) method is utilized to perform thermo-chemical simulation of the pultrusion process of a composite rod. Preliminary, the model is applied for a simple setup without die and heaters and the results match well with those obtained e

  15. Optimization of the Thermosetting Pultrusion Process by Using Hybrid and Mixed Integer Genetic Algorithms

    Baran, Ismet; Tutum, Cem C.; Hattel, Jesper H.


    In this paper thermo-chemical simulation of the pultrusion process of a composite rod is first used as a validation case to ensure that the utilized numerical scheme is stable and converges to results given in literature. Following this validation case, a cylindrical die block with heaters is added

  16. Optimization of the Thermosetting Pultrusion Process by Using Hybrid and Mixed Integer Genetic Algorithms

    Baran, Ismet; Tutum, Cem C.; Hattel, Jesper H.


    In this paper thermo-chemical simulation of the pultrusion process of a composite rod is first used as a validation case to ensure that the utilized numerical scheme is stable and converges to results given in literature. Following this validation case, a cylindrical die block with heaters is added

  17. The effect of thermal contact resistance on the thermosetting pultrusion process

    Baran, Ismet; Tutum, Cem Celal; Hattel, Jesper Henri


    In the present study the control volume based finite difference (CV/FD) method is utilized to perform thermo-chemical simulation of the pultrusion process of a composite rod. Preliminary, the model is applied for a simple setup without die and heaters and the results match well with those obtained...

  18. Half esters and coating compositions comprising reactions products of half esters and polyepoxides

    Blaauw, R.; Mulder, W.J.; Koelewijn, R.; Boswinkel, G.


    The present invention relates to half esters based on dicarboxylic acid derivatives and dimer fatty diols, wherein the dimer fatty dio ls are based on dimerised and/or trimerised and/or oligomerised unsaturated fatty acids. The present invention further relates to resin compositions based on the hal

  19. Advanced composites take a powder

    Holty, D.W. (Custom Composite Materials, Inc., Atlanta, GA (United States))


    To a professional chemist with more than 25 years of industrial experience, the world of advanced composites is a fascinating new venue. Here resins and fibers come together in a completely synergistic partnership, achieving marvels of strength and light weight that make advanced composite materials virtually the only solution for challenging applications. In the late 1980s, Professor John Muzzy of the Georgia Institute of Technology, was intrigued by the physical properties of thermoplastics, and he developed a new way to bring the thermoplastic resins together with high-performance fibers. As part of the work Muzzy did with Lockheed and NASA he demonstrated that electrostatic powder coating was an attractive new method for combining thermoplastic resins with reinforcing fibers. Presentation of this work by Lockheed at a government-industry conference led to a new project for Muzzy, sponsored by NASA Langley. Powder prepregging proved to be the attractive alternative that NASA was looking for. While working on powder prepregging with LaRC-TPI, Muzzy and his colleagues developed methods for exposing all of the fibers to the powder to improve the distribution of the resin on the tow, a continuous bundle of filaments. Optimal resin distribution was achieved by spreading the moving tow. A very flexible towpreg was produced by maintaining the spread tow through the powder coating chamber and into the oven, where the resin particles were fused to the individual filaments. Muzzy's invention has enabled Custom Composite Materials, Inc. to offer resin/fiber combinations based on thermoplastic resins such as nylon and polypropylene. Beyond the expected advantages over epoxy thermoset systems, they are beginning to exploit a fundamental property of thermoplastic resins: viscoelasticity, which can be defined as the resistance to flow as a function of applied stress. Thermoplastics have a much higher viscoelasticity than thermosets.

  20. Discovery of a Novel Linoleate Dioxygenase of Fusarium oxysporum and Linoleate Diol Synthase of Colletotrichum graminicola.

    Sooman, Linda; Oliw, Ernst H


    Fungal pathogens constitute serious threats for many forms of life. The pathogenic fungi Fusarium and Colletotrichum and their formae speciales (f. spp.) infect many types of crops with severe consequences and Fusarium oxysporum can also induce keratitis and allergic conditions in humans. These fungi code for homologues of dioxygenase-cytochrome P450 (DOX-CYP) fusion proteins of the animal heme peroxidase (cyclooxygenase) superfamily. The objective was to characterize the enzymatic activities of the DOX-CYP homologue of Colletotrichum graminicola (EFQ34869) and the DOX homologue of F. oxysporum (EGU79548). The former oxidized oleic and linoleic acids in analogy with 7,8-linoleate diol synthases (LDSs), but with the additional biosynthesis of 8,11-dihydroxylinoleic acid. The latter metabolized fatty acids to hydroperoxides with broad substrate specificity. It oxidized 20:4n-6 and 18:2n-6 to hydroperoxides with an R configuration at the (n-10) positions, and other n-6 fatty acids in the same way. [11S-(2)H]18:2n-6 was oxidized with retention and [11R-(2)H]18:2n-6 with loss of deuterium, suggesting suprafacial hydrogen abstraction and oxygen insertion. Fatty acids of the n-3 series were oxidized less efficiently and often to hydroperoxides with an R configuration at both (n-10) and (n-7) positions. The enzyme spans 1426 amino acids with about 825 residues in the N-terminal domain with DOX homology and 600 residues at the C-terminal domain without homology to other enzymes. We conclude that fungal oxylipins can be formed by two novel subfamilies of cyclooxygenase-related DOX.

  1. Fingerprinting of traditional Chinese medicines on the C18-Diol mixed-mode column in online or offline two-dimensional liquid chromatography on the single column modes.

    Wang, Qing; Tong, Ling; Yao, Lin; Zhang, Peng; Xu, Li


    In the present study, a mixed-mode stationary phase, C18-Diol, was applied for fingerprint analysis of traditional Chinese medicines. Hydrophobic, hydrogen bonding and electrostatic interactions were demonstrated to contribute the retention separately or jointly, which endowed the C18-Diol stationary phase with distinct selectivity compared to the bare C18 one. The separation of total alkaloids extracted from Fritillaria hupehensis was compared on the C18-Diol and conventional C18 column with the greater resolving power and better symmetry responses on the former one. Besides, a novel two-dimensional liquid chromatography on the single column (2D-LC-1C) was realized on C18-Diol with the offline mode for the alcohol extract of Fritillaria hupehensis and online mode for Ligusticum chuanxiong Hort. The early co-eluted extracted components with great polarity on the first dimension were reinjected on the same column and well separated on the second dimension. The results exhibited that the two complementary RPLC and HILIC modes on C18-Diol stationary phase enhanced the separation capacity and revealed more abundant chemical information of the sample, which was a powerful tool in analyzing complex herbal medicines.

  2. Wood-plastic composites as promising green-composites for automotive industries!

    Ashori, Alireza


    Wood-plastic composite (WPC) is a very promising and sustainable green material to achieve durability without using toxic chemicals. The term WPCs refers to any composites that contain plant fiber and thermosets or thermoplastics. In comparison to other fibrous materials, plant fibers are in general suitable to reinforce plastics due to relative high strength and stiffness, low cost, low density, low CO2 emission, biodegradability and annually renewable. Plant fibers as fillers and reinforcements for polymers are currently the fastest-growing type of polymer additives. Since automakers are aiming to make every part either recyclable or biodegradable, there still seems to be some scope for green-composites based on biodegradable polymers and plant fibers. From a technical point of view, these bio-based composites will enhance mechanical strength and acoustic performance, reduce material weight and fuel consumption, lower production cost, improve passenger safety and shatterproof performance under extreme temperature changes, and improve biodegradability for the auto interior parts.

  3. The C32 alkane-1,15-diol as a proxy of late Quaternary riverine input in coastal margins

    Lattaud, Julie; Dorhout, Denise; Schulz, Hartmut; Castañeda, Isla S.; Schefuß, Enno; Sinninghe Damsté, Jaap S.; Schouten, Stefan


    The study of past sedimentary records from coastal margins allows us to reconstruct variations in terrestrial input into the marine realm and to gain insight into continental climatic variability. There are numerous organic proxies for tracing terrestrial input into marine environments but none that strictly reflect the input of river-produced organic matter. Here, we test the fractional abundance of the C32 alkane 1,15-diol relative to all 1,13- and 1,15-long-chain diols (FC32 1, 15) as a tracer of input of river-produced organic matter in the marine realm in surface and Quaternary (0-45 ka) sediments on the shelf off the Zambezi and nearby smaller rivers in the Mozambique Channel (western Indian Ocean). A Quaternary (0-22 ka) sediment record off the Nile River mouth in the eastern Mediterranean was also studied for long-chain diols. For the Mozambique Channel, surface sediments of sites most proximal to Mozambique rivers showed the highest F1, 15 - C32 (up to 10 %). The sedimentary record shows high (15-35 %) pre-Holocene F1, 15 - C32 and low (caused the Zambezi River mouth to become more distal to our study site, thereby decreasing riverine input at the core location. Some small discrepancies are observed between the records of the BIT index and FC32 1, 15 for Heinrich Event 1 (H1) and the Younger Dryas (YD), which may be explained by a change in soil sources in the catchment area rather than a change in river influx. Like for the Mozambique Channel, a significant correlation between FC32 1, 15 and the BIT index (r2 = 0.38, p changes in the catchment area.

  4. Emerging Trends in Polymer Matrix Composites .

    Vikas M. Nadkarni


    Full Text Available The performance characteristics of PMC products are determined by the microstructure developed during the processing of composite materials. The structure development in processing is the result of integration of process parameters and inherent material characteristics. The properties of PMCs can thus be manipulated through both changes in the materials composition and process conditions. The present article illustrates the scientific approach followed in engineering of matrix materials and optimization of the processing conditions with specific reference to case studies on toughening of thermosetting resins and structure development in injection molding of thermoplastic composites. A novel approach is demonstrated for toughening of unsaturated polyester resins that involves the use of reactive liquid polymers chemically bonded to the matrix. The use of processing science is demonstrated by the significant effect of the mold temperature on the crystallinity and properties of molded poly (phenylene sulfide, a high performance engineering thermoplastic. An interactive approach is proposed for specific product and applications development.

  5. The synthesis and determination of the octacoordinated structure of Pr(III) and Nd(III) complexes with β-diketones and diols in non aqueous solutions: evidence of some participation of π-electron density of diols with Pr(III) and Nd(III) in complexation

    Misra, Sudhindra N.; Devi, M. Indira


    The synthesized complexes are of the general structure Ln(β-diketonate) 3 diol (where β-diketonate = benzoyl acetonate (bzac), dibenzoyl methanoate (dbm) and thionyl trifluoroacetonate (ttfa) and (diols) (= butane-1,4- and cis-butene-1,4-diols). The absorption intensity data in non aqueous solvents has been analysed in terms of Judd Ofelt intensity Tλ(λ = 2, 4, 6) parameters for electric dipole 4f-4f transitions. β-diketones are bidentate and function as monofunctional ligands coordinating through oxygen donor atoms forming substantially stable chelate rings, while diols behave as neutral biodentate ligands coordinating through oxygen. β-diketone ligands differ only in the substituents R 1 and R 2 (Fig. 1) while diols differ in the nature of the bond formed between second and third carbon atoms of the molecules. These small chemical and structural differences have been shown to produce significant variation of oscillator strength of certain absorption bands. Again, their relative perturbations of 4f-4f transition intensities are quite evident in Tλ-parameters estimated for different complexes. Attempts have been made to correlate between the intensity parameter Tλ and oscillator strengths determined from observed spectra of these complexes. The intensity analysis of absorption spectral bands have given sufficient evidence of some sort of interaction between Pr(III) and Nd(III) with π-electron density of the double bond found in butene-1,4-diol.

  6. New example of spontaneous resolution among aryl glycerol ethers: 3-(2,6-dichlorophenoxy)propane-1,2-diol

    Bredikhina, Zemfira A.; Kurenkov, Alexey V.; Zakharychev, Dmitry V.; Krivolapov, Dmitry B.; Bredikhin, Alexander A.


    Using a set of simple tests, based on the properties of ideal conglomerate phase diagrams, it has been suggested to the conglomerate-formative nature of 3-(2,6-dichlorophenoxy)-propane-1,2-diol 1. Additional arguments have been drawn during the study of a single crystal X-ray diffraction study of the compound. The crystal packing details have been evaluated and discussed. Racemic 1 have been resolved into individual (S)- and (R)-components by a preferential crystallization procedure.

  7. Direct synthesis of 1,4-diols from alkenes by iron-catalyzed aerobic hydration and C-H hydroxylation.

    Hashimoto, Takuma; Hirose, Daisuke; Taniguchi, Tsuyoshi


    Various 1,4-diols are easily accessible from alkenes through iron-catalyzed aerobic hydration. The reaction system consists of a user-friendly iron phthalocyanine complex, sodium borohydride, and molecular oxygen. Furthermore, the effect of additional ligands on the iron complex was examined for a model reaction. The second hydroxy group is installed by direct C(sp(3))-H oxygenation, which is based on a [1,5] hydrogen shift process of a transient alkoxy radical that is formed by formal hydration of the olefin.

  8. New thermally stable polyesters based on 2,5-pyridinedicarbonyl dichloride and aromatic diols: Synthesis and characterization

    Hossein Nasr Isfahani; Khalil Faghihi


    Six new thermally stable polyesters (4a-f) were synthesized through the solution polycondensation reaction of 2,5-pyridine dicarbonyldichloride (2) with six aromatic diols in N,N'-dimethyl acetamide (DMAc) solution and in the presence of pyridine as a base. The polycondensation reactions produce a series of new polyesters (4a-f) in high yields, and inherent viscosity between 0.30 and 0.55 dL/g. The resulting polyesters were characterized by elemental analysis, viscosity measurements, thermal gravimetric analysis (TGA and DTG), solubility test, Fourier transform infrared (FT-IR) spectroscopy and gel permeation chromatography (GPC).

  9. An Investigation of Stimulating the Autoclave Curing Process of Resin Matrix/Fiber Reinforced Composite Material,Ⅰ: Process model


    A mathematical model is made which describes the curing process of composites constructed from continuous fiber-reinforced, thermosetting resin matrix prepreg materials, and the consolidation of the composite is developed. The model provides the variation of temperature distribution, the cure reaction process in the resin, the resin flow and fibers stress inside the composite, and the void variation and the residual stress distribution. It can be used to illustrate the mechanism of curing process and optimize the cure cycle of composite material in order to ensure the quality of a product.

  10. Aligned short-fibre reinforced thermosets - Experiments and analysis lend little support for established theory

    Piggott, M. R.; Ko, M.; Chuang, H. Y.

    Experiments with epoxy resins reinforced with aligned short carbon fibers give results which disagree sharply with traditional fiber reinforcement theory based on interface yielding and slip and the concept of the critical fiber aspect ratio. Earlier results and evidence from interface studies are therefore reviewed, and it is shown that, as the carbon/polymer interface is brittle, the progressive interface failure process previously envisaged almost certainly does not take place. Furthermore, a careful reading of the sources of data relating to the yielding and slip theory indicates that the evidence in support of it is very weak. Thus, the idea of the critical fiber aspect ratio, borrowed from the metallurgists, may not be appropriate for short-fiber reinforced plastics. Instead, a process involving brittle fiber debonds should be considered. These debonds could trigger matrix cracking and hence explain the anomalously low composite breaking strains observed when the breaking strain of the fiber is greater than that of the polymer, and other properties of aligned short-fiber composites.

  11. Conglomerate formative precursor of chiral drug timolol: 3-(4-Morpholino-1,2,5-thiadiazol-3-yloxy)-propane-1,2-diol

    Bredikhin, Alexander A.; Zakharychev, Dmitry V.; Fayzullin, Robert R.; Bredikhina, Zemfira A.; Gubaidullin, Aidar T.


    Solid state properties of 3-(4-N-morpholino-1,2,5-thiadiazol-3-yloxy)-propane-1,2-diol 3, the synthetic precursor of popular drug timolol, have been investigated. The original solubility test, the data of X-ray diffraction and DSC methods indicate that the compound is prone to spontaneous resolution. Diol 3 crystallizing from both enantiopure or racemic feed material forms "guaifenesin-like" crystal packing in which the classic H-bonded bilayers, framed in both sides by hydrophobic molecular fragments, act as the basic supramolecular motif. The main chain conformation of the molecules in the crystals of diol 3 differs from that in the guaifenesin crystals, and this fact changes the absolute configuration of spiral columns formed by intermolecular hydrogen bonds in crystals of 3 as compared with guaifenesin crystals.

  12. Effects of Solvent Diols on the Synthesis of ZnFe₂O₄ Particles and Their Use as Heterogeneous Photo-Fenton Catalysts.

    Anchieta, Chayene Gonçalves; Cancelier, Adriano; Mazutti, Marcio Antonio; Jahn, Sérgio Luiz; Kuhn, Raquel Cristine; Gündel, Andre; Chiavone-Filho, Osvaldo; Foletto, Edson Luiz


    A solvothermal method was used to prepare zinc ferrite spinel oxide (ZnFe₂O₄) using ethylene glycol and 1,4 butanediol as solvent diols, and the influence of diols on the physical properties of ZnFe₂O₄ particles was investigated. The produced particles were characterized by X-ray powder diffraction (XRD), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR) and nitrogen adsorption isotherms, and the catalytic activity for the organic pollutant decomposition by heterogeneous photo-Fenton reaction was investigated. Both solvents produced particles with cubic spinel structure. Microporous and mesoporous structures were obtained when ethylene glycol and 1,4 butanediol were used as diols, respectively. A higher pore volume and surface area, as well as a higher catalytic activity for the pollutant degradation were found when 1,4 butanediol was used as solvent.

  13. Effects of Solvent Diols on the Synthesis of ZnFe2O4 Particles and Their Use as Heterogeneous Photo-Fenton Catalysts

    Chayene Gonçalves Anchieta


    Full Text Available A solvothermal method was used to prepare zinc ferrite spinel oxide (ZnFe2O4 using ethylene glycol and 1,4 butanediol as solvent diols, and the influence of diols on the physical properties of ZnFe2O4 particles was investigated. The produced particles were characterized by X-ray powder diffraction (XRD, atomic force microscopy (AFM, Fourier transform infrared spectroscopy (FTIR and nitrogen adsorption isotherms, and the catalytic activity for the organic pollutant decomposition by heterogeneous photo-Fenton reaction was investigated. Both solvents produced particles with cubic spinel structure. Microporous and mesoporous structures were obtained when ethylene glycol and 1,4 butanediol were used as diols, respectively. A higher pore volume and surface area, as well as a higher catalytic activity for the pollutant degradation were found when 1,4 butanediol was used as solvent.

  14. Stability and in vivo behavior of Rh[16aneS4-diol]211 at complex: a potential precursor for astatine radiopharmaceuticals.

    Pruszyński, Marek; Łyczko, Monika; Bilewicz, Aleksander; Zalutsky, Michael R


    The heavy halogen (211)At is of great interest for targeted radiotherapy because it decays by the emission of short-range, high-energy α-particles. However, many astatine compounds that have been synthesized are unstable in vivo, providing motivation for seeking other (211)At labeling strategies. One relatively unexplored approach is to utilize prosthetic groups based on astatinated rhodium (III) complex stabilized with a tetrathioether macrocyclic ligand - Rh[16aneS(4)-diol](211)At. The purpose of the current study was to evaluate the in vitro and in vivo stability of this complex in comparison to its iodine analog - Rh[16aneS(4)-diol](131)I. Rh[16aneS(4)-diol](211)At and Rh[16aneS(4)-diol](131)I complexes were synthesized and purified by HPLC. The stability of both complexes was evaluated in vitro by incubation in phosphate-buffered saline (PBS) and human serum at different temperatures. The in vivo behavior of the two radiohalogenated complexes was assessed by a paired-label biodistribution study in normal Balb/c mice. Both complexes were synthesized in high yield and purity. Almost no degradation was observed for Rh[16aneS(4)-diol](131)I in PBS over a 72 h incubation. The astatinated analog exhibited good stability in PBS over 14 h. A slow decline in the percentage of intact complex was observed for both tracers in human serum. In the biodistribution study, retention of (211)At in most tissues was higher than that of (131)I at all time points, especially in spleen and lungs. Renal clearance of Rh[16aneS(4)-diol](211)At and Rh[16aneS(4)-diol](131)I predominated, with 84.1 ± 2.3% and 94.6 ± 0.9% of injected dose excreted via the urine at 4 h. The Rh[16aneS(4)-diol](211)At complex might be useful for constructing prosthetic groups for the astatination of biomolecules and further studies are planned to evaluate this possibility. Copyright © 2014 Elsevier Inc. All rights reserved.

  15. Toughening of PMR composites by gradient semi-interpenetrating networks

    Johnston, N. J.; Srinivasan, K.; Peter, R. H.


    The toughening of the PMR-15 and LARC RP-46 high temperature thermosetting polyimides is presently attempted through the construction of a semiinterpenetrating network at ply interfaces through the use of the Matrimid 5218 thermoplastic polyimide powder, whose 315-320 glass transition temperature is compatible with the PMR matrices. The 60 vol pct fiber composites thus prepared for the two resins, with and without toughening, were comprehensively characterized in flexure, tension, intralaminar and short beam shear, compression and quasi-isotropic short-block compression, as well as modes I and II interlaminar fracture toughness and compression after impact.

  16. Cross-Linked Dependency of Boronic Acid-Conjugated Chitosan Nanoparticles by Diols for Sustained Insulin Release

    Nabil A. Siddiqui


    Full Text Available Boronic acids have been widely investigated for their potential use as glucose sensors in glucose responsive polymeric insulin delivery systems. Interactions between cyclic diols and boronic acids, anchored to polymeric delivery systems, may result in swelling of the delivery system, releasing the drug. In this study, 4-formylphenylboronic acid conjugated chitosan was formulated into insulin containing nanoparticles via polyelectrolyte complexation. The nanoparticles had an average diameter of 140 ± 12.8 nm, polydispersity index of 0.17 ± 0.1, zeta potential of +19.1 ± 0.69 mV, encapsulation efficiency of 81% ± 1.2%, and an insulin loading capacity of 46% ± 1.8% w/w. Changes in size of the nanoparticles and release of insulin were type of sugar- and concentration-dependent. High concentration of diols resulted in a sustained release of insulin due to crosslink formation with boronic acid moieties within the nanoparticles. The formulation has potential to be developed into a self-regulated insulin delivery system for the treatment of diabetes.

  17. Preparation and surface active properties of oxypropylated diol monoesters of fatty acids with an amide oxime terminal group

    Eissa, A. M.F.


    Full Text Available Locally produced non-edible oil, namely, rice bran oil (R.B.O. was utilized as starting materials for preparing new nonionic surfactant. Oxypropylated diol monoesters of linoleic and rice bran oil fatty acids were prepared. Also amide oxime derivatives were obtained. Surface active properties of these compounds were measured. Under neutral condition amide eximes served as nonionic surfactants and their properties were similar to other oxypropylated monoesters.

    Se ha utilizado un aceite no comestible de producción local, denominado, aceite de salvado de arroz (R.B.O. como materia prima para la preparación de nuevos tensioactivos no iónicos. Se prepararon diol monoésteres oxipropilados de ácido linoleico y ácidos grasos de aceite de salvado de arroz. También se obtuvieron los derivados de amido oxima. Se midieron las propiedades de tensión superficial de estos compuestos. Bajo condiciones neutras las amido eximas sirvieron como tensioactivos no iónicos y sus propiedades fueron similares a los de otros monoésteres oxipropilados.

  18. Superparamagnetic Ironoxide Nanoparticles via Ligand Exchange Reactions: Organic 1,2-Diols as Versatile Building Blocks for Surface Engineering

    Robert Sachsenhofer


    Full Text Available A method for the preparation of ligand-covered superparamagnetic iron oxide nanoparticles via exchange reactions is described. 1,2-diol-ligands are used to provide a stable binding of the terminally modified organic ligands onto the surface of γ-Fe2O3-nanoparticles (r∼4 nm. The 1,2-diol-ligands are equipped with variable terminal functional groups (i.e., hydrogen bonding moieties, azido- bromo-, fluorescent moieties and can be easily prepared via osmium tetroxide-catalyzed 1,2-dihydroxylation reactions of the corresponding terminal alkenes. Starting from octylamine-covered Î��-Fe2O3-nanoparticles, ligand exchange was effected at 50∘C over 24–48 hours, whereupon complete ligand exchange is taking place as proven by thermogravimetric (TGA- and IR-spectroscopic measurements. A detailed kinetic analysis of the ligand exchange reaction was performed via TGA analysis, demonstrating a complete ligand exchange after 24 hours. The method offers a simple approach for the generation of various γ-Fe2O3-nanoparticles with functional organic shells in a one-step procedure.

  19. A Review on the Mechanical Modeling of Composite Manufacturing Processes

    Baran, Ismet; Cinar, Kenan; Ersoy, Nuri;


    approaches. The process models as well as applications focusing on the prediction of residual stresses and shape distortions taking place in composite manufacturing are discussed in this study. The applications on both thermoset and thermoplastic based composites are reviewed in detail.......The increased usage of fiber reinforced polymer composites in load bearing applications requires a detailed understanding of the process induced residual stresses and their effect on the shape distortions. This is utmost necessary in order to have more reliable composite manufacturing since...... the residual stresses alter the internal stress level of the composite part during the service life and the residual shape distortions may lead to not meeting the desired geometrical tolerances. The occurrence of residual stresses during the manufacturing process inherently contains diverse interactions...

  20. Structural design of composite sealing systems for automotive applications

    Tarnowski, T. [Dow Chemical Co., Southfield, MI (United States)


    New applications for composites in under-the-hood closure systems such as engine valve covers, transmission side covers, oil pans, and timing chain covers are developing rapidly. The primary driving forces are lighter weight of finished components, integrated designs, improved isolation of engine noise, improved materials systems, and matured manufacturing processes for composite materials. Thermoset-based composite materials, especially those based on high-temperature resistant epoxy vinylester matrices, offer improved elevated-temperature performance with respect to thermoplastic composites. This paper presents the current state-of-the-art design, engineering and optimization techniques for engine closure systems. The performance requirements of systems such as valve covers and oil pans are explained in detail. Techniques for long-term structural stiffness evaluation, vibration performance assessment and noise transmission estimation are described. The material characterization required to develop design allowables for long-term, high-temperature composite applications are also included.

  1. Multi-layered, membrane-integrated microfluidics based on replica molding of a thiol-ene epoxy thermoset for organ-on-a-chip applications.

    Sticker, Drago; Rothbauer, Mario; Lechner, Sarah; Hehenberger, Marie-Therese; Ertl, Peter


    In this study we have investigated a photosensitive thermoset (OSTEMER 322-40) as a complementary material to readily fabricate complex multi-layered microdevices for applications in life science. Simple, versatile and robust fabrication of multifunctional microfluidics is becoming increasingly important for the development of customized tissue-, organ- and body-on-a-chip systems capable of mimicking tissue interfaces and biological barriers. In the present work key material properties including optical properties, vapor permeability, hydrophilicity and biocompatibility are evaluated for cell-based assays using fibroblasts, endothelial cells and mesenchymal stem cells. The excellent bonding strength of the OSTEMER thermoset to flexible fluoropolymer (FEP) sheets and poly(dimethylsiloxane) (PDMS) membranes further allows for the fabrication of integrated microfluidic components such as membrane-based microdegassers, microvalves and micropumps. We demonstrate the application of multi-layered, membrane-integrated microdevices that consist of up to seven layers and three membranes that specially confine and separate vascular cells from the epithelial barrier and 3D tissue structures.

  2. Flow channel design of a multi-cavity mold by filling simulation for thermosets. Netsu kokasei jushi ryudo kaiseki ni yoru cavity tasuko tori kanagata no ryuro sekkei

    Saeki, J. (Hitachi Ltd., Tokyo (Japan)); Kaneda, A. (Hitachi Chemical Co. Ltd., Tokyo (Japan))


    A study was made on the flow channel design of a multi-cavity mold by filling simulation for thermosets. A practical analytic method was developed for the calculation of pressure losses at various locations in the channel following the estimation of viscosity change in the thermosets in the mold with optional shape. The runner and gate are designed for equal flow distribution to each cavity, and a newly developed model and a conventional type model were trially made for various evaluation using the conditions set at the time of designing. Ideal filling was achieved with the newly developed type model, and the design method of the type was confirmed to be reasonable. Characteristic values were studied which can be considered to give effect on the deformation of gold wires and void formation in molded devices. The effects on the prevention of gold wire deformation, decrease in void formation, and widening formation margin were confirmed. By the developed mold designing method, less diameter gold wire may be used without decreasing the quality of the package. 10 refs., 11 figs., 5 tabs.

  3. Additives to reduce susceptibility of thermosets and thermoplastics to erosion from atomic oxygen

    Orwoll, Robert A.


    Polymeric materials have many attractive features such as light weight, high strength, and broad applicability in the form of films, fibers, and molded objects. In low earth orbit (LEO), these materials, when exposed on the exterior of the spacecraft, have the serious disadvantage of being susceptible to erosion by atomic oxygen (AO). AO is the most common chemical species at LEO altitudes. AO can be an extremely efficient oxidizing agent as was apparent from the extensive erosion of organic films exposed in STS missions. The mechanism for erosion involves the reaction of oxygen atoms at the surface of the substrate to form small molecular species. The susceptibility of polymeric materials varies with their chemical composition. Films with silicon atoms incorporated in the molecular structures have large coefficients of thermal expansion. This limits their utility. In an alternative approach additives were sought that mix physically and form a protective oxide layer when the film is exposed to AO. A large number of organic compounds containing silicon, germanium, or tin atoms were screened. Most were found to have very limited solubility in the polyetherimide (Ultem) films that were being protected from AO. However, one, bis(triphenyl tin) oxide, (BTO), is miscible in Ultem up to about 25 percent. Films of Ultem polyimide containing up to 25 wt percent BTO were prepared by evaporation of solvent from a solution of Ultem and BTO. The effects of AO on these films were simulated in the oxygen atmosphere of a radio frequency glow-discharge chamber. In the second part of this study, atoms were incorporated in epoxy resins. Experiments are in progress to measure the resistance of films of the cured epoxy to AO in the discharge chamber.

  4. Chemical recycling of scrap composites

    Allred, Ronald E.; Salas, Richard M.


    There are no well-developed technologies for recycling composite materials other than grinding to produce fillers. New approaches are needed to reclaim these valuable resources. Chemical or tertiary recycling, conversion of polymers into low molecular weight hydrocarbons for reuse as chemicals or fuels, is emerging as the most practical means for obtaining value from waste plastics and composites. Adherent Technologies is exploring a low-temperature catalytic process for recycling plastics and composites. Laboratory results show that all types of plastics, thermosets as well as thermoplastics, can be converted in high yields to valuable hydrocarbon products. This novel catalytic process runs at 200 C, conversion times are rapid, the process is closed and, thus, nonpolluting, and no highly toxic gas or liquid products have been observed so no negative environmental impact will result from its implementation. Tests on reclamation of composite materials show that epoxy, imide, and engineering thermoplastic matrices can be converted to low molecular weight hydrocarbons leaving behind the reinforcing fibers for reuse as composite reinforcements in secondary, lower-performance applications. Chemical recycling is also a means to dispose of sensitive or classified organic materials without incineration and provides a means to eliminate or reduce mixed hazardous wastes containing organic materials.

  5. Shape-morphing composites with designed micro-architectures

    Rodriguez, Jennifer N.; Zhu, Cheng; Duoss, Eric B.; Wilson, Thomas S.; Spadaccini, Christopher M.; Lewicki, James P.


    Shape memory polymers (SMPs) are attractive materials due to their unique mechanical properties, including high deformation capacity and shape recovery. SMPs are easier to process, lightweight, and inexpensive compared to their metallic counterparts, shape memory alloys. However, SMPs are limited to relatively small form factors due to their low recovery stresses. Lightweight, micro-architected composite SMPs may overcome these size limitations and offer the ability to combine functional properties (e.g., electrical conductivity) with shape memory behavior. Fabrication of 3D SMP thermoset structures via traditional manufacturing methods is challenging, especially for designs that are composed of multiple materials within porous microarchitectures designed for specific shape change strategies, e.g. sequential shape recovery. We report thermoset SMP composite inks containing some materials from renewable resources that can be 3D printed into complex, multi-material architectures that exhibit programmable shape changes with temperature and time. Through addition of fiber-based fillers, we demonstrate printing of electrically conductive SMPs where multiple shape states may induce functional changes in a device and that shape changes can be actuated via heating of printed composites. The ability of SMPs to recover their original shapes will be advantageous for a broad range of applications, including medical, aerospace, and robotic devices.

  6. (E-2-((4R,5R-5-((Benzyloxymethyl-2,2-dimethyl-1,3-dioxolan-4-ylbut-2-ene-1,4-diol

    Carlos R. Carreras


    Full Text Available The synthesis of (E-2-((4R,5R-5-((benzyloxymethyl-2,2-dimethyl-1,3-dioxolan-4-ylbut-2-ene-1,4-diol by a one-step reduction of the appropriate 2-substituted butenolide is reported. Product characterization was carried out by IR, 1H NMR, 13C NMR, MS, elemental analysis and optical rotation.

  7. Cork suberin molecular structure: stereochemistry of the C18 epoxy and vic-diol ω-hydroxyacids and α,ω-diacids analyzed by NMR.

    Santos, Sara; Cabral, Vanessa; Graça, José


    Suberin is the biopolyester that protects the secondary tissues of plants against environmental variability and aggressions. Cork suberin is composed mostly of C18 ω-hydroxyacids and α,ω-diacids, 9,10-substituted with an unsaturation, an epoxide ring, or a vic-diol group. Although determinant for suberin macromolecular structure, the stereochemistry of these monomers is poorly studied, sometimes with contradictory results. An NMR technique was used here to assign the configuration of the 9,10-epoxy and 9,10-diol groups in C18 suberin acids, comparing the chemical shifts of diagnostic (1)H and (13)C signals with the ones of model compounds, before and after conversion of the vic-diol group into benzylidene acetal derivatives. The relative configuration was proved to be cis in the C18 9,10-epoxy and threo in the C18 9,10-diol suberin acids. These monomers were present in suberin probably as racemic mixtures, as shown by polarimetry. The revealed stereochemistry allows the suberin macromolecule to be built as an ordered array of midchain kinked C18 acids, reinforced by intramolecular hydrogen bonding.

  8. Method of controlling a resin curing process. [for fiber reinforced composites

    Webster, Charles Neal (Inventor); Scott, Robert O. (Inventor)


    The invention relates to an analytical technique for controlling the curing process of fiber-reinforced composite materials that are formed using thermosetting resins. The technique is the percent gel method and involves development of a time-to-gel equation as a function of temperature. From this equation a rate-of-gel equation is then determined, and a percent gel is calculated which is the product of rate-of-gel times time. Percent gel accounting is used to control the proper pressure application point in an autoclave cure process to achieve desired properties in a production composite part.

  9. Tribological properties of epoxy composite materials for marine and river transport

    Buketov, A. V.; Maruschak, P. O.; Brailo, N. V.; Akimov, A. V.; Kobelnik, O. S.; Panin, S. V.


    Tribological properties of epoxy composites filled with thermoplastics and dispersed particles under sea water environment were analyzed. It has been revealed that the composition, sliding friction conditions, as well as the marine environment, substantially affect the tribological properties of the materials. The improvement of tribological properties of epoxycomposite thermosetting plastics after their filling with thermoplastic polyamide PA-6 granules under friction in sea water environment has been proved. The recommendations on applying the developed material in friction parts for marine and river transport were formulated.

  10. Effects of 3-beta-diol, an androgen metabolite with intrinsic estrogen-like effects, in modulating the aquaporin-9 expression in the rat efferent ductules

    Hess Rex A


    Full Text Available Abstract Background Fluid homeostasis is critical for normal function of the male reproductive tract and aquaporins (AQP play an important role in maintenance of this water and ion balance. Several AQPs have been identified in the male, but their regulation is not fully comprehended. Hormonal regulation of AQPs appears to be dependent on the steroid in the reproductive tract region. AQP9 displays unique hormonal regulation in the efferent ductules and epididymis, as it is regulated by both estrogen and dihydrotestosterone (DHT in the efferent ductules, but only by DHT in the initial segment epididymis. Recent data have shown that a metabolite of DHT, 5-alpha-androstane-3-beta-17-beta-diol (3-beta-diol, once considered inactive, is also present in high concentrations in the male and indeed has biological activity. 3-beta-diol does not bind to the androgen receptor, but rather to estrogen receptors ER-alpha and ER-beta, with higher affinity for ER-beta. The existence of this estrogenic DHT metabolite has raised the possibility that estradiol may not be the only estrogen to play a major role in the male reproductive system. Considering that both ER-alpha and ER-beta are highly expressed in efferent ductules, we hypothesized that the DHT regulation of AQP9 could be due to the 3-beta-diol metabolite. Methods To test this hypothesis, adult male rats were submitted to surgical castration followed by estradiol, DHT or 3-beta-diol replacement. Changes in AQP9 expression in the efferent ductules were investigated by using immunohistochemistry and Western blotting assay. Results Data show that, after castration, AQP9 expression was significantly reduced in the efferent ductules. 3-beta-diol injections restored AQP9 expression, similar to DHT and estradiol. The results were confirmed by Western blotting assay. Conclusion This is the first evidence that 3-beta-diol has biological activity in the male reproductive tract and that this androgen metabolite has

  11. Characterization of polysulfone-epoxy/amine interphase for bonding themoplastic composites

    Immordino, K.M.; McKnight, S.H.; Gillespie, J.W. Jr. [Univ. of Delaware, Newark, DE (United States)


    Thermoplastic matrix composites offer several advantages over thermoset matrix composites such as higher interlaminar toughness and infinite shelf life and rapid manufacturing. However, traditional welding techniques for joining thermoplastics require intimate contact between the components, localized heating at the interface and moderate consolidation pressure. Assembly tolerances represent a challenge in scaling welding techniques to large structures where any gaps in the bondline may result in overheating and poor joint quality and performance. Thermoset adhesives offer a low pressure solution to fill gaps. However joining thermoplastic composite components with structural thermoset adhesives often requires elaborate surface treatment of the thermoplastic composite adherents. These surface treatments have several limitations in production environments including finite shelf life, cost, and possible restrictions on part size and shape. These limitations may potentially hinder the widespread use of these materials in structural applications. Other methods for enhancing the bond performance are available. Previous work at the authors` institution has shown that adhesion between thermoplastic composites and epoxy-based adhesives is improved in instances where polymer interdiffusion across the interface is suspected. The improved joint performance has been attributed to interfacial diffusion of the adhesive pre-polymers into the thermoplastic material during processing. Upon final cure, bonding is believed to be enhanced through entanglements between the thermoplastic polymer chains and the network structure of the adhesive. Optimization of this bonding process requires an understanding of the rate of diffusion of the adhesive prepolymers into the thermoplastic and the structure and properties of the interfacial region. This paper focuses on the diffusion study.

  12. Highly sensitive determination of 2,4,6-trinitrotoluene and related byproducts using a diol functionalized column for high performance liquid chromatography.

    Burcu Gumuscu

    Full Text Available In this work, a new detection method for complete separation of 2,4,6-trinitrotoluene (TNT; 2,4-dinitrotoluene (2,4-DNT; 2,6-dinitrotoluene (2,6-DNT; 2-aminodinitrotoluene (2-ADNT and 4-aminodinitrotoluene (4-ADNT molecules in high-performance liquid-chromatography (HPLC with UV sensor has been developed using diol column. This approach improves on cost, time, and sensitivity over the existing methods, providing a simple and effective alternative. Total analysis time was less than 13 minutes including column re-equilibration between runs, in which water and acetonitrile were used as gradient elution solvents. Under optimized conditions, the minimum resolution between 2,4-DNT and 2,6-DNT peaks was 2.06. The recovery rates for spiked environmental samples were between 95-98%. The detection limits for diol column ranged from 0.78 to 1.17 µg/L for TNT and its byproducts. While the solvent consumption was 26.4 mL/min for two-phase EPA and 30 mL/min for EPA 8330 methods, it was only 8.8 mL/min for diol column. The resolution was improved up to 49% respect to two-phase EPA and EPA 8330 methods. When compared to C-18 and phenyl-3 columns, solvent usage was reduced up to 64% using diol column and resolution was enhanced approximately two-fold. The sensitivity of diol column was afforded by the hydroxyl groups on polyol layer, joining the formation of charge-transfer complexes with nitroaromatic compounds according to acceptor-donor interactions. Having compliance with current requirements, the proposed method demonstrates sensitive and robust separation.

  13. Universal reaction mechanism of boronic acids with diols in aqueous solution: kinetics and the basic concept of a conditional formation constant.

    Furikado, Yuki; Nagahata, Tomomi; Okamoto, Takuya; Sugaya, Tomoaki; Iwatsuki, Satoshi; Inamo, Masahiko; Takagi, Hideo D; Odani, Akira; Ishihara, Koji


    To establish a detailed reaction mechanism for the condensation between a boronic acid, RB(OH)2, and a diol, H2L, in aqueous solution, the acid dissociation constants (Ka(BL)) of boronic acid diol esters (HBLs) were determined based on the well-established concept of conditional formation constants of metal complexes. The pKa values of HBLs were 2.30, 2.77, and 2.00 for the reaction systems, 2,4-difluorophenylboronic acid and chromotropic acid, 3-nitrophenylboronic acid and alizarin red S, and phenylboronic acid and alizarin red S, respectively. A general and precise reaction mechanism of RB(OH)2 with H2L in aqueous solution, which can serve as a universal reaction mechanism for RB(OH)2 and H2L, was proposed on the basis of (a) the relative kinetic reactivities of the RB(OH)2 and its conjugate base, that is, the boronate ion, toward H2L, and (b) the determined pKa values of HBLs. The use of the conditional formation constant, K', based on the main reaction: RB(OH)2 + H2L (K1)⇌ RB(L)(OH)(-) + H3O(+) instead of the binding constant has been proposed for the general reaction of uncomplexed boronic acid species (B') with uncomplexed diol species (L') to form boronic acid diol complex species (esters, BL') in aqueous solution at pH 5-11: B' + L' (K')⇌ BL'. The proposed reaction mechanism explains perfectly the formation of boronic acid diol ester in aqueous solution. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Synthesis, Properties and Applications of Biodegradable Polymers Derived from Diols and Dicarboxylic Acids: From Polyesters to Poly(ester amides

    Angélica Díaz


    Full Text Available Poly(alkylene dicarboxylates constitute a family of biodegradable polymers with increasing interest for both commodity and speciality applications. Most of these polymers can be prepared from biobased diols and dicarboxylic acids such as 1,4-butanediol, succinic acid and carbohydrates. This review provides a current status report concerning synthesis, biodegradation and applications of a series of polymers that cover a wide range of properties, namely, materials from elastomeric to rigid characteristics that are suitable for applications such as hydrogels, soft tissue engineering, drug delivery systems and liquid crystals. Finally, the incorporation of aromatic units and α-amino acids is considered since stiffness of molecular chains and intermolecular interactions can be drastically changed. In fact, poly(ester amides derived from naturally occurring amino acids offer great possibilities as biodegradable materials for biomedical applications which are also extensively discussed.

  15. Myeloperoxidase - 463A variant reduces benzo(a)pyrene diol epoxide DNA adducts in skin of coal tar treated patients

    Rojas, M.; Godschalk, R.; Alexandrov, K.; Cascorbi, I.; Kriek, E.; Ostertag, J.; Van Schooten, F.J.; Bartsch, H. [German Cancer Research Center, Heidelberg (Germany). Div. of Toxicology & Cancer Risk Factors


    The skin of atopic dermatitis patients provides an excellent model to study the role of inflammation in benzo(a)pyrene (BaP) activation, since these individuals are often topically treated with ointments containing high concentrations of BaP. The authors determined, by HPLC with fluorescence detection, the BaP diol epoxide (BPDE)-DNA adduct levels in human skin after topical treatment with coal tar and their modulation by the -453G into A myeloperoxidase (MPO) polymorphism, which reduces MPO mRNA expression. The data show for the first time: (i) the in vivo formation of BPDE-DNA adducts in human skin treated with coal tar; (ii) that the MPO-463AA/AG genotype reduced BPDE-DNA adduct levels in human skin.

  16. Synthesis of 1,3-Amino Alcohols, 1,3-Diols, Amines, and Carboxylic Acids from Terminal Alkynes.

    Zeng, Mingshuo; Herzon, Seth B


    The half-sandwich ruthenium complexes 1-3 activate terminal alkynes toward anti-Markovnikov hydration and reductive hydration under mild conditions. These reactions are believed to proceed via addition of water to metal vinylidene intermediates (4). The functionalization of propargylic alcohols by metal vinylidene pathways is challenging owing to decomposition of the starting material and catalytic intermediates. Here we show that catalyst 2 can be employed to convert propargylic alcohols to 1,3-diols in high yield and with retention of stereochemistry at the propargylic position. The method is also amenable to propargylic amine derivatives, thereby establishing a route to enantioenriched 1,3-amino alcohol products. We also report the development of formal anti-Markovnikov reductive amination and oxidative hydration reactions to access linear amines and carboxylic acids, respectively, from terminal alkynes. This chemistry expands the scope of products that can be prepared from terminal alkynes by practical and high-yielding metal-catalyzed methods.

  17. Preparation of CoFe2O4/SiO2 Nanocomposites at Low Temperatures Using Short Chain Diols

    Thomas Dippong


    Full Text Available The preparation of 70% CoFe2O4/30% SiO2 (wt% nanocomposites by sol-gel method using three short chain diols (1,2-ethanediol, 1,3-propanediol, and 1,4-butanediol as chelators was studied. The Fourier transformed infrared spectra and X-ray diffraction patterns were used to confirm the formation of nanocomposites. The X-ray diffraction analysis showed that the chain length of the carboxylates embedded in the silica matrix influences the formation of crystallized cobalt ferrite as single phase at low temperatures. The influence of the methylene groups number in the precursors and annealing temperature on the nanocrystallite size was revealed. The stability of the obtained compounds was determined by calculation of thermodynamic parameters.

  18. Application of high-strength biodegradable polyurethanes containing different ratios of biobased isomannide and poly (ϵ-caprolactone) diol.

    Lim, Dong-In; Park, Hyung-Seok; Park, Jeong-Hui; Knowles, Jonathan C; Gong, Myoung-Seon


    Biodegradable-biocompatible polyurethanes were prepared with fixed hexamethylene diisocyanate and varying ratios of isomannide and poly(ϵ-caprolactone) diol using a simple one-step polymerization without a catalyst. The polyurethane structures were confirmed by (1)H-nuclear magnetic resonance, Fourier transform infrared spectroscopy, and gel permeation chromatography. The glass transition temperatures were determined by thermal analysis to be between 25°C and 30°C. Degradation tests performed at 37°C in phosphate buffer produced mass losses of 5%-10% after 8 weeks. After 5 days of culture, using osteoblastic cells, the relative cell number on all the polyurethane films was only slightly lower than that of an optimized tissue culture plastic. These polymers offer significant promise with a simplistic synthesis and controlled degradation.

  19. Selective monoprotection of 1,n-terminal Diols in supercritical carbon dioxide: a striking example of solvent tunable desymmetrization.

    Licence, Peter; Gray, William K; Sokolova, Maia; Poliakoff, Martyn


    The reaction between 1,n-terminal diols (n = 3 or 6) with simple alcohols (MeOH, EtOH, and n-PrOH) in supercritical CO(2) over an acid catalyst (Amberlyst 15) leads to two possible products, a mono- and a bis-ether. At 150 degrees C, the selectivity of the reaction with 1,6-hexanediol and MeOH can be switched from 1:20 in favor of the bis-ether at 50 bar to 9:1 in favor of the desymmetrized mono-ether at 200 bar. It is demonstrated that the switch in selectivity is associated with the phase state of the reaction mixture, with monophasic conditions favoring the mono-ether and biphasic conditions favoring the bis-ether. A rationalization of this effect is also presented.

  20. Di-μ-bromido-bis-[bromido(di-2-pyridylmethane-diol-κN,N')copper(II)] dihydrate.

    Westcott, Barry L; Kopp-Vaughn, Kristin M; Daniels, Lee M; Zeller, Matthias


    The centrosymmetric title complex, [Cu(2)Br(4)(C(11)H(10)N(2)O(2))(2)]·2H(2)O, was one of three complexes isolated by slow evaporation of an acetonitrile reaction mixture of CuBr(2) with di-2-pyridyl ketone (1:1 molar ratio). The title complex contains a 1:1 metal-to-ligand ratio of copper(II) with the hydrated form of the ligand di-2-pyridylmethane-diol. The copper centers are bridged by bromide donors, leading to a Cu-Cu distance of 4.090 (6) Å. The crystals form as non-merohedral twins with two components related by a 180° rotation around the normal to [100]; the selected sample had a twin ratio of 0.63:0.37.

  1. Synthesis, Characterizations and Investigation of Electrochemical Behaviours of 4-[(2-Hydroxyphenyliminomethyl]benzene-1,3-diol

    Aysen D. Mulazimoglu


    Full Text Available This Schiff base ligand, 4-[(2-hydroxyphenylimino methyl]benzene-1,3-diol (HIBD was synthesized by reaction of 2-aminophenol and 2,4-dihydroxybenzaldehyde. The ligand was characterized by elemental analysis, FT-IR and 1H-NMR. Electrochemical behaviors were investigated on the glassy carbon electrode (GC surface with cyclic voltammetry (CV. The modification of HIBD on the GC was performed in +0.3 V and +2,8 V potential range using 100 mV s-1 scanning rate having 5 cycle. For the characterization of the modified surfaces 1 mM ferrocene redox probe in 0,1 M tetrabutylammonium tetrafluoroborate (TBATFB and 1 mM ferricyanide redox probe in 0.1 M H2SO4 were used.

  2. Formation and reduction of 3-monochloropropane-1,2-diol esters in peanut oil during physical refining.

    Li, Chang; Li, Linyan; Jia, Hanbing; Wang, Yuting; Shen, Mingyue; Nie, Shaoping; Xie, Mingyong


    In the present study, lab-scale physical refining processes were investigated for their effects on the formation of 3-monochloropropane-1,2-diol (3-MCPD) esters. The potential precursors, partial acylglycerols and chlorines were determined before each refining step. 3-MCPD esters were not detected in degummed and bleached oil when the crude oils were extracted by solvent. While in the hot squeezed crude oils, 3-MCPD esters were detected with low amounts. 3-MCPD esters were generated with maximum values in 1-1.5h at a certain deodorizing temperature (220-260°C). Chlorine seemed to be more effective precursor than partial acylglycerol. By washing bleached oil before deodorization with ethanol solution, the precursors were removed partially and the content of 3-MCPD esters decreased to some extent accordingly. Diacetin was found to reduce 3-MCPD esters effectively.

  3. Highly conductive, multi-layer composite precursor composition to fuel cell flow field plate or bipolar plate

    Jang, Bor Z.; Zhamu, Aruna; Guo, Jiusheng


    This invention provides a moldable, multiple-layer composite composition, which is a precursor to an electrically conductive composite flow field plate or bipolar plate. In one preferred embodiment, the composition comprises a plurality of conductive sheets and a plurality of mixture layers of a curable resin and conductive fillers, wherein (A) each conductive sheet is attached to at least one resin-filler mixture layer; (B) at least one of the conductive sheets comprises flexible graphite; and (C) at least one resin-filler mixture layer comprises a thermosetting resin and conductive fillers with the fillers being present in a sufficient quantity to render the resulting flow field plate or bipolar plate electrically conductive with a conductivity no less than 100 S/cm and thickness-direction areal conductivity no less than 200 S/cm.sup.2.

  4. Studies on synthesis and activation mechanism of mitomycin dimers connected by 1,2-dithiolane and diol linkers.

    Kim, Hyoung Rae; Kim, Jae Jin; Park, Jung Jae; Lee, Sang Hyup


    We report the synthetic and mechanistic studies on a new cyclic disulfide mitomycin dimer, 7-N,7'-N'-(1″,2″-dithiolanyl-3″,5″-dimethylenyl)bismitomycin C (8), and a diol mitomycin dimer, 7-N,7'-N'-(2″,4″-dihydroxy-1″,5″-pentanediyl)bismitomycin C (9). Mitomycin 8 is a dimer connected by a 1,2-dithiolane (a five-membered cyclic disulfide) linker, and was specifically designed to undergo nucleophilic activation and double DNA alkylations leading to efficient production of DNA interstrand cross-link (DNA ISC) adducts. Disulfide cleavage in 8 would generate two thiol groups that could serve as probes to activate two mitomycin rings. At first, the target mitomycin 8 was synthesized using mitomycin A (1) and the key intermediate, cyclic disulfide (10), which was prepared through a seven-step synthetic sequence. Diol mitomycin 9 was also synthesized from 1 and diamine salt 13. Next, kinetic studies using solvolysis reaction revealed that the activation rates of 8 were much higher than those of 9 and mitomycin C (2) under nucleophilic conditions provided by Et(3)P presumably due to the presence of a cyclic disulfide unit in 8. These findings led us to propose a nucleophilic activation pathway for 8. Then, DNA ISC experiments further revealed that the levels of DNA ISC caused by 8 in the presence of Et(3)P were much higher (97%) than those by 9 (5%) and 2 (4%). More importantly, mitomycin 8 underwent much faster activation and produced slightly higher levels of DNA ISC than the previously reported mitomycins 5-7. Overall, we concluded that 8 was highly efficient for both nucleophilic activation and corresponding DNA ISC formation, and that this differentiation came from the crucial function of the cyclic disulfide unit in 8.

  5. Investigations of the mechanical properties of bi-layer and trilayer fiber reinforced composites

    Jayakrishna, K.; Balasubramani, K.; Sultan, M. T. H.; Karthikeyan, S.


    Natural fibers are renewable raw materials with an environmental-friendly properties and they are recyclable. The mechanical properties of bi-layer and tri-layer thermoset polymer composites have been analyzed. The bi-layer composite consists of basalt and jute mats, while the tri-layer composite consists of basalt fiber, jute fiber and glass fiber mats. In both cases, the epoxy resin was used as the matrix and PTFE as a filler in the composites. The developed trilayer natural fiber composite can be used in various industrial applications such as automobile parts, construction and manufacturing. Furthermore, it also can be adopted in aircraft interior decoration and designed body parts. Flexural, impact, tensile, compression, shear and hardness tests, together with density measurement, were conducted to study the mechanical properties of both bi-layer and tri-layer composites. From the comparison, the tri-layer composite was found to perform in a better way in all tests.

  6. Intelligent Molding Proceeding of Composites and Intelligent Manufacturing Systems for Composite Materials


    The technology of Intelligent cure operation is set forth according to developing tedency of smart material and structure. Intelligent-sy s tem-based tool was developed in order to operate the autoclave cure of a fiber r einforced thermosetting matrix composite laminate in an optimal manner.The objec tive function is comforts for minimizing the total cure time,uniforming the tem perature distribution,controling exothermal and minimizing the process-induced r esidual stresses in the laminate.Data is analyzed on-line to determine the t r ends in real-time. The results from application of this overall strategy for the curing of composites are presented.

  7. Fractography of composite delamination

    Bascom, W. D.


    The microdamage that occurs for Mode 1 and Mode 2 delamination was examined by potting delaminated specimens in a clear epoxy, sectioning through the damage, polishing the cut sections and examining using light microscopy. For Mode 1 delamination of unidirectional carbon fiber reinforced plastic (CFRP) composites, the major observation was fiber bridging including large ligaments of fiber bundles. The Mode 2 delamination of unidirectional laminates revealed a very narrow crack opening with only occasional fiber bridging. Impact testing by repetitive impacts with increasing energy was studied and it was found that this technique does not discern changes in the type of damage with increasing cumulative impact energy. Instead, the changes in the impact response, notably stiffness, are the result of changes in the extent of damage. For laminates with a brittle thermoplastic matrix, 3501-6, there were distinct changes in stiffness that corresponded to the development of through the thickness damage and then to the extension of the damage to the specimen edges. For PEEK and polycarbonate, the changes in stiffness were not as abrupt as for the thermoset. None the less, the damage progressed in the same manner.

  8. Epoxy/anhydride thermosets modified with end-capped star polymers with poly(ethyleneimine cores of different molecular weight and poly(ε–caprolactone arms

    C. Acebo


    Full Text Available Multiarm star polymers, with a hyperbranched poly(ethyleneimine (PEI core and poly(ε-caprolactone (PCL arms end-capped with acetyl groups were synthesized by ring-opening polymerization of ε-caprolactone from PEI cores of different molecular weight. These star polymers were used as toughening agents for epoxy/anhydride thermosets. The curing process was studied by calorimetry, thermomechanical analysis and infrared spectroscopy. The final properties of the resulting materials were determined by thermal and mechanical tests. The addition of the star polymers led to an improvement up to 130% on impact strength and a reduction in the thermal stresses up to 55%. The structure and molecular weight of the modifier used affected the morphology of the resulting materials. Electron microscopy showed phase-separated morphologies with nano-sized fine particles well adhered to the epoxy/anhydride matrix when the higher molecular weight modifier was used.

  9. Thiol-ene thermosets exploiting surface reactivity for layer-by-layer structures and control of penetration depth for selective surface reactivity

    Daugaard, Anders Egede; Westh, Andreas; Pereira Rosinha Grundtvig, Ines

    Thiol-ene thermosets have been shown to be an efficient platform for preparation of functional polymer surfaces. Especially the effectiveness and versatility of the system has enabled a large variety of network properties to be obtained in a simple and straight-forward way. Due to its selectivity...... properties across freestanding samples is presented. The appraoch is further exploited for preparation of surface structures down to features of 25 µm scale by use of an absorber and simple masking.The combination of masking and absorbers were similarly used to prepare a reactor with controlled surface...... properties as shown in Figure 1. Here fully sealed reactors (Figure 1a) were prepared modularly by a combination of thiol-ene and thiol-epoxy curing reactions. The reactors were functionalized in different patterns on the top side of the assembled reactor, illustrating the effectiveness of absorbers...

  10. Advanced Thermoset Nanocomposites Project

    National Aeronautics and Space Administration — Low-cost, environmentally compatible synthesis methods are used to prepare silicate nanoparticles with surface areas, surface polarity and hierarchical lamellar and...

  11. 碳酸乙二酯与二醇反应制备聚碳酸酯二元醇%Synthesis of Polycarbonate Diol Through the Reaction of Ethylene Carbonate with Diol

    李金丽; 周宏勇; 李云庆; 王家喜


    A series of linear aliphatic polycarbonate diols (APC) with defined structure were synthesized by using ethylene carbonate (EC), 1,4-butanediol, and 1,6-hexanediol as the raw materials promoted by zinc acetate or zinc nitrate. The effect of reaction temperature, time and the amount of catalyst on the structure and number average molecular weight of polycarbonate was investigated. The structures and number average molecular weight were characterized and calculated by means of NMR spectroscopy. The number average molecular weight (Mn) of polycarbonate with l]-hydroxylethyl and/or c0-hydroxylalkyl as end groups is in range of 300 to 560 for reaction of 1, 4-butanediol and 700 to 980 for reaction of 1,6-hexanediol. The ether unit from the reaction of 1,4-butandiol can be less than 3%(mol). While the ether unit from the reaction of 1,6-hexandiol can be less up to 0.24% (tool). The reaction mechanism of ethylene carbonate with diol is proposed.%以碳酸乙二酯、1,4-丁二醇和1,6-己二醇为原料,醋酸锌、硝酸锌为催化剂,考察了反应温度、反应时间等条件对碳酸乙二酯与二元醇反应的影响,制备出结构规整的以β-羟乙基、ω-羟烷氧基为端基的聚碳酸酯二元醇。产物经核磁共振波谱表征,1,4-丁二醇反应的聚碳酸酯二元醇的数均分子量为300-560,产物中由脱羰基反应形成的醚键链段含量可小于3%,1,6-己二醇反应的聚碳酸酯二元醇的数均分子量为700-980,产物中醚键链段含量可降低至0.24%。最后探讨了碳酸乙二酯与二元醇的反应机理。


    Post, Brian K [ORNL; Love, Lonnie J [ORNL; Duty, Chad [University of Tennessee (UTK) and Oak Ridge National Laboratory (ORNL); Vaidya, Uday [University of Tennessee, Knoxville (UTK); Pipes, R. Byron [Purdue University; Kunc, Vlastimil [ORNL


    Oak Ridge National Laboratory s Big Area Additive Manufacturing (BAAM) technology permits the rapid production of thermoplastic composite molds using a carbon fiber filled Acrylonitrile-Butadiene-Styrene (ABS) thermoplastic. Demonstration tools (i.e. 0.965 m X 0.559 m X 0.152 m) for composite part fabrication have been printed, coated, and finished with a traditional tooling gel. We present validation results demonstrating the stability of thermoplastic printed molds for room temperature Vacuum Assisted Resin Transfer Molding (VARTM) processes. Arkema s Elium thermoplastic resin was investigated with a variety of reinforcement materials. Experimental results include dimensional characterization of the tool surface using laser scanning technique following demolding of 10 parts. Thermoplastic composite molds offer rapid production compared to traditionally built thermoset molds in that near-net deposition allows direct digital production of the net geometry at production rate of 45 kg/hr.

  13. Recycling solid residues recovered from glass fibre-reinforced composites – A review applied to wind turbine blade materials

    Beauson, Justine; Lilholt, Hans; Brøndsted, Povl


    to face large amount of future wind turbine (WT) blades coming to EoL. Among the EoL solutions available for WT blades, i.e. reuse, remanufacturing, recycling, incineration or disposal, this literature review focuses on recycling and particularly the recycling of shredded composite (SC) materials...... and recovered glass fibre (GF) into new polymer composite. WT blades are mainly made of glass fibre reinforced polymer (GFRP) using thermosetting resins. Shredding this material and recovering GF are possible recycling solutions for WT blade. Based on a detailed literature review, the formulations of new...

  14. Effect of natural fibers and bio-resins on mechanical properties in hybrid and non-hybrid composites

    Fragassa, Cristiano


    The aim of the present experimental investigation was to perform a comparative analysis concerning the influence on mechanical properties of natural fibers and/or bio-resins in reinforced thermoset composites. Flax and basalt fibers were selected as natural reinforcements, as single constituents or in hybrid combination. Glass synthetic fibers were used for comparison. Eco-friendly matrixes, both epoxy or vinylester, were considered and compared with composites based on traditional resins. Samples were fabricated by hand lay-up and resin infusion techniques. Cures were accelerated and controlled by applying heat and pressure in autoclave. Tensile, flexural and impact tests were carried out according to ASTM standards.

  15. Experimental Study of Monitoring and Controlling of Composite Cure Process in Autoclave Featured with Fiber Optic Sensor


    With the aid of the latest fiber optic sensing technology, parameters in the cure process of thermosetting resin-matrix composite, such as temperature, viscosity, void and residual stress, can be monitored entirely and efficiently. In this paper, experiment results of viscosity measurement in composite cure process in autoclave using fiber optic sensors are presented. Based on the sensed information, a computer program is utilized to control the cure process. With this technology,the cure process becomes more apparent and controllable, which will greatly improve the cured products and reduce the cost.

  16. Phase behavior and crystal structure of 3-(1-naphthyloxy)- and 3-(4-indolyloxy)-propane-1,2-diol, synthetic precursors of chiral drugs propranolol and pindolol

    Bredikhin, Alexander A.; Gubaidullin, Aidar T.; Bredikhina, Zemfira A.; Fayzullin, Robert R.; Samigullina, Aida I.; Zakharychev, Dmitry V.


    Valuable precursors of popular chiral drugs propranolol and pindolol, 3-(1-naphthyloxy)-propane-1,2-diol 3 and 3-(4-indolyloxy)-propane-1,2-diol 4 were investigated by IR spectroscopy, DSC, and X-ray diffraction methods. Both compounds, crystallizing from enantiopure feed material, form "guaifenesin-like" crystal packing in which the classic H-bonded bilayers, framed in both sides by hydrophobic fragments of the molecules, acts as the basic crystal-forming motif. Diol 4 prone to spontaneous resolution and conserves its packing pattern crystallizing from racemate. Under the same conditions, diol 3 forms weakly stable solid racemic compound. Some reasons for such a behavior are identified and discussed.

  17. N-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-ylacetamide–naphthalene-2,3-diol (1/1

    Abdullah M. Asiri


    Full Text Available In the reaction of naphthalene-2,3-diol and 4-aminoantipyrine in the presence of acetic acid, the amine function is acetylated and the resulting acetamide co-crystallizes with the diol in the title compound, C13H15N3O2·C10H8O2, with 1:1 molar stoichiometry. The two components are linked by two O–H...O=C hydrogen bonds. One of the hydroxy groups interacts with the pyrazolone carbonyl O atom and the other hydroxy group interacts with the amide O atom of another component, generating a chain motif. Adjacent chains are linked into a layer motif via N—H...O interactions involving only the heterocyclic acetamide component.

  18. Microwave-Assisted Kinetic Resolution of Homochiral (Z-Cyclooct-5-ene-1,2-diol and (Z-2-Acetoxycyclooct-4-enyl Acetate Using Lipases

    Hervé Rouillard


    Full Text Available Over the last decade, the use of biocatalysts has become an attractive alternative to conventional chemical methods, especially for organic synthesis, due to their unusual properties. Among these enzymes, lipases are the most widely used, because they are cheap, easily available, cofactor-free, and have broad substrate specificity. Combined to microwave heating in non-aqueous medium, recent results suggest that irradiation may influence the enzyme activity. This Communication reports the benefits of lipases and the microwave irradiation on the kinetic resolution of racemic homochiral (Z-cyclooct-5-ene-1,2-diol and (Z-2-acetoxycyclooct-4-enyl acetate. In order to best achieve the kinetic resolution, different parameters were studied including the type of lipase, the temperature, the impact of microwave power compared to conventional heating. Optimization of the reaction parameters lead to the obtainment of highly enriched or enantiopure diols and diesters in a clean, efficient and safe way.

  19. TEM and SEM observations of super-structures constructed in organogel systems from a combination of boronic-acid-appended bola-amphiphiles with chiral diols

    Koumoto, Kazuya; Yamashita, Tadahiro; Kimura, Taro; Luboradzki, Roman; Shinkai, Seiji


    Two bola-amphiphilic α,ω-diboronic acids separated by a (CH2)11 or (CH2)12 group were synthesized. Complexation with chiral diols readily gave new amphiphiles end-capped with the chiral substituents. Some of these acted as good gelators of organic solvents. Transmission electron microscope and scanning electron microscope observations established that a variety of super-structures are created in the organogels, depending on the solvents and the structure of the chiral end-cap groups. In most cases, the fibrous aggregates, the network structure which is the driving-force for gelation, showed a helical higher-order structure reflecting the chirality of the end-cap groups. The results indicate that the combinatorial approach utilizing boronic acid functions and diol compounds is useful in creating a variety of new super-structures in the gel phase.

  20. Supramolecular Arrangement in Styphnic Acid and Naphthalene-1,4-diol (1 : 1 through a Novel Synthetic Rote for Styphnic Acid

    Moamen S. Refat


    Full Text Available The chemical preparation and crystal structure of styphnic acid and naphthalene-1,4-diol (1 : 1 (I have been reported. The compound crystallizes in the orthorhombic system in space group Pnma and cell parameters a=6.6712(2, b=16.8267(7, c=13.6450(5 Å and V=1531.71(10 Å3, and Z=4. Crystal structure has been determined and refined to R=0.0576. The crystal structure of I, the asymmetric unit, contains C6H2N3O7, C10H7O, and it is a half portion of both styphnic acid and naphthalene-1,4-diol. The O1–H1⋯O2 intramolecular hydrogen bond was found between the O–H and a nitro group in the styphnic acid unit.

  1. QSPR models based on molecular mechanics and quantum chemical calculations. 1. Construction of Boltzmann averaged descriptors for alkanes, alcohols, diols, ethers and cyclic compounds

    Dyekjær, Jane Dannow; Rasmussen, Kjeld; Jonsdottir, Svava Osk


    Values for nine descriptors for QSPR (quantitative structure-property relationships) modeling of physical properties of 96 alkanes, alcohols, ethers, diols, triols and cyclic alkanes and alcohols in conjunction with the program Codessa are presented. The descriptors are Boltzmann-averaged by sele...... der Waals energies and the molecular polarizabilities, which correlate very well with boiling points. Five more simple descriptors that only depend on the molecular constitutional formula are also discussed briefly....

  2. Carbonate phosphonium salts as catalysts for the transesterification of dialkyl carbonates with diols. The competition between cyclic carbonates and linear dicarbonate products.

    Selva, Maurizio; Caretto, Alessio; Noè, Marco; Perosa, Alvise


    At 90-120 °C, in the presence of methylcarbonate and bicarbonate methyltrioctylphosphonium salts as catalysts ([P8881][A]; [A] = MeOCO2 and HOCO2), the transesterification of non-toxic dimethyl- and diethyl-carbonate (DMC and DEC, respectively) with 1,X-diols (2 ≤ X ≤ 6) proceeds towards the formation of cyclic and linear products. In particular, 1,2-propanediol and ethylene glycol afford propylene- and ethylene-carbonate with selectivity and yields up to 95 and 90%, respectively; while, the reaction of DMC with higher diols such 1,3-butanediol, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol produce linear C8-C10 dicarbonates of general formula MeOC(O)O∼∼∼OC(O)OMe as the almost exclusive products. Of note, these dicarbonate derivatives are not otherwise accessible in good yields by other conventional base catalyzed methods. Among 1,3-diols, the only exception was 2-methyl 2,4-pentandiol that yields the corresponding cyclic carbonate, i.e. 4,4,6-trimethyl-1,3-dioxan-2-one. In no one case, polycarbonates are observed. Such remarkable differences of product distributions are ascribed to the structure (branching and relative position of OH groups) of diols and to the role of cooperative (nucleophilic and electrophilic) catalysis which has been proved for onium salts. The investigated carbonate salts are not only effective in amounts as low as 0.5 mol%, but they are highly stable and recyclable.

  3. (R,R)-Butane-2,3-diol dehydrogenase from Bacillus clausii DSM 8716(T): Cloning and expression of the bdhA-gene, and initial characterization of enzyme.

    Muschallik, Lukas; Molinnus, Denise; Bongaerts, Johannes; Pohl, Martina; Wagner, Torsten; Schöning, Michael J; Siegert, Petra; Selmer, Thorsten


    The gene encoding a putative (R,R)-butane-2,3-diol dehydrogenase (bdhA) from Bacillus clausii DSM 8716(T) was isolated, sequenced and expressed in Escherichia coli. The amino acid sequence of the encoded protein is only distantly related to previously studied enzymes (identity 33-43%) and exhibited some uncharted peculiarities. An N-terminally StrepII-tagged enzyme variant was purified and initially characterized. The isolated enzyme catalyzed the (R)-specific oxidation of (R,R)- and meso-butane-2,3-diol to (R)- and (S)-acetoin with specific activities of 12U/mg and 23U/mg, respectively. Likewise, racemic acetoin was reduced with a specific activity of up to 115U/mg yielding a mixture of (R,R)- and meso-butane-2,3-diol, while the enzyme reduced butane-2,3-dione (Vmax 74U/mg) solely to (R,R)-butane-2,3-diol via (R)-acetoin. For these reactions only activity with the co-substrates NADH/NAD(+) was observed. The enzyme accepted a selection of vicinal diketones, α-hydroxy ketones and vicinal diols as alternative substrates. Although the physiological function of the enzyme in B. clausii remains elusive, the data presented herein clearly demonstrates that the encoded enzyme is a genuine (R,R)-butane-2,3-diol dehydrogenase with potential for applications in biocatalysis and sensor development. Copyright © 2017. Published by Elsevier B.V.

  4. 3D-Printing of Meso-structurally Ordered Carbon Fiber/Polymer Composites with Unprecedented Orthotropic Physical Properties

    Lewicki, James P.; Rodriguez, Jennifer N.; Zhu, Cheng; Worsley, Marcus A.; Wu, Amanda S.; Kanarska, Yuliya; Horn, John D.; Duoss, Eric B.; Ortega, Jason M.; Elmer, William; Hensleigh, Ryan; Fellini, Ryan A.; King, Michael J.


    Here we report the first example of a class of additively manufactured carbon fiber reinforced composite (AMCFRC) materials which have been achieved through the use of a latent thermal cured aromatic thermoset resin system, through an adaptation of direct ink writing (DIW) 3D-printing technology. We have developed a means of printing high performance thermoset carbon fiber composites, which allow the fiber component of a resin and carbon fiber fluid to be aligned in three dimensions via controlled micro-extrusion and subsequently cured into complex geometries. Characterization of our composite systems clearly show that we achieved a high order of fiber alignment within the composite microstructure, which in turn allows these materials to outperform equivalently filled randomly oriented carbon fiber and polymer composites. Furthermore, our AM carbon fiber composite systems exhibit highly orthotropic mechanical and electrical responses as a direct result of the alignment of carbon fiber bundles in the microscale which we predict will ultimately lead to the design of truly tailorable carbon fiber/polymer hybrid materials having locally programmable complex electrical, thermal and mechanical response.

  5. 3D-Printing of Meso-structurally Ordered Carbon Fiber/Polymer Composites with Unprecedented Orthotropic Physical Properties

    Lewicki, James P.; Rodriguez, Jennifer N.; Zhu, Cheng; Worsley, Marcus A.; Wu, Amanda S.; Kanarska, Yuliya; Horn, John D.; Duoss, Eric B.; Ortega, Jason M.; Elmer, William; Hensleigh, Ryan; Fellini, Ryan A.; King, Michael J.


    Here we report the first example of a class of additively manufactured carbon fiber reinforced composite (AMCFRC) materials which have been achieved through the use of a latent thermal cured aromatic thermoset resin system, through an adaptation of direct ink writing (DIW) 3D-printing technology. We have developed a means of printing high performance thermoset carbon fiber composites, which allow the fiber component of a resin and carbon fiber fluid to be aligned in three dimensions via controlled micro-extrusion and subsequently cured into complex geometries. Characterization of our composite systems clearly show that we achieved a high order of fiber alignment within the composite microstructure, which in turn allows these materials to outperform equivalently filled randomly oriented carbon fiber and polymer composites. Furthermore, our AM carbon fiber composite systems exhibit highly orthotropic mechanical and electrical responses as a direct result of the alignment of carbon fiber bundles in the microscale which we predict will ultimately lead to the design of truly tailorable carbon fiber/polymer hybrid materials having locally programmable complex electrical, thermal and mechanical response. PMID:28262669

  6. Preliminary neutron and ultrahigh-resolution X-ray diffraction studies of the aspartic proteinase endothiapepsin cocrystallized with a gem-diol inhibitor

    Tuan, Han-Fang [Spallation Neutron Source, Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge, TN 37831 (United States); Erskine, Peter [Laboratory for Protein Crystallography, Centre for Amyloidosis and Acute Phase Proteins, UCL Department of Medicine (Hampstead Campus), Rowland Hill Street, London NW3 2PF (United Kingdom); Langan, Paul [Bioscience Division, Mailstop M888, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Department of Chemistry, University of Toledo, Toledo, OH 53606 (United States); Cooper, Jon [Laboratory for Protein Crystallography, Centre for Amyloidosis and Acute Phase Proteins, UCL Department of Medicine (Hampstead Campus), Rowland Hill Street, London NW3 2PF (United Kingdom); Coates, Leighton, E-mail: [Spallation Neutron Source, Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge, TN 37831 (United States); Department of Chemistry, University of Toledo, Toledo, OH 53606 (United States)


    Three data sets have been collected on endothiapepsin complexed with the gem-diol inhibitor PD-135,040: a high-resolution synchrotron X-ray data set, a room-temperature X-ray data set and a neutron diffraction data set. Until recently, it has been impossible to grow large protein crystals of endothiapepsin with any gem-diol inhibitor that are suitable for neutron diffraction. Endothiapepsin has been cocrystallized with the gem-diol inhibitor PD-135,040 in a low solvent-content (39%) unit cell, which is unprecedented for this enzyme–inhibitor complex and enables ultrahigh-resolution (1.0 Å) X-ray diffraction data to be collected. This atomic resolution X-ray data set will be used to deduce the protonation states of the catalytic aspartate residues. A room-temperature neutron data set has also been collected for joint refinement with a room-temperature X-ray data set in order to locate the H/D atoms at the active site.

  7. Unraveling the adsorption mechanism of aromatic and aliphatic diols on the TiO2 surface: a density functional theory analysis.

    Giorgi, Giacomo; Fujisawa, Jun-ichi; Segawa, Hiroshi; Yamashita, Koichi


    Understanding the adsorption mechanism of organic molecules on inorganic semiconductors is of great importance for generating and control functions in organic-inorganic materials. Here we have comprehensively investigated, by means of the density functional theory, the adsorption structure and energetic stability of aliphatic and aromatic diols on TiO2 using ethylene glycol, 1,2-n-decanediol, and catechol. Our calculations clearly show that the non-dissociative bidentate adsorption is more stable than the dissociative one for the aliphatic diol, both at low and high coverage conditions, result far differently from many other chemical anchor cases for which the dissociative mechanism usually prevails. On the other hand, for catechol the dissociative bidentate is the most stable at low coverage conditions, whereas, surprisingly, increasing the coverage with catechol makes the non-dissociative mechanism the most stable one, revealing possible coexistence of a dissociative and non-dissociative anchoring at high coverage. This work unraveled a variety of adsorption fashions of the diol compounds in conjunction with the impact of the coverage effect, highly dependent on the nature of the lateral chain of the anchor group.

  8. Carbon fiber resin matrix interphase: effect of carbon fiber surface treatment on composite performance

    Lehmann, S.; Megerdigian, C.; Papalia, R.


    Carbon fibers are supplied by various manufacturers with a predetermined level of surface treatment and matrix compatible sizings. Surface treatment of the carbon fiber increases the active oxygen content, the polarity and the total free surface energy of the fiber surface. This study is directed toward determining the effect of varying carbon fiber surface treatment on the composite performance of thermoset matrix resins. The effect of varying fiber surface treatment on performance of a promising proprietary sizing is also presented. 6 references, 11 figures.

  9. Hard and soft computing models of composite curing process looking toward monitoring and control

    Rubino, F.; Carlone, P.; Aleksendrić, D.; Ćirović, V.; Sorrentino, L.; Bellini, C.


    The curing process of thermosetting resins plays a key role on the final quality of the composite material components. Soft computing techniques proved to be an efficient method to control and optimize the curing process, replacing the conventional experimental and numerical approaches. In this paper artificial neural network (ANN) and fuzzy logic control (FLC) were implemented together to predict and control the temperature and degree of cure profile during the autoclave curing process. The obtained outcomes proved the capability of ANNs and FLC with respect to the hard computing methods.

  10. Advanced composite structural concepts and materials technologies for primary aircraft structures: Advanced material concepts

    Lau, Kreisler S. Y.; Landis, Abraham L.; Chow, Andrea W.; Hamlin, Richard D.


    To achieve acceptable performance and long-term durability at elevated temperatures (350 to 600 F) for high-speed transport systems, further improvements of the high-performance matrix materials will be necessary to achieve very long-term (60,000-120,000 service hours) retention of mechanical properties and damage tolerance. This report emphasizes isoimide modification as a complementary technique to semi-interpenetrating polymer networks (SIPN's) to achieve greater processibility, better curing dynamics, and possibly enhanced thermo-mechanical properties in composites. A key result is the demonstration of enhanced processibility of isoimide-modified linear and thermo-setting polyimide systems.

  11. Separation and analysis of cis-diol-containing compounds by boronate affinity-assisted micellar electrokinetic chromatography.

    Wang, Heye; Lü, Chenchen; Li, Hengye; Chen, Yang; Zhou, Min; Ouyang, Jian; Liu, Zhen


    Cis-diol-containing compounds (CDCCs) are usually highly hydrophilic compounds and are therefore difficult to separate by conventional reversed-phase-based micellar electrokinetic chromatography (MEKC) due to poor selectivity. Here, we report a new method, called boronate affinity-assisted micellar electrokinetic chromatography (BAA-MEKC), to solve this issue. A boronic acid with a hydrophobic alkyl chain was added to the background electrolyte, which acted as a modifier to adjust the selectivity. CDCCs can covalently react with the boronic acid to form negatively charged surfactant-like complexes, which can partition into micelles formed with a cationic surfactant. Thus, CDCCs can be separated according to the differential partition constants of their boronic acid complexes between the micellar phase and the surrounding aqueous phase. To verify this method, eight nucleosides were employed as the test compounds and their separation confirmed that the combination of boronate affinity interaction with MEKC can effectively enhance the separation of CDCCs. The effects of experimental conditions on the separation were investigated. Finally, the BAA-MEKC method was applied to the separation and analysis of nucleosides extracted from human urine. BAA-MEKC exhibited better selectivity and improved separation as compared with conventional MEKC and CZE. Successful quantitative analysis of urinary nucleosides by BAA-MEKC was demonstrated.

  12. [Research on the modification of Kevlar fiber by polypropylene glycol and cis-2-butene-1,4-diol].

    Zheng, Yu-ying; Wang, Can-yao; Fu, Ming-lian; Cai, Wei-long; Wang, Liang-en


    The mechanism of the modification of Kevlar fiber by polypropylene glycol(PPG) and cis-2-butene-1, 4-diol was studied in the paper, the authors learned the esterification of toluene-2, 4-diisocyanate (TDI) onto Kevlar fiber by infrared spectrum. In the mean time, the infrared spectrograms of the productions which steadily disposed by PPG and butendiol were analysed respectively, the result showed that the intensity of the bands was reinforced at about 1700-1720 cm(-1) after the samples were steadily disposed, that is to say, the group of --NCO has been stabilized into --NHCO group, the effect of steady disposal was obvious; but the disposal effect of butendiol was apparently better than PPG's at the same condition. Finally, the authors compared the influence of different mol rates between TDI and butendiol on the productions. Based onthe consequence, excessive butendiol would prevent the Kevlar fiber from farther reaction, therefore, the mol rate between TDI and butendiol should approach 1:1.

  13. Polycondensation of dicarboxylic acids and diols in water catalyzed by surfactant-combined catalysts and successive chain extension.

    Takasu, Akinori; Takemoto, Aki; Hirabayashi, Tadamichi


    Direct dehydration polycondensation of dicarboxylic acids and alcohols was carried out by surfactant-combined Brønsted and Lewis acids. This procedure did not require the removal of water, because the esterification was established at the interface of the emulsion in water. Emulsion polycondensations of 1,9-nonanediol (1,9-ND) and dodecanedioic acid (DDA) (the molar ratio of dicarboxylic acid to diol = 1:1) were carried out at 80 degrees C for 48 h in the presence of 16 wt % DBSA. The corresponding polyester (M(w) = 10.1 x 10(3)) was obtained in an excellent yield (99%). Chain extension in the emulsion was carried out using hexamethylene diisocyanate as the chain extender. SEC measurements indicated the expected shift to higher molecular weight region (M(w) = 11.4 x 10(3), M(w)/M(n) = 3.4) compared with parent polyester (M(w) = 4.5 x 10(3), M(w)/M(n) = 2.2).

  14. Structural and vibrational study of a neurotransmitter molecule: Dopamine [4-(2-aminoethyl) benzene-1,2-diol].

    Jha, Omkant; Yadav, T K; Yadav, R A


    Structural and vibrational studies for the most stable conformer of dopamine {4-(2-Aminoethyl) benzene-1, 2-diol} have been carried out at the DFT/B3LYP/6-311++G** level using the Gaussian 09 software. The IR and Raman spectra have been recorded and analyzed in light of the computed vibrational parameters using the DFT and the PEDs computed with the help of the GAR2PED software. Some of the fundamentals have considerably changed frequencies in going from benzene to dopamine. Except the rocking and wagging modes of the NH2 group the other four modes are pure group modes. The rocking and wagging modes of the NH2 group show mixing with the other modes. The two OH stretching vibrations are highly localized modes. The Kekule phenyl ring stretching mode is found to remain almost unchanged. The HOMO-LUMO study suggests the existence of charge transfer within the molecule and the energy gap supports the pharmacological active property of the dopamine molecule. The NBO analysis has been carried out to understand the proper and improper hydrogen bonding. Copyright © 2017. Published by Elsevier B.V.

  15. Enzymatic conversion of dihydroflavonols to flavan-3,4-diols using flower extracts of Dianthus caryophyllus L. (carnation).

    Stich, K; Eidenberger, T; Wurst, F; Forkmann, G


    Flavonoid analysis and supplementation experiments with dihydroflavonols and leucocyanidin on two cyanic, two acyanic and one white/red-variegated flowering strain of Dianthus caryophyllus (carnation) showed that in the acyanic strains recessive alleles (aa) of the gene A interrupt the anthocyanin pathway between dihydroflavonols and leucoanthocyanidins. The instability in the variegated strain involves the same step and is obviously caused by the multiple allele a (var) . In confirmation of these results, dihydroflavonol 4-reductase activity could be demonstrated in enzyme extracts from cyanic flowers and cyanic parts of variegated flowers but not in preparations from acyanic flowers or acyanic parts. The enzyme catalyzes the stereospecific reduction of (+)dihydrokaempferol to (+)-3,4-leucopelargonidin with NADPH as cofactor. A pH optimum around 7.0 and a temperature optimum at 30° C was determined, but the reduction reaction also proceeded at low temperatures. (+)Dihydroquercetin and (+)dihydromyricetin were also reduced to the respective flavan-3,4-cis-diols by the enzyme preparations from carnation flowers, and were even better substrates than dihydrokaempferol.

  16. Supramolecular structural, thermal properties and biological activity of 3-(2-methoxyphenoxy)propane-1,2-diol metal complexes

    Mahmoud, Walaa H.; Mahmoud, Nessma F.; Mohamed, Gehad G.; El-Bindary, Ashraf A.; El-Sonbati, Adel Z.


    New bi- and trivalent transition metal complexes of ligand 3-(2-methoxyphenoxy)propane-1,2-diol (GFS) were synthesized. The ligand and complexes were characterized via: melting point, UV/Visible, IR, 1H NMR, mass and diffused reflectance spectroscopy. The molecular structure of the investigated ligand (GFS) is optimized theoretically and the quantum chemical parameters are calculated. In addition, the complexes were characterized based on conductivity measurement, thermal analysis and biological activity. The infrared spectral study of GFS and its complexes, act as monobasic tridentate through the oxygen atom of hydroxyl group and two etheric oxygen atoms. Also, coordination to the unprotonated oxygen is evidenced from the disappearance of the OH signal in the 1H NMR spectra after complexation. The thermogravimetric analysis of the complexes shows metal oxide remaining as the final product. The compounds were tested against four bacterial species; two Gram positive bacteria (Bacillus subtilis and Staphylococcus aureus) and two Gram negative bacteria (Escherichia coli and Pseudomonas aeruginosa) as well as antifungal activity against (Candida albicans). The complexes showed significant activities against Gram positive bacteria than Gram negative bacteria. [Cd(GFS)Cl(H2O)2] complex showed remarkable antifungal activity. However, some complexes showed more chemotherapeutic efficiency than the parent GFS drug. The drug and complexes were also screened for their in vitro anticancer activity against the Breast cell line (MFC7) and the results obtained show that they exhibit a considerable anticancer activity.

  17. Preparation of Acetylated Guar Gum – Unsaturated Polyester Composites & Effect of Water on Their Properties

    David D’Melo


    Full Text Available Guar gum has seen extensive use in blends, however, its application as a filler in thermoset composites has as yet not been investigated. The effect of the addition of guar gum and its acetyl derivatives on the kinetics of water diffusion in unsaturated polyester composites was studied. The effect of water on the mechanical properties of the composites was studied with respect to the nature of filler, filler concentration and time of immersion. All the mechanical properties were observed to decrease on exposure to water. Further, it was observed that acetylated guar gum, with a degree of substitution of 0.21, showed the best mechanical properties, surpassing the other filled composites and that of the pure unsaturated polyester. Thus, acetylated guar gum showed promise as eco-friendly filler in composite formulation.

  18. Latent Hardeners for the Assembly of Epoxy Composites

    Palmieri, Frank; Wohl, Christopher J.; Connell, John W.; Mercado, Zoar; Galloway, Jordan


    Large-scale composite structures are commonly joined by secondary bonding of molded-and-cured thermoset components. This approach may result in unpredictable joint strengths. In contrast, assemblies made by co-curing, although limited in size by the mold, result in stable structures, and are certifiable for commercial aviation because of structural continuity through the joints. Multifunctional epoxy resins were prepared that should produce fully-cured subcomponents with uncured joining surfaces, enabling them to be assembled by co-curing in a subsequent out-of-autoclave process. Aromatic diamines were protected by condensation with a ketone or aldehyde to form imines. Properties of the amine-cured epoxy were compared with those of commercially available thermosetting epoxy resins and rheology and thermal analysis were used to demonstrate the efficacy of imine protection. Optimum conditions to reverse the protecting chemistry in the solid state using moisture and acid catalysis were determined. Alternative chemistries were also investigated. For example, chain reaction depolymerization and photoinitiated catalysts would be expected to minimize liberation of volatile organic content upon deprotection and avoid residual reactive species that could damage the resin. Results from the analysis of protected and deprotected resins will be presented.

  19. AC Electric Field Activated Shape Memory Polymer Composite

    Kang, Jin Ho; Siochi, Emilie J.; Penner, Ronald K.; Turner, Travis L.


    Shape memory materials have drawn interest for applications like intelligent medical devices, deployable space structures and morphing structures. Compared to other shape memory materials like shape memory alloys (SMAs) or shape memory ceramics (SMCs), shape memory polymers (SMPs) have high elastic deformation that is amenable to tailored of mechanical properties, have lower density, and are easily processed. However, SMPs have low recovery stress and long response times. A new shape memory thermosetting polymer nanocomposite (LaRC-SMPC) was synthesized with conductive fillers to enhance its thermo-mechanical characteristics. A new composition of shape memory thermosetting polymer nanocomposite (LaRC-SMPC) was synthesized with conductive functionalized graphene sheets (FGS) to enhance its thermo-mechanical characteristics. The elastic modulus of LaRC-SMPC is approximately 2.7 GPa at room temperature and 4.3 MPa above its glass transition temperature. Conductive FGSs-doped LaRC-SMPC exhibited higher conductivity compared to pristine LaRC SMP. Applying an electric field at between 0.1 Hz and 1 kHz induced faster heating to activate the LaRC-SMPC s shape memory effect relative to applying DC electric field or AC electric field at frequencies exceeding1 kHz.

  20. 复合材料小尺寸螺栓的成型工艺方法探讨%Discussion on Molding Process of Smallsize Composite Bolts



    复合材料螺栓已经广泛应用到汽车、航天、航空等各个领域,其中小尺寸螺栓的热塑性注塑工艺成型方法也比较成熟,但热固性模压工艺成型的方法还处于研究阶段,本文通过对热塑性注塑成型的工艺方法和热固性模压成型的工艺方法的对比,阐明热固性模压成型的工艺方法的优、劣势,并对热固性模压成型的工艺方法进行分析和探讨。%Composite bolts are widely used in the fields of automobiles ,aerospace ,aviation and so on .Thermoplastic in-fusion process for smallsize bolts is mature ,but thermosetting mould pressing is still in research .In this paper ,by the com-parison of the two processes ,the advantages and disadvantages of the thermosetting mould pressing are illustrated ; mean-while,the thermosetting mould pressing is also analyzed and discussed .

  1. Use of Guided Acoustic Waves to Assess the Effects of Thermal-Mechanical Cycling on Composite Stiffness

    Seale, Michael D.; Madaras, Eric I.


    The introduction of new, advanced composite materials into aviation systems requires it thorough understanding of the long-term effects of combined thermal and mechanical loading. As part of a study to evaluate the effects of thermal-mechanical cycling, it guided acoustic (Lamb) wave measurement system was used to measure the bending and out-of-plane stiffness coefficients of composite laminates undergoing thermal-mechanical loading. The system uses a pulse/receive technique that excites an antisymmetric Lamb mode and measures the time-of-flight over a wide frequency range. Given the material density and plate thickness, the bending and out-of-plane shear stiffnesses are calculated from a reconstruction of the velocity dispersion curve. A series of 16 and 32-ply composite laminates were subjected to it thermal-mechanical loading profile in load frames equipped with special environmental chambers. The composite systems studied were it graphite fiber reinforced amorphous thermoplastic polyimide and it graphite fiber reinforced bismaleimide thermoset. The samples were exposed to both high and low temperature extremes its well as high and low strain profiles. The bending and out-of-plane stiffnesses for composite sample that have undergone over 6,000 cycles of thermal-mechanical loading are reported. The Lamb wave generated elastic stiffness results have shown decreases of up to 20% at 4,936 loading cycles for the graphite/thermoplastic samples and up to 64% at 4,706 loading cycles for the graphite/thermoset samples.

  2. Metabolomics reveals increased isoleukotoxin diol (12,13-DHOME) in human plasma after acute Intralipid infusion.

    Edwards, Lindsay M; Lawler, Nathan G; Nikolic, Sonja B; Peters, James M; Horne, James; Wilson, Richard; Davies, Noel W; Sharman, James E


    Intralipid is a fat emulsion that is regularly infused into humans and animals. Despite its routine use, Intralipid infusion can cause serious adverse reactions, including immunosuppression. Intralipid is a complex mix of proteins, lipids, and other small molecules, and the effect of its infusion on the human plasma metabolome is unknown. We hypothesized that untargeted metabolomics of human plasma after an Intralipid infusion would reveal novel insights into its effects. We infused Intralipid and saline into 10 healthy men in a double-blind, placebo-controlled experiment and used GC/MS, LC/MS, and NMR to profile the small-molecule composition of their plasma before and after infusion. Multivariate statistical analysis of the 40 resulting plasma samples revealed that after Intralipid infusion, a less-well-characterized pathway of linoleic acid metabolism had resulted in the appearance of (9Z)-12,13-dihydroxyoctadec-9-enoic acid (12,13-DHOME, P plasma 12,13-DHOME. Given that 12,13-DHOME is known to directly affect neutrophil function, we conclude that untargeted metabolomics may have revealed a hitherto-unknown mechanism of intralipid-induced immunosuppression.


    Yi-hu Song; Qiang Zheng; Zheng-zheng Lai


    Environmentally friendly thermosetting composites were successfully prepared by conventional blending wheat gluten as matrix.glycerol as plasticizer and silica as filler followed by thermo-molding of the mixture at 120℃.The strong interfacial interaction between silica particles and gluten proteins leaded to an increase in storage modulus and a decrease in loss factor as revealed by dynamic mechanical analysis.The moisture absorption and elongation at break decrease while Young's modulus and tensile strength increase with increasing silica content from 0 to 10 wt%.However,the moisture absorption and mechanical properties show discontinuous changes at a silica content of 6 wt%.The glycerol content also has a marked influence on the moisture absorption and mechanical properties of the composites with a constant gluten-to-silica ratio.

  4. Fire performance of composite materials for offshore use. Paper 2

    Gibson, A.G.; Chandler, H.W.; Wilcox, J.A.D.; Wu, Y.-S. [Newcastle upon Tyne Univ. (United Kingdom). Dept. of Mechanical, Materials, and Mfg. Engineering; Hume, J. [Warrington Fire Research Centre (London) Ltd. (United Kingdom)


    This paper discusses the results of a study of the fire performance of composites based on E-glass woven rovings and four different thermosetting resin systems: polyester, vinyl ester, epoxy and phenolic. It was found that, in terms of ignitability, heat release, smoke and toxicity, the phenolic resins were in a different performance class to the others. It was also found that, in thick sections, composite laminates showed a surprisingly slow rate of burn-through in furnace tests and lower than expected heat release. This phenomenon has led to applications in heat and fire protection. A model for laminate degradation in fire demonstrates that this effect is associated with the endothermic decomposition of the resin. The effect appears to occur with all classes of resin. (Author)

  5. Heating of thermoplastic-based unidirectional composite prepregs

    Wang, X.; Weber, M.E.; Charrier, J.M. (McGill Univ., Montreal (Canada))


    Thermoplastic-based prepregs offer a potential for faster manufacture of composite products than with thermoset-based prepregs. The winding or controlled placement of thermoplastic-based prepreg tapes requires the rapid heating of the moving tape, just prior to its contact with the substrate on the mandrel. In the case of complex shapes, geometrical constraints and significant variations in tape speeds in the course of manufacture, make it particularly desirable to be able to model the heating process. A mathematical model and its experimental verification for convection/conduction heat transfer to and through either a homogeneous thermoplastic material, or thermoplastic-based unidirectional composites featuring glass, aramid and carbon fibers, is discussed. 12 refs.

  6. Carbon fiber content measurement in composite

    Wang, Qiushi

    Carbon fiber reinforced polymers (CFRPs) have been widely used in various structural applications in industries such as aerospace and automotive because of their high specific stiffness and specific strength. Their mechanical properties are strongly influenced by the carbon fiber content in the composites. Measurement of the carbon fiber content in CFRPs is essential for product quality control and process optimization. In this work, a novel carbonization-in-nitrogen method (CIN) is developed to characterize the fiber content in carbon fiber reinforced thermoset and thermoplastic composites. In this method, a carbon fiber composite sample is carbonized in a nitrogen environment at elevated temperatures, alongside a neat resin sample. The carbon fibers are protected from oxidization while the resin (the neat resin and the resin matrix in the composite sample) is carbonized under the nitrogen environment. The residue of the carbonized neat resin sample is used to calibrate the resin carbonization rate and calculate the amount of the resin matrix in the composite sample. The new method has been validated on several thermoset and thermoplastic resin systems and found to yield an accurate measurement of fiber content in carbon fiber polymer composites. In order to further understand the thermal degradation behavior of the high temperature thermoplastic polymer during the carbonization process, the mechanism and the kinetic model of thermal degradation behavior of carbon fiber reinforced poly (phenylene sulfide) (CPPS) are studied using thermogravimetry analysis (TGA). The CPPS is subjected to TGA in an air and nitrogen atmosphere at heating rates from 5 to 40°C min--1. The TGA curves obtained in air are different from those in nitrogen. This demonstrates that weight loss occurs in a single stage in nitrogen but in two stages in air. To elucidate this difference, thermal decomposition kinetics is analyzed by applying the Kissinger, Flynn-Wall-Ozawa, Coat-Redfern and

  7. Preparation and surface active properties of oxypropylated α-hydroxyacids, α-hydroxyesters and α-, β-alkane diols

    Shaker, N. O.


    Full Text Available A series of a-hydroxyacids RCH(OHCO2H, α-hydroxyesters RCH(OHCO2CH3 and α, β-alkane diols was synthetized and condensed with 5-20 moles propylene oxide to obtain nonionic surfactants. Some of the physicochemical properties and the biodegradability of these products were examined. The results showed that the best wetting properties were obtained by the addition of 15 oxypropylene groups to methyl α-hydroxymyristate. The α-hydroxymyristic acid with 20 moles of propylene oxide gave the highest foam. Biodegradation studies indicated that increasing both the chain length of the hydrophobic alkyl chain or the number of oxypropylene groups in the adduct decreased biodegradation.

    Una serie de α-hidroxiácidos RCH(OHCO2H, α-hidroxiésteres RCH(OHCO2CH3 y α, β-alcanodioles se sintetizaron y condensaron con 5-20 moles de óxido de propileno para obtener tensioactivos no iónicos. Se examinaron algunas propiedades fisicoquímicas y de biodegradabilidad de estos productos. Los resultados mostraron que las mejores propiedades humectantes se obtuvieron por adición de 15 grupos oxipropilenos a α-hidroximiristato de metilo.
    El ácido α-hidroximirístico con 20 moles de óxido de propileno dio la espuma más poderosa. Estudios de biodegradación indicaron que tanto el aumento de la longitud de cadena de los grupos alquilo hidrofóbicos como el número de grupos oxipropilenos en el aducto disminuyeron la biodegradación.

  8. Feasibility and Manufacturing Considerations of Hemp Textile Fabric Utilized in Pre-Impregnated Composites

    Osusky, Gregory

    This study investigates the fabrication and mechanical properties of semicontinuous, hemp fiber reinforced thermoset composites. This research determines if off-the-shelf refined woven hemp fabric is suitable as composite reinforcement using resin pre-impregnated method. Industrial hemp was chosen for its low cost, low resource input as a crop, supply chain from raw product to refined textile and biodegradability potential. Detail is placed on specimen fabrication considerations. Lab testing of tension and compression is conducted and optimization considerations are examined. The resulting composite is limited in mechanical properties as tested. This research shows it is possible to use woven hemp reinforcement in pre-impregnated processed composites, but optimization in mechanical properties is required to make the process commercially practical outside niche markets.

  9. Small angle neutron scattering study on the aggregation behaviour of PEO–PPO–PEO copolymers in the presence of a hydrophobic diol

    B Bharatiya; V K Aswal; P Bahadur


    Small angle neutron scattering (SANS) measurements on aqueous solutions of four polyethylene oxide–polypropylene oxide–polyethylene oxide block copolymers (commercially known as Pluronic®)F88, P85, F127 and P123 in the presence of hydrophobic C14Diol (also known as Surfynol® 104) reveal information on micellization, micellar size and micellar transitions. While most hydrophilic F88 (with least PPO/PEO ratio) remained unimers in water at 30◦ C, other copolymers formed micellar solutions. Surfynol® 104 is sparingly soluble in water to only about ∼ 0.1 wt%, but on addition to pluronic solution, it gets incorporated in the micellar region of block copolymer which leads to increase in aggregation number and transformation of spherical to ellipsoidal micelles. The added diol-induced micellization in F88, though hydrophilic copolymers F88 and F127 did not show any appreciable micellar growth or shape changes as observed for P85 and P123 (which are comparatively more hydrophobic). The SANS results on copolymer pairs with same molecular weight PPO but different % PEO (viz. F88 and P85, F127 and P123) and with same molecular weight PEO but different PPO (F88 and F127) reveal that the copolymer with large PPO/PEO ratio facilitate micellar transition in the presence of diol. An increase in temperature and presence of added electrolyte (sodium chloride) in the solution further enhances these effects. The micellar parameters for these systems were found out using available software and are reported.

  10. Steviamine, a new class of indolizidine alkaloid [(1R,2S,3R,5R,8aR-3-hydroxymethyl-5-methyloctahydroindolizine-1,2-diol hydrobromide

    Amber L. Thompson


    Full Text Available X-ray crystallographic analysis of the title hydrobromide salt, C10H20N+·Br−, of (1R,2S,3R,5R,8aR-3-hydroxymethyl-5-methyloctahydroindolizine-1,2-diol defines the absolute and relative stereochemistry at the five chiral centres in steviamine, a new class of polyhydroxylated indolizidine alkaloid isolated from Stevia rebaudiana (Asteraceae leaves. In the crystal structure, molecules are linked by intermolecular O—H...Br and N—H...Br hydrogen bonds, forming double chains around the twofold screw axes along the b-axis direction. Intramolecular O—H...O interactions occur.

  11. A New Convenient Method for the Resolution of 1, 1'-Binaphthalene-2, 2'-diol Via a Phosphite Using (-)-Menthol as Resolving Agent


    (-)-Menthol reacts with phosphorus trichloride to afford menthyl phosphorodichloridite 2,which further reacts with racemic 1, 1'-binaphthalene-2, 2'-diol to give phosphite (±)-3 in the presence of triethylamine. +(±)-3 can be easily separated by fractional crystallization to form the crystal (+)-(S)-3 and the mother liquor (-)-(R)-3. Then both the crystal and the mother liquor are treated with AcOH-H20 to obtain enantiomeric pure (-)-(S)-1 and (+)-(R)-1 respectively, with enantiomeric excess up to 99.7%.

  12. Boron-Catalyzed Regioselective Deoxygenation of Terminal 1,2-Diols to 2-Alkanols Enabled by the Strategic Formation of a Cyclic Siloxane Intermediate.

    Drosos, Nikolaos; Morandi, Bill


    The selective deoxygenation of polyols is a frontier in our ability to harness the stereochemical and structural complexity of natural and synthetic feedstocks. Herein, we describe a highly active and selective boron-based catalytic system for the selective deoxygenation of terminal 1,2-diols at the primary position, a process that is enabled by the transient formation of a cyclic siloxane. The method provides an ideal complement to well-known catalytic asymmetric reactions to prepare synthetically challenging chiral 2-alkanols in nearly perfect enantiomeric excess, as illustrated in a short synthesis of the anti-inflammatory drug (R)-lisofylline.

  13. Synthesis and characterization of new polyesters based on 2,5-bis[(4-chloro carboxyanilino)carbonyl]pyridine and aromatic diols

    Khalil; Faghihi


    Six new polyesters 7a-f were synthesized through the solution polycondensation reaction of diacid chloride 5 with six aromatic diols 6a-f in N,N-dimethyl acetamide(DMAc) as solvent in the presence of pyridine as base.The polycondensation reaction produced a series of novel polyester containing pyridyl moiety in the main chain in high yields with inherent viscosities between 0.35 and 0.54 dL/g.The resulted polymers were fully characterized by means of FT-IR spectroscopy,elemental analyses,inherent viscosi...

  14. 4-Acetyl-12,13-epoxyl-9-trichothecene-3,15-diol isolated from the fruiting bodies of Isariajaponica Yasuda induces apoptosis of human leukemia cells (HL-60).

    Oh, G S; Hong, K H; Oh, H; Pae, H O; Kim, I K; Kim, N Y; Kwon, T O; Shin, M K; Chung, H T


    The fruiting bodies of Isaria fungi have been traditionally used in Korea to treat cancer. An apoptosis-inducing compound, 4-acetyl-12,13-epoxyl-9-trichothecene-3,15-diol, was isolated from the methanol extract of fruiting bodies of Isaria japonica Yasuda by bioassay-guided fractionation. The apoptosis of the human leukemia cells (HL-60) by the compound was accessed by propidium iodide-staining flow cytometric analysis, and apoptosis-inducing activity at IC50 concentration (10 nmol/l) was further confirmed by a nuclear morphological change, a ladder pattern of internucleosomal DNA fragmentation, and an activation of caspase-3.

  15. 5-Cholesten-3β,25-Diol 3-Sulfate Decreases Lipid Accumulation in Diet-Induced Nonalcoholic Fatty Liver Disease Mouse Model

    Xu, Leyuan; Kim, Jin Koung; Bai, Qianming; Zhang, Xin; Kakiyama, Genta; Min, Hae-Ki; Sanyal, Arun J; Pandak, William M.; Ren, Shunlin


    Sterol regulatory element-binding protein-1c (SREBP-1c) increases lipogenesis at the transcriptional level, and its expression is upregulated by liver X receptor α (LXRα). The LXRα/SREBP-1c signaling may play a crucial role in the pathogenesis of nonalcoholic fatty liver disease (NAFLD). We previously reported that a cholesterol metabolite, 5-cholesten-3β,25-diol 3-sulfate (25HC3S), inhibits the LXRα signaling and reduces lipogenesis by decreasing SREBP-1c expression in primary hepatocytes. T...

  16. Volumetric Properties of the Mixture Ethane-1,2-diol C2H6O2 + C6H10O Cyclohexanone (VMSD1111, LB4980_V)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Ethane-1,2-diol C2H6O2 + C6H10O Cyclohexanone (VMSD1111, LB4980_V)' providing data from direct low-pressure measurement of mass density at variable mole fraction and constant temperature, in the single-phase region(s).

  17. Volumetric Properties of the Mixture Ethane-1,2-diol C2H6O2 + C6H10O Cyclohexanone (VMSD1212, LB4988_V)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Ethane-1,2-diol C2H6O2 + C6H10O Cyclohexanone (VMSD1212, LB4988_V)' providing data by calculation of molar excess volume from low-pressure density measurements at variable mole fraction and constant temperature.

  18. A new class of fluorescent boronic acids that have extraordinarily high affinities for diols in aqueous solution at physiological pH.

    Cheng, Yunfeng; Ni, Nanting; Yang, Wenqian; Wang, Binghe


    The boronic acid group is an important recognition moiety for sensor design. Herein, we report a series of isoquinolinylboronic acids that have extraordinarily high affinities for diol-containing compounds at physiological pH. In addition, 5- and 8-isoquinolinylboronic acids also showed fairly high binding affinities towards D-glucose (K(a)=42 and 46 M(-1), respectively). For the first time, weak but encouraging binding of cis-cyclohexanediol was found for these boronic acids. Such binding was coupled with significant fluorescence changes. Furthermore, 4- and 6-isoquinolinylboronic acids also showed the ability to complex methyl α-D-glucopyranose (K(a)=3 and 2 M(-1), respectively).

  19. Hydroformylation of olefins and reductive carbonylation of aryl halides with syngas formed ex situ from dehydrogenative decarbonylation of hexane-1,6-diol

    Christensen, Stig Holden; Olsen, Esben Paul Krogh; Rosenbaum, Jascha;


    A variety of primary alcohols have been investigated as convenient substrates for the ex situ delivery of carbon monoxide and molecular hydrogen in a two-chamber reactor. The gaseous mixture is liberated in one chamber by an iridium-catalysed dehydrogenative decarbonylation of the alcohol...... and then consumed in the other chamber in either a rhodium-catalysed hydroformylation of olefins or a palladium-catalysed reductive carbonylation of aryl halides. Hexane-1,6-diol was found to be the optimum alcohol for both reactions where moderate to excellent yields were obtained of the product aldehydes...

  20. Pyriculins A and B, two monosubstituted hex-4-ene-2,3-diols and other phytotoxic metabolites produced by Pyricularia grisea isolated from buffelgrass (Cenchrus ciliaris)

    Marco Masi; Susan Meyer; Marcin Gorecki; Alessandro Mandoli; Lorenzo Di Bari; Gennaro Pescitelli; Alessio Cimmino; Massimo Cristofaro; Suzette Clement; Antonio Evidente


    Pyricularia grisea has been identified as a foliar pathogen on buffelgrass (Cenchrus ciliaris) in North America and was studied as a potential source of phytotoxins for buffelgrass control. Two monosubstituted hex‐4‐ene‐2,3‐diols, named pyriculins A and B, were isolated from its culture filtrate organic extract together with (10S,11S)‐(−)‐epipyriculol, trans‐3...

  1. Development of new biomass-based furan/glass composites manufactured by the double-vacuum-bag technique

    Dominguez, Juan Carlos; Madsen, Bo


    The present study addresses the development of new biomass-based furan resin/glass fibre composites manufactured by the double-vacuum-bag technique using a two-stage cure cycle to allow removal of water from the resin. The volumetric composition and mechanical properties of the composites...... of conventional thermosetting/glass composites, but with lower strength. The findings of the present study show that a more efficient water removal during manufacturing, a lower porosity content and a less brittle stress–strain behaviour of the furan matrix are to be addressed to further improve the properties...... are measured and analysed with focus on the porosity content. The so-called matrix correlated porosity factor is determined to be 0.096, meaning that the furan matrix itself contains 8.8% porosity. In the optimal case of no matrix porosity, stiffness of the composites compares well with the stiffness...

  2. Multi-Scaled Modeling the Mechanical Properties of Tubular Composites Reinforced with Innovated 3D Weft Knitted Spacer Fabrics

    Omrani, Elahe; Hasani, Hossein; Dibajian, Sayed Houssain


    Textile composites of 3D integrated spacer configurations have been recently focused by several researchers all over the world. In the present study, newly-designed tubular composites reinforced with 3D spacer weft knitted fabrics were considered and the effects of their structural parameters on some applicable mechanical properties were investigated. For this purpose, two different samples of 3D spacer weft knitted textile types in tubular form were produced on an electronic flat knitting machine, using glass/nylon hybrid yarns. Thermoset tubular-shaped composite parts were manufactured via vacuum infusion molding process using epoxy resin. The mechanical properties of the produced knitted composites in term of external static and internal hydrostatic pressures were evaluated. Resistance of the produced composites against the external static and internal hydrostatic pressures was numerically simulated using multi-scale modeling method. The finding revealed that there is acceptable correlation between experimental and theoretical results.

  3. Development of analytical methods for the gas chromatographic determination of 1,2-epoxy-3-butene, 1,2:3,4-diepoxybutane, 3-butene-1,2-diol, 3,4-epoxybutane-1,2-diol and crotonaldehyde from perfusate samples of 1,3-butadiene exposed isolated mouse and rat livers

    Bhowmik, S.; Schuster, A.; Filser, J.G.


    Mutagenicity and carcinogenicity of 1,3-butadiene (BD) highly probably results from epoxide metabolites as 1,2-epoxy-3-butene (EB), 1,2:3,4-diepoxybutane (DEB) and 3,4-epoxybutane-1,2-diol (EBD). A further metabolite crotonaldehyde (CA) has also been discussed to be relevant. So far, in BD exposed rodents only EB and DEB concentrations had been quantified. However, the methods used were either not very sensitive or instrumentally expensive. Therefore, the goal of the present work was to establish simple analytical methods selective and sensitive enough to determine all of these compounds and a further secondary BD intermediate, 3-butene-1,2-diol (B-diol), in BD exposed rodent livers. The once-through perfused liver system was chosen for testing the applicability of the methods to be developed, since it enables BD exposures of this quantitatively most relevant metabolising organ near to the in-vivo situation. All the metabolites were extracted from the aqueous perfusion medium and analysed using a gas chromatograph equipped with a mass selective detector (GC/MS) in the PCI mode. (orig.)

  4. Design of Active Composites


    long chain diol (either a polyether or polyester) with excess isocyanate to form a prepolymer , followed by the addition of a short chain diol that...acts as a chain extender to link the prepolymers together. Due to the thermodynamic imicisibility of segments of PU, phase separation into a flexible...during the initial prepolymer reactions the NCO:OH ratio is always greater than 2 due to use of excess isocyanate to used to cap the ends of the

  5. Inhibition Behaviour of 2-butine1, 4diol and Tartrate Salt, and Their Synergistic Effects on Corrosion of AA3003 Aluminium Alloy in 0.5% NaCl Solution

    Taghi Shahrabi; Alireza Yazdzad; Mirghasem Hosseini


    This work intends to investigate the inhibition behaviour of 2-butine 1, 4diol and potassium sodium tartrate and their synergistic effects on 3003 aluminium alloy corrosion in 0.5% NaCl solution. Experiments were carried out by electrochemical impedance spectroscopy (EIS) and Tafel polarization method in a three-electrode cell. It was concluded that the inhibition efficiencies increased with an increase in the concentrations of inhibitors. For 2-butinel, 4diol and tartrate salt, the optimum in the inhibition efficiency, at room temperature and neutral pH, was observed for concentrations close to 10-3 mol/L and 1.5×10-3mol/L, respectively. The electrochemical results illustrated that 2-butine1, 4diol and tartrate salt, have significant synergistic inhibition effects on corrosion of 3003 aluminium alloy in 0.5% NaCl solution. The optimum ratio of concentrations for tartrate to alcohol was 2:1.

  6. In Silico/In Vivo Insights into the Functional and Evolutionary Pathway of Pseudomonas aeruginosa Oleate-Diol Synthase. Discovery of a New Bacterial Di-Heme Cytochrome C Peroxidase Subfamily

    Mónica Estupiñán; Daniel Álvarez-García; Xavier Barril; Pilar Diaz; Angeles Manresa


    As previously reported, P. aeruginosa genes PA2077 and PA2078 code for 10S-DOX (10S-Dioxygenase) and 7,10-DS (7,10-Diol Synthase) enzymes involved in long-chain fatty acid oxygenation through the recently described oleate-diol synthase pathway. Analysis of the amino acid sequence of both enzymes revealed the presence of two heme-binding motifs (CXXCH) on each protein. Phylogenetic analysis showed the relation of both proteins to bacterial di-heme cytochrome c peroxidases (Ccps), similar to Xa...

  7. Preparation and characterization of novel thermoset polyimide and polyimide-peo doped with LiCF3SO3

    M. H. Ugur


    Full Text Available This paper deals with the synthesis and characterization of a new type of anhydrous ionic conducting lithium doped membranes consist of polyimide (PI, poly (ethylene oxide (PEO and lithium trifluoromethanesulfonate (LiCF3SO3 for solid polymer electrolyte (SPE. For this purpose, different molar ratios of lithium salt (Li-salt solution are added into poly (amic acid (PAA intermediate prepared from the reaction of 3,3',4,4'-benzophenon tetracarboxylic dianhydride (BTDA and 4,4'-oxydianiline (ODA. PEO is incorporated into PAA since it forms more stable complexes and possess high ionic conductivities. Then, Li-salt containing PAA solutions are imidized by thermal process. The effect of interaction between host polymer and Li-salt is characterized by FT-IR (Fourier Transform Infrared spectroscopy and SEM (scanning electron micrsocopy. The conductivities of Li-salt and PEO containing PI composite membranes are in the range of 10–7–10–5 S•cm–1. The conductivity increases with incorporation of PEO. Thermogravimetric analysis results reveal that the PI/PEO/LiCF3SO3 composite polymer electrolyte membranes are thermally stable up to 500°C.

  8. Alcohol-, diol-, and carbohydrate-substituted indenoisoquinolines as topoisomerase I inhibitors: investigating the relationships involving stereochemistry, hydrogen bonding, and biological activity.

    Peterson, Katherine E; Cinelli, Maris A; Morrell, Andrew E; Mehta, Akhil; Dexheimer, Thomas S; Agama, Keli; Antony, Smitha; Pommier, Yves; Cushman, Mark


    The DNA-relaxing enzyme topoisomerase I (Top1) can be inhibited by heterocyclic compounds such as indolocarbazoles and indenoisoquinolines. Carbohydrate and hydroxyl-containing side chains are essential for the biological activity of indolocarbazoles. The current study investigated how similar functionalities could be "translated" to the indenoisoquinoline system and how stereochemistry and hydrogen bonding affect biological activity. Herein is described the preparation and assay of indenoisoquinolines substituted with short-chain alcohols, diols, and carbohydrates. Several compounds (including those derived from sugars) display potent Top1 poisoning and antiproliferative activities. The Top1 poisoning activity of diol-substituted indenoisoquinolines is dependent upon stereochemistry. Although the effect is striking, molecular modeling and docking studies do not indicate any reason for the difference in activity due to similar calculated interactions between the ligand and Top1-DNA complex and ambiguity about the binding mode. A stereochemical dependence was also observed for carbohydrate-derived indenoisoquinolines. Although similar trends were observed in other classes of Top1 inhibitors, the exact nature of this effect has yet to be elucidated.

  9. Interaction of benzo[a]pyrene diol epoxide isomers with human serum albumin: Site specific characterisation of adducts and associated kinetics

    Motwani, Hitesh V.; Westberg, Emelie; Törnqvist, Margareta


    Carcinogenicity of benzo[a]pyrene {B[a]P, a polycyclic aromatic hydrocarbon (PAH)} involves DNA-modification by B[a]P diol epoxide (BPDE) metabolites. Adducts to serum albumin (SA) are not repaired, unlike DNA adducts, and therefore considered advantageous in assessment of in vivo dose of BPDEs. In the present work, kinetic experiments were performed in relation to the dose (i.e. concentration over time) of different BPDE isomers, where human SA (hSA) was incubated with respective BPDEs under physiological conditions. A liquid chromatography (LC) tandem mass spectrometry methodology was employed for characterising respective BPDE-adducts at histidine and lysine. This strategy allowed to structurally distinguish between the adducts from racemic anti- and syn-BPDE and between (+)- and (‑)-anti-BPDE, which has not been attained earlier. The adduct levels quantified by LC-UV and the estimated rate of disappearance of BPDEs in presence of hSA gave an insight into the reactivity of the diol epoxides towards the N-sites on SA. The structure specific method and dosimetry described in this work could be used for accurate estimation of in vivo dose of the BPDEs following exposure to B[a]P, primarily in dose response studies of genotoxicity, e.g. in mice, to aid in quantitative risk assessment of PAHs.

  10. Diacyltransferase Activity and Chain Length Specificity of Mycobacterium tuberculosis PapA5 in the Synthesis of Alkyl β-Diol Lipids

    Touchette, Megan H.; Bommineni, Gopal R.; Delle Bovi, Richard J.; Gadbery, John; Nicora, Carrie D.; Shukla, Anil K.; Kyle, Jennifer E.; Metz, Thomas O.; Martin, Dwight W.; Sampson, Nicole S.; Miller, W. T.; Tonge, Peter J.; Seeliger, Jessica C.


    Although classified as Gram-positive bacteria, Corynebacterineae possess an asymmetric outer membrane that imparts structural and thereby physiological similarity to more distantly related Gram-negative bacteria. Like lipopolysaccharide in Gram-negative bacteria, lipids in the outer membrane of Corynebacterineae have been associated with the virulence of pathogenic species such as Mycobacterium tuberculosis (Mtb). For example, Mtb strains that lack long, branched-chain alkyl esters known as dimycocerosates (DIMs) are significantly attenuated in model infections. The resultant interest in the biosynthetic pathway of these unusual virulence factors has led to the elucidation of many of the steps leading to the final esterification of the alkyl beta-diol, phthiocerol, with branched-chain fatty acids know as mycocerosates. PapA5 is an acyltransferase implicated in these final reactions. We here show that PapA5 is indeed the terminal enzyme in DIM biosynthesis by demonstrating its dual esterification activity and chain-length preference using synthetic alkyl beta-diol substrate analogues. Applying these analogues to a series of PapA5 mutants, we also revise a model for the substrate binding within PapA5. Finally, we demonstrate that the Mtb Ser/Thr kinase PknB modifies PapA5 on three Thr residues, including two (T196, T198) located on an unresolved loop. These results clarify the DIM biosynthetic pathway and suggest possible mechanisms by which DIM biosynthesis may be regulated by the post-translational modification of PapA5.

  11. In vitro antioxidant and antimicrobial activity cycloart-23-ene-3β,25-diol(B2) isolated fromPongamia pinnata(L. Pierre)

    Sachin L Badole; Anand A Zanwar; Abhijeet N Khopade; Subhash L Bodhankar


    Objective:To evaluate the in-vitro antioxidant and antimicrobial activity of cycloart-23-ene-3β,25-diol (called asB2) isolated from stem bark ofPongamia pinnata.Methods:In vitro antioxidant activity ofB2 was determined by methods for determination ofDPPHradical scavenging, reducing power, superoxide anion radical scavenging, hydroxyl radical scavenging, hydrogen peroxide scavenging, metal chelating and nitric oxide radical scavenging at the doses of20, 40, 60, 80 and100 μg/mL, respectively. β-tocopherol with same concentration was used as a standard antioxidant.In vitro antimicrobial activity of B2was determined by cup plate method in different concentration range of10-100 μg/mL.Results: The results indicated that dose dependent % reduction againstDPPH radical, reducing power, superoxide anion radical scavenging, hydroxyl radical scavenging, metal chelating, hydrogen peroxide scavenging and nitric oxide radical scavenging byB2 and β-tocopherol.Conclusions:It is concluded that cycloart23-ene-3β, 25 diol (B2) showed dose dependent antioxidant activity.B2 showed more DPPHradical scavenging, reducing power, superoxide scavenging, hydroxyl radical scavenging, metal chelating scavenging, hydrogen peroxide radical scavenging and nitric oxide radical scavenging activity than β-tocopherol and in case of antimicrobial activityB2 exhibited broad-spectrum activity against bacteria and strong activity against yeast type of fungi.

  12. Selective Enrichment and MALDI-TOF MS Analysis of Small Molecule Compounds with Vicinal Diols by Boric Acid-Functionalized Graphene Oxide

    Zhang, Jing; Zheng, Xiaoling; Ni, Yanli


    In this study, a 4-vinylphenylboronic acid-functionalized graphene oxide (GO) material was prepared via atom-transfer radical polymerization (ATRP) method and applied for the first time as a novel matrix for the selective enrichment and analysis of small-molecule compounds with vicinal diols, which have been the focus of intense research in the field of life science, by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) in positive-ion mode. There are two main factors playing a decisive role in assisting laser D/I process comparing to some traditional matrices: (1) GO provides π-conjugated system by itself for laser absorption and energy transfer; (2) the modified 4-vinylphenylboronic acid can selectively capture small-molecule compounds with vicinal diols. The results demonstrate that the novel material has distinct advantages over previously reported matrices in enriching and assisting the highly efficient ionization of target molecules for mass spectrometry analysis. This work indicates a new application branch for graphene-based matrices and provides an alternative solution for small-molecules analysis.

  13. Characterization of a novel 8R,11S-linoleate diol synthase from Penicillium chrysogenum by identification of its enzymatic products.

    Shin, Kyung-Chul; Seo, Min-Ju; Oh, Deok-Kun


    To identify novel fatty acid diol synthases, putative candidate sequences from Penicillium species were analyzed, and hydroxy fatty acid production by crude Penicillium enzyme extracts was assessed. Penicillium chrysogenum was found to produce an unknown dihydroxy fatty acid, a candidate gene implicated in this production was cloned and expressed, and the expressed enzyme was purified. The product obtained by the reaction of the purified enzyme with linoleic acid was identified as 8R,11S-dihydroxy-9,12(Z,Z)-octadecadienoic acid (8R,11S-DiHODE). The catalytic efficiency of this enzyme toward linoleic acid was the highest among the unsaturated fatty acids tested, indicating that this enzyme was a novel 8R,11S-linoleate diol synthase (8R,11S-LDS). A sexual stage in the life cycle of P. chrysogenum has recently been discovered, and 8R,11S-DiHODE produced by 8R,11S-LDS may constitute a precocious sexual inducer factor, responsible for regulating the sexual and asexual cycles of this fungus.

  14. Characterization of a novel 8R,11S-linoleate diol synthase from Penicillium chrysogenum by identification of its enzymatic products[S

    Shin, Kyung-Chul; Seo, Min-Ju; Oh, Deok-Kun


    To identify novel fatty acid diol synthases, putative candidate sequences from Penicillium species were analyzed, and hydroxy fatty acid production by crude Penicillium enzyme extracts was assessed. Penicillium chrysogenum was found to produce an unknown dihydroxy fatty acid, a candidate gene implicated in this production was cloned and expressed, and the expressed enzyme was purified. The product obtained by the reaction of the purified enzyme with linoleic acid was identified as 8R,11S-dihydroxy-9,12(Z,Z)-octadecadienoic acid (8R,11S-DiHODE). The catalytic efficiency of this enzyme toward linoleic acid was the highest among the unsaturated fatty acids tested, indicating that this enzyme was a novel 8R,11S-linoleate diol synthase (8R,11S-LDS). A sexual stage in the life cycle of P. chrysogenum has recently been discovered, and 8R,11S-DiHODE produced by 8R,11S-LDS may constitute a precocious sexual inducer factor, responsible for regulating the sexual and asexual cycles of this fungus. PMID:26681780

  15. Synthesis and intravenous infusion into the rat of glyceryl bisacetoacetate, 1-acetoacetamido-2, 3-propane diol, and partially reduced glucosyl pentaacetoacetate.

    Birkhahn, R H; Clemens, R J; Hubbs, J C


    The efficacy of parenteral nutrition could be improved by finding a more effective energy source. Esters of short-chain fatty acids have exhibited some promise as alternatives to glucose. The present study reports on two new esters and one amide, each containing acetoacetate as the organic acid. The three compounds: glyceryl bisacetoacetate, N-2',3'-dihydroxypropyl-3-oxo-butanamide (1-acetoacetamido-2,3-propane diol), and partially reduced glucosyl pentaacetoacetate, were synthesized and then continuously infused into rats for 7 d. The infusion rate provided 50% of the rats' estimated metabolic energy requirements, and rats were fed with a reduced-energy oral diet that provided the remaining 50% of energy plus adequate protein. Rat groups for each compound were: (1) experimental-compound-infused and ad libitum-fed, (2) isoenergetic glucose-infused and pairfed, and (3) saline infused and pair-fed. Body-weight changes, N losses and N retention were measured daily. All rats died from partially reduced glucosyl pentaacetoacetate infusion at 100% and 50% of the intended rate. Rats infused with 1-acetoacetamido-2,3-propane diol failed to gain weight and to increase the plasma ketone-body concentration. Glyceryl bisacetoacetate produced hyperketonaemia, and weight gain and N variables that were similar to those for glucose-infused rats. It was concluded that only glyceryl bisacetoacetate would make a satisfactory parenteral nutrient.

  16. Synthesis and characterization of new hydroxycarboxylate compounds obtained in the redox reaction between Fe(NO{sub 3}){sub 3} and diol

    Stefanescu, O., E-mail: [Politehnica University of Timisoara, Faculty of Industrial Chemistry and Environmental Engineering, P-ta Victoriei No. 2, Timisoara, RO-300006 (Romania); Vlase, T.; Vlase, G.; Doca, N. [West University of Timisoara, Research Center for Thermal Analysis in Environmental Problems, Str. Pestalozzi No. 16, Timisoara, RO-300115 (Romania); Stefanescu, M. [Politehnica University of Timisoara, Faculty of Industrial Chemistry and Environmental Engineering, P-ta Victoriei No. 2, Timisoara, RO-300006 (Romania)


    Highlights: {yields} New hydroxycarboxylate compounds obtained in the redox reaction Fe(NO{sub 3}){sub 3}-diols. {yields} Octahedral stereochemistry with [Fe(III)O{sub 6}] chromophore for the synthesized complexes. {yields} Fe(III) glyoxylate and succinate as precursors of iron oxide {gamma}-Fe{sub 2}O{sub 3} nanoparticles. - Abstract: The paper presents experimental studies and structural investigations of two new Fe(III) hydroxycarboxylate coordination compounds. The homopolynuclear complex combinations of Fe(III) glyoxylate and succinate type were obtained in the redox reaction between Fe(NO{sub 3}){sub 3} and diols (1,2-ethanediol and 1,4-butanediol). The synthesized coordination compounds and the products formed during their thermal conversion were characterized by thermal analysis (in air and nitrogen), FT-IR and UV-VIS spectrometry, Moessbauer spectrometry, electron microscopy and XRD. By thermal decomposition of the complex combinations, at 300 {sup o}C, the well crystallized pure phase {gamma}-Fe{sub 2}O{sub 3} as nanoparticles were formed.

  17. Winding of fibre composites; Vikling af fiberkompositter

    Lystrup, Aage


    Within the project 'Storage of hydrogen in advanced high pressure vessels' under the PSO-R AND D 2005 program one of the tasks is to describe the technology, which is used for manufacturing of fibre reinforced pressure vessels. Fibre reinforced pressure vessels for high pressures are manufactured by winding structural load bearing fibres around a mandrel or an internal liner. There are two different types of cylindrical pressure vessels: 1) Cylinders with thick metal liner, where only the cylindrical part is over wrapped with hoop windings, and 2) cylinders with a thin metal or polymer liner, where both the cylindrical part and the end domes are over wrapped with more layers with different fibre orientations (helical and hoop windings). This report describes the fundamental principles for filament winding of fibre reinforced polymer composites. After a short introduction to the advanced fibre composites, their properties and semi-raw materials used for fibre composites, the focus is on the process parameters, which have influence on the material quality of filament wound components. The report is both covering winding of fibre reinforced thermo-setting polymers as well as thermoplastic polymers, and there are references to vendors of filament winding machines, accessory equipment and computer software for design and manufacturing of filament wound components. (au)

  18. Winding of fibre composites; Vikling af fiberkompositter

    Lystrup, Aage


    Within the project 'Storage of hydrogen in advanced high pressure vessels' under the PSO-R AND D 2005 program one of the tasks is to describe the technology, which is used for manufacturing of fibre reinforced pressure vessels. Fibre reinforced pressure vessels for high pressures are manufactured by winding structural load bearing fibres around a mandrel or an internal liner. There are two different types of cylindrical pressure vessels: 1) Cylinders with thick metal liner, where only the cylindrical part is over wrapped with hoop windings, and 2) cylinders with a thin metal or polymer liner, where both the cylindrical part and the end domes are over wrapped with more layers with different fibre orientations (helical and hoop windings). This report describes the fundamental principles for filament winding of fibre reinforced polymer composites. After a short introduction to the advanced fibre composites, their properties and semi-raw materials used for fibre composites, the focus is on the process parameters, which have influence on the material quality of filament wound components. The report is both covering winding of fibre reinforced thermo-setting polymers as well as thermoplastic polymers, and there are references to vendors of filament winding machines, accessory equipment and computer software for design and manufacturing of filament wound components. (au)


    Yan-yan Yang; Kai-zhou Zhang; Yi-hu Song; Qiang Zheng


    Environment friendly thermosetting composites were prepared by blending wheat gluten (WG) and rice protein (RP) at different weight ratios with glycerol as plasticizer followed by compression molding the mixture at 120C to crosslink the proteins. Reducing agent of sodium bisulfate and sodium sulfite and crosslinking agent formaldehyde were used to adjust the properties of the composites. Morphology, moisture absorption and tensile properties were evaluated. The results showed that formaldehyde could increase tensile strength of the composites without significant influence on Young's modulus and elongation at break. On the other hand, reducing agents could improve tensile strength and extensibility simultaneously, which was much marked at WG/RP ratios from 7/3 to 3/7.

  20. Energy absorption and failure response of silk/epoxy composite square tubes: Experimental

    Oshkovr, Simin Ataollahi; Taher, Siavash Talebi; A. Eshkoor, Rahim


    This paper focuses on natural silk/epoxy composite square tubes energy absorption and failure response. The tested specimens were featured by a material combination of different lengths and same numbers of natural silk/epoxy composite layers in form of reinforced woven fabric in thermosetting epoxy...... resin. Tubes were compressed in INSTRON 5567 with a loading capacity of 30 kN. This research investigates the influence of the wall lengths on the compressive response and also failure mode of the tested tubes are analysed. The load–displacement behaviour of square tubes recorded during the test. Since...... natural woven silk has been used as textile in centuries but due to rare study of this fabric as reinforcement material for composites, the results of this paper can be considerable. Outcomes from this paper might be helpful to guide the design of crashworthy structures....

  1. Mathematical Model For Autoclave Curing Of Unsaturated Polyester Based Composite Materials

    Adnan A. Abdul Razak


    Full Text Available Heat transfer process involved in the autoclave curing of fiber-reinforced thermosetting composites is investigated numerically. A model for the prediction of the temperature and the extent of the reaction across the laminate thickness during curing process in the autoclave of unsaturated polyester based composite has been developed. The governing equation for one dimensional heat transfer, and accounting for the heat generation due to the exothermic cure reaction in the composites had been used.  It was found that the temperature at the central of the laminate increases up to the external imposed temperature, because of the thermal conductivity of the resin and fiber. The heat generated by the exothermic reaction of the resin is not adequately removed; the increase in the temperature at the center increases the resins rate reaction, which in turn generates more heat.

  2. Neutron scattering as a probe of liquid crystal polymer-reinforced composite materials

    Hjelm, R.P.; Douglas, E.P.; Benicewicz, B.C.; Langlois, D.A.


    This is the final report of a three-year Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). This research project sought to obtain nanoscale and molecular level information on the mechanism of reinforcement in liquid crystal polymer (LCP)-reinforced composites, to realize molecular-reinforced LCP composites, and to test the validity of the concept of molecular reinforcement. Small-angle neutron scattering was used to study the structures in the ternary phase diagram of LCP with liquid crystal thermosets and solvent on length scales ranging from 1-100 nm. The goal of the scattering measurements is to understand the phase morphology and degree of segregation of the reinforcing and matrix components. This information helps elucidate the physics of self assembly in these systems. This work provides an experimental basis for a microengineering approach to composites of vastly improved properties.

  3. Natural-fiber-reinforced polymer composites in automotive applications

    Holbery, James; Houston, Dan


    In the past decade, natural-fiber composites with thermoplastic and thermoset matrices have been embraced by European car manufacturers and suppliers for door panels, seat backs, headliners, package trays, dashboards, and interior parts. Natural fibers such as kenaf, hemp, flax, jute, and sisal offer such benefits as reductions in weight, cost, and CO2, less reliance on foreign oil sources, and recyclability. However, several major technical considerations must be addressed before the engineering, scientific, and commercial communities gain the confidence to enable wide-scale acceptance, particularly in exterior parts where a Class A surface finish is required. Challenges include the homogenization of the fiber's properties and a full understanding of the degree of polymerization and crystallization, adhesion between the fiber and matrix, moisture repellence, and flame-retardant properties, to name but a few.

  4. Expert model process control of composite materials in a press

    Saliba, Tony E.; Quinter, Suzanne R.; Abrams, Frances L.

    An expert model for the control of the press processing of thermoset composite materials has been developed. The knowledge base written using the PC PLUS expert system shell was interfaced with models written in FORTRAN. The expert model, which is running on a single computer with a single processor, takes advantage of the symbol-crunching capability of LISP and the number crunching capability of FORTRAN. The Expert Model control system is a qualitative-quantitative process automation (QQPA) system since it includes both quantitative model-based and qualitative rule-based expert system operations. Various physical and mechanical properties were measured from panels processed using the two cycles. Using QQPA, processing time has been reduced significantly without altering product quality.

  5. High performance carbon-carbon composites

    Lalit M Manocha


    Carbon-carbon composites rank first among ceramic composite materials with a spectrum of properties and applications in various sectors. These composites are made of fibres in various directions and carbonaceous polymers and hydrocarbons as matrix precursors. Their density and properties depend on the type and volume fraction of reinforcement, matrix precursor used and end heat treatment temperature. Composites made with thermosetting resins as matrix precursors possess low densities (1.55–1.75 g/cm3) and well-distributed microporosity whereas those made with pitch as the matrix precursor, after densification exhibit densities of 1.8–2.0 g/cm3 with some mesopores, and those made by the CVD technique with hydrocarbon gases, possess intermediate densities and matrices with close porosities. The former (resin-based) composites exhibit high flexural strength, low toughness and low thermal conductivity, whereas the latter (pitch- and CVD-based) can be made with very high thermal conductivity (400–700 W/MK) in the fibre direction. Carbon-carbon composites are used in a variety of sectors requiring high mechanical properties at elevated temperatures, good frictional properties for brake pads in high speed vehicles or high thermal conductivity for thermal management applications. However, for extended life applications, these composites need to be protected against oxidation either through matrix modification with Si, Zr, Hf etc. or by multilayer oxidation protection coatings consisting of SiC, silica, zircon etc.

  6. The composite reinforcement production in digital manufacturing: experimental validation of the heat transfer and cure modeling results

    Kazakov, I.; Krasnovskii, A.; Kutin, A.


    The experimental validation of the heat transfer and cure modeling results for 8-mm fiber-reinforced thermosetting composite reinforcement is reported in this article. The temperature and degree of cure of composite reinforcement are predicted using a two-dimensional heat transfer and curing model. The model uses the infrared radiant heating theory and takes into account the heat transfer between the composite rod and the surrounding air. The implicit finite difference method was used to solve the system of governing equations. The results obtained using mathematical model was compared to experimental data: the temperature field inside the composite reinforcement was measured by means of naked thermocouple; Differential Scanning Calorimetry (DSC) was used to measure the degree of cure of the final product. Calculated and measured temperature and degree of cure fields were in good agreement.

  7. The assessment of metal fiber reinforced polymeric composites

    Chung, Wenchiang R.


    Because of their low cost, excellent electrical conductivity, high specific strength (strength/density), and high specific modulus (modulus/density) short metal fiber reinforced composites have enjoyed a widespread use in many critical applications such as automotive industry, aircraft manufacturing, national defense, and space technology. However, little data has been found in the study of short metal fibrous composites. Optimum fiber concentration in a resin matrix and fiber aspect ratio (length-to-diameter ratio) are often not available to a user. Stress concentration at short fiber ends is the other concern when the composite is applied to a load-bearing application. Fracture in such composites where the damage will be initiated or accumulated is usually difficult to be determined. An experimental investigation is therefore carefully designed and undertaken to systematically evaluate the mechanical properties as well as electrical properties. Inconel 601 (nickel based) metal fiber with a diameter of eight microns is used to reinforce commercially available thermoset polyester resin. Mechanical testing such as tensile, impact, and flexure tests along with electrical conductivity measurements is conducted to study the feasibility of using such composites. The advantages and limitations of applying chopped metal fiber reinforced polymeric composites are also discussed.

  8. Carotenoid composition and vitamin A value of an Argentinian squash (Cucurbita moschata).

    González, E; Montenegro, M A; Nazareno, M A; López de Mishima, B A


    The carotenoid composition of butternut squash (Cucurbita moschata) cultivated in the province of Santiago del Estero, Argentina, was determined. The main carotenoids isolated were identified as beta-carotene (beta,beta-carotene), alpha-carotene (beta,epsilon-carotene), and lutein (beta,epsilon-carotene-3,3'-diol) and the minor carotenoids, as phytofluene (7,8,11,12,7',8'-hexahydro-psi,psi-carotene), zeta-carotene (7,8,7',8'-tetrahydro-psi,psi-carotene), neurosporene (7,8-dihydro-psi,psi-carotene), violaxanthin (5,6,5',6'- diepoxy-5,6,5',6'-tetrahydro-beta,beta-carotene-3,3'-diol) and neoxanthin (5,6-epoxy-6,7-didehydro-5,6,5',6'-tetrahydro-beta,beta- carotene-3,5,3'-triol). In some samples, 5,6,5',6'-beta-carotene diepoxide, (5,6,5',6'-diepoxy-5,6,5',6'-tetrahydro-beta,beta-carotene) and flavoxanthin (5,8-epoxy-5,8-dihydro-beta,epsilon-carotene-3,3'-diol) were detected. The presence of cis-isomers of beta,beta-carotene was also detected by HPLC. The vitamin A value obtained was 432 micrograms RE/100 g fresh sample, which indicates that this vegetable is an important source of provitamin A.

  9. Ruthenium-complex catalyzed N-(cyclo)alkylation of aromatic amines with diols. Selective synthesis of N-(n-hydroixyalkyl)anilines of type PhNH(CH2)nOH and of some bioactive arylpiperazines,

    Koten, G. van; Abbenhuis, R.A.T.M.; Boersma, J.


    A new class of well-defined neutral mono-, and dicationic ruthenium(II) complexes containing a neutral terdentate donor system [C5H3N(CH2E)(2)-2,6] (E = PPh2 (PNP) or NMe2 (NN'N)) has been found effective as catalyst precursor in N-(cyclo)alkylation reactions of aromatic amines with diols

  10. Recyclable epoxy resins: An example of green approach for advanced composite applications

    Cicala, Gianluca; Rosa, Daniela La; Musarra, Marco; Saccullo, Giuseppe; Banatao, Rey; Pastine, Stefan


    Automotive composite applications are increasingly growing due to demand for lightweight structures to comply to the requirements for fuel reduction. HP-RTM is gaining relevance as one of the preferred production technologies for high volume applications. The BMW i3 life module being a notable example of HP-RTM application. The key aspects of HP-RTM are the short injection times (i.e. less than 1min) and the fast curing of the thermoset resins (i.e. less than 10min). The choice of using thermosets poses relevant issues for their limited recycling options. The standard recycling solution is the incineration but, this solution poses some concerns in terms of global environmental impact. Novel solutions are presented in this work based on the use of recyclable epoxy systems. In our work the results of experimentation carried out by our group with cleavable ammines by Connora Technologies and bioepoxy resins by Entropy Resins will be discussed. The multiple uses of recycled matrices obtained treating the recyclable epoxy resins are discussed in the framework of a "cradle" to "crave" approach. Finally, Life Cycle Assessment (LCA) is used to evaluate the environmental benefits of the proposed approach.

  11. Repression of tropolone production and induction of a Burkholderia plantarii pseudo-biofilm by carot-4-en-9,10-diol, a cell-to-cell signaling disrupter produced by Trichoderma virens.

    Wang, Mengcen; Hashimoto, Makoto; Hashidoko, Yasuyuki


    The tropolone-tolerant Trichoderma virens PS1-7 is a biocontrol agent against Burkholderia plantarii, causative of rice seedling blight. When exposed to catechol, this fungus dose-dependently produced carot-4-en-9,10-diol, a sesquiterpene-type autoregulatory signal molecule that promotes self-conidiation of T. virens PS1-7 mycelia. It was, however, uncertain why T. virens PS1-7 attenuates the symptom development of the rice seedlings infested with B. plantarii. To reveal the antagonism by T. virens PS1-7 against B. plantarii leading to repression of tropolone production in a coculture system, bioassay-guided screening for active compounds from a 3-d culture of T. virens PS1-7 was conducted. As a result, carot-4-en-9,10-diol was identified and found to repress tropolone production of B. plantarii from 10 to 200 µM in a dose-dependent manner as well as attenuate virulence of B. plantarii on rice seedlings. Quantitative RT-PCR analysis revealed that transcriptional suppression of N-acyl-L-homoserine lactone synthase plaI in B. plantarii was the main mode of action by which carot-4-en-9,10-diol mediated the quorum quenching responsible for repression of tropolone production. In addition, the unique response of B. plantarii to carot-4-en-9,10-diol in the biofilm formed in the static culture system was also found. Although the initial stage of B. plantarii biofilm formation was induced by both tropolone and carot-4-en-9,10-diol, it was induced in different states. Moreover, the B. plantarii biofilm that was induced by carot-4-en-9,10-diol at the late stage showed defects not only in matrix structure but also cell viability. Our findings demonstrate that carot-4-en-9,10-diol released by T. virens PS1-7 acts as an interkingdom cell-to-cell signaling molecule against B. plantarii to repress tropolone production and induces pseudo-biofilm to the cells. This observation also led to another discovery that tropolone is an autoregulatory cell-to-cell signaling molecule of B

  12. Repression of tropolone production and induction of a Burkholderia plantarii pseudo-biofilm by carot-4-en-9,10-diol, a cell-to-cell signaling disrupter produced by Trichoderma virens.

    Mengcen Wang

    Full Text Available BACKGROUND: The tropolone-tolerant Trichoderma virens PS1-7 is a biocontrol agent against Burkholderia plantarii, causative of rice seedling blight. When exposed to catechol, this fungus dose-dependently produced carot-4-en-9,10-diol, a sesquiterpene-type autoregulatory signal molecule that promotes self-conidiation of T. virens PS1-7 mycelia. It was, however, uncertain why T. virens PS1-7 attenuates the symptom development of the rice seedlings infested with B. plantarii. METHODOLOGY/PRINCIPAL FINDINGS: To reveal the antagonism by T. virens PS1-7 against B. plantarii leading to repression of tropolone production in a coculture system, bioassay-guided screening for active compounds from a 3-d culture of T. virens PS1-7 was conducted. As a result, carot-4-en-9,10-diol was identified and found to repress tropolone production of B. plantarii from 10 to 200 µM in a dose-dependent manner as well as attenuate virulence of B. plantarii on rice seedlings. Quantitative RT-PCR analysis revealed that transcriptional suppression of N-acyl-L-homoserine lactone synthase plaI in B. plantarii was the main mode of action by which carot-4-en-9,10-diol mediated the quorum quenching responsible for repression of tropolone production. In addition, the unique response of B. plantarii to carot-4-en-9,10-diol in the biofilm formed in the static culture system was also found. Although the initial stage of B. plantarii biofilm formation was induced by both tropolone and carot-4-en-9,10-diol, it was induced in different states. Moreover, the B. plantarii biofilm that was induced by carot-4-en-9,10-diol at the late stage showed defects not only in matrix structure but also cell viability. CONCLUSIONS/SIGNIFICANCE: Our findings demonstrate that carot-4-en-9,10-diol released by T. virens PS1-7 acts as an interkingdom cell-to-cell signaling molecule against B. plantarii to repress tropolone production and induces pseudo-biofilm to the cells. This observation also led to

  13. Bis(1,10-phenanthroline-κ2N,N′(sulfato-κ2O,O′cobalt(II propane-1,3-diol solvate

    Kai-Long Zhong


    Full Text Available The title compound, [Co(SO4(C12H8N22]·C3H8O2, was obtained unexpectedly as a by-product during an attempt to synthesize a mixed-ligand complex of CoII with 1,10-phenanthroline (phen and melamine via a solvothermal reaction. The CoII metal ions are in a distorted octahedral coordination environment formed by four N atoms from two chelating phen ligands and two O atoms from a bidentate sulfate ligand. The two chelating N2C2 groups are almost perpendicular to each other [dihedral angle = 80.06 (8°]. A twofold rotation axis passes through the Co and S atoms, and also through the central C atom of the propane-1,3-diol solvent molecule. Intermolecular O—H...O hydrogen bonds help to stabilize the structure.

  14. Computational and NMR Spectroscopic Evidence for Stereochemistry-Dependent Conformations of 2,2,6,6-Tetramethylpiperidinyl-Masked 1,2-Diols.

    Fought, Ellie L; Chatterjee, Shreyosree; Windus, Theresa L; Chen, Jason S


    2,2,6,6-Tetramethylpiperidinyl-masked 1,2-diols exhibited stereochemistry-dependent hydroxyl proton chemical shifts: ca. 7 ppm for the syn diastereomer and ca. 2 ppm for the anti diastereomer. A computational search for low energy geometries revealed that the syn isomer favors a six-membered ring hydrogen bond to nitrogen and the anti isomer favors a five-membered ring hydrogen bond to oxygen. The computed low energy conformations were found to have a large difference in hydroxyl proton shielding that was reflected in the experimental chemical shift difference. This chemical shift difference was observed in a broad range of solvents, and thus may be useful as a stereochemical probe. The stereochemistry-dependent conformation and chemical shift signature appeared to be due to a syn pentane interaction between the gem-dimethyl groups on the 2,2,6,6-tetramethylpiperidinyl moiety.

  15. Theoretical studies and spectroscopic characterization of novel 4-methyl-5-((5-phenyl-1,3,4-oxadiazol-2-yl)thio)benzene-1,2-diol

    Soleimani Amiri, Somayeh; Makarem, Somayeh; Ahmar, Hamid; Ashenagar, Samaneh


    The structural, electronic, and spectroscopic properties of 4-methyl-5-((5-phenyl-1,3,4 oxadiazol-2-yl)thio)benzene-1,2-diol (MPOTB) have been carried out at ab initio and DFT levels. A detailed study of geometrical parameters, Infrared spectrum, chemical shifts (13C NMR, 1H NMR), and electronic properties of the title compound is presented. The correlation between the theoretical and the experimental 13C, and 1H chemical shifts of MPOTB were about 1.02-1.03 and 0.98-1.00, respectively. The electronic properties, such as molecular electrostatic potential, NBO atomic charges, HOMO and LUMO energies were performed at above levels. Rather high hardness of MPOTB introduces it as a stable molecule. As a result, the calculated findings were compared with the observed values and generally found to be in good agreement.

  16. Carbon fiber composite characterization in adverse thermal environments.

    Gomez-Vasquez, Sylvia; Brown, Alexander L.; Hubbard, Joshua A.; Ramirez, Ciro J.; Dodd, Amanda B.


    The behavior of carbon fiber aircraft composites was studied in adverse thermal environments. The effects of resin composition and fiber orientation were measured in two test configurations: 102 by 127 millimeter (mm) test coupons were irradiated at approximately 22.5 kW/m{sup 2} to measure thermal response, and 102 by 254 mm test coupons were irradiated at approximately 30.7 kW/m{sup 2} to characterize piloted flame spread in the vertically upward direction. Carbon-fiber composite materials with epoxy and bismaleimide resins, and uni-directional and woven fiber orientations, were tested. Bismaleimide samples produced less smoke, and were more resistant to flame spread, as expected for high temperature thermoset resins with characteristically lower heat release rates. All materials lost approximately 20-25% of their mass regardless of resin type, fiber orientation, or test configuration. Woven fiber composites displayed localized smoke jetting whereas uni-directional composites developed cracks parallel to the fibers from which smoke and flames emanated. Swelling and delamination were observed with volumetric expansion on the order of 100% to 200%. The purpose of this work was to provide validation data for SNL's foundational thermal and combustion modeling capabilities.

  17. Finite element modeling of consolidation of composite laminates

    Xiangqiao Yan


    Advanced fiber reinforced polymer composites have been increasingly applied to various structural corn-ponents.One of the important processes to fabricate high performance laminated composites is an autoclave assisted prepreg lay-up.Since the quality of laminated composites is largely affected by the cure cycle,selection of an appropriate cure cycle for each application is important and must be opti-mized.Thus.some fundamental model of the consolidation and cure processes is necessary for selecting suitable param-eters for a specific application.This article is concerned with the "flow-compaction" model during the autoclave process-ing of composite materials.By using a weighted residual method,two-dimensional finite element formulation for the consolidation process of thick thermosetting composites is presented and the corresponding finite element code is developed.Numerical examples.including comparison of the present numerical results with one-dimensional and two-dimensional analytical solutions,are given to illustrate the accuracy and effectiveness of the proposed finite element formulation.In addition,a consolidation simulation of As4/3501-6 graphite/epoxy laminate is carried out and compared with the experimental results available in the literature.

  18. Corrosion inhibition property of polyester-groundnut shell biodegradable composite.

    Sounthari, P; Kiruthika, A; Saranya, J; Parameswari, K; Chitra, S


    The use of natural fibers as reinforcing materials in thermoplastics and thermoset matrix composites provide optimistic environmental profits with regard to ultimate disposability and better use of raw materials. The present work is focused on the corrosion inhibition property of a polymer matrix composite produced by the use of groundnut shell (GNS) waste. Polyester (PE) was synthesized by condensation polymerization of symmetrical 1,3,4-oxadiazole and pimelic acid using sodium lauryl sulfate as surfactant. The polyester-groundnut shell composite (PEGNS) was prepared by ultrasonication method. The synthesized polyester-groundnut shell composite was characterized by FT-IR, TGA and XRD analysis. The corrosion inhibitory effect of PEGNS on mild steel in 1M H2SO4 was investigated using gravimetric method, electrochemical impedance spectroscopy, potentiodynamic polarization, atomic absorption spectroscopy and scanning electron microscopy. The results showed that PEGNS inhibited mild steel corrosion in acid solution and indicated that the inhibition efficiency increased with increasing inhibitor concentration and decrease with increasing temperature. The composite inhibited the corrosion of mild steel through adsorption following the Langmuir adsorption isotherm. Changes in the impedance parameters Rt, Cdl, Icorr, Ecorr, ba and bc suggested the adsorption of PEGNS onto the mild steel surface, leading to the formation of protective film.

  19. Tribological behaviour of unidirectional carbon fibre-reinforced epoxy composites

    Şahin, Y.; De Baets, P.


    Tribological behaviour of unidirectional carbon fibre-reinforced epoxy composites containing 42wt.% (CU42) and 52wt.% (CU52) carbon fibres fabricated by moulding technique was investigated on a pin-on-flat plate configuration. It is the first time to measure static and dynamic coefficient of frictions and wear rates of epoxy composites under heavy loading conditions. Microstructures of composites were examined by scanning electron microscopy (SEM). The experimental results indicated the carbon fiber improved the tribological properties of thermoset epoxy by reducing wear rate, but increased the coefficient of friction. At higher load, average wear rates were about 10.8x10-5 mm3/N.m for composites while it was about 38.20x10-5 mm3/N.m for epoxy resin. The wear rate decreased with decreasing load while friction coefficient increased with decreasing load. Moreover, friction coefficient of composites of CU42 tested at 90 N load was measured to be in the range 0.35 and 0.13 for static and dynamic component, respectively.

  20. Hybrid yarn for thermoplastic fibre composites. Summary of technical results

    Lystrup, Aa.


    This report is a summary of the technical results obtained within the framework program: `Hybrid Yarn for Thermoplastic Fibre Composites`. The program which started at the 15th of June 1994 and expired at the 31st of December 1997, was a framework program under the Danish Materials Technology Program, MUP2. A new type of hybrid yarn for production of fibre composites with thermoplastic matrix material is developed and tested. A hybrid yarn is a commingled textured yarn consisting of structural fibres and thermoplastic fibres. In a subsequent heating and consolidation process the plastic fibres melt and become the matrix material in the formed fibre composite material. Two types of processing technology are developed and studied: Vacuum consolidation and press consolidation. Vacuum consolidation of hybrid yarn fabrics is suitable for fabrication of larger parts such as wind turbine blades, and press consolidation is a fast process suitable for smaller parts such as automobile body parts. To demonstrate the potential for industrial use of the developed hybrid yarn and process technologies a section of a wind turbine blade, an inspection cover and a car door-post have been produced. An environmental evaluation of the manufacture of hybrid yarn and composites shows that the use of the hybrid yarn is a gain for both the working environment and the external environment, compared to the use of thermosetting polymer composites. (au)

  1. 3,3',4,4',5-Pentachlorobiphenyl (PCB 126) Decreases Hepatic and Systemic Ratios of Epoxide to Diol Metabolites of Unsaturated Fatty Acids in Male Rats.

    Wu, Xianai; Yang, Jun; Morisseau, Christophe; Robertson, Larry W; Hammock, Bruce; Lehmler, Hans-Joachim


    Disruption of the homeostasis of oxygenated regulatory lipid mediators (oxylipins), potential markers of exposure to aryl hydrocarbon receptor (AhR) agonists, such as 3,3',4,4',5-pentachlorobiphenyl (PCB 126), is associated with a range of diseases, including nonalcoholic fatty liver disease and nonalcoholic steatohepatitis. Here we test the hypothesis that PCB 126 exposure alters the levels of oxylipins in rats. Male Sprague-Dawley rats (5-weeks old) were treated over a 3-month period every 2 weeks with intraperitoneal injections of PCB 126 in corn oil (cumulative doses of 0, 19.8, 97.8, and 390 µg/kg b.w.; 6 injections total). PCB 126 treatment caused a reduction in growth rates at the highest dose investigated, a dose-dependent decrease in thymus weights, and a dose-dependent increase in liver weights. Liver PCB 126 levels increased in a dose-dependent manner, while levels in plasma were below or close to the detection limit. The ratios of several epoxides to diol metabolites formed via the cytochrome P450 (P450) monooxygenase/soluble epoxide hydrolase (sEH) pathway from polyunsaturated fatty acids displayed a dose-dependent decrease in the liver and plasma, whereas levels of oxylipins formed by other metabolic pathways were generally not altered by PCB 126 treatment. The effects of PCB 126 on epoxide-to-diol ratios were associated with an increased CYP1A activity in liver microsomes and an increased sEH activity in liver cytosol and peroxisomes. These results suggest that oxylipins are potential biomarkers of exposure to PCB 126 and that the P450/sEH pathway is a therapeutic target for PCB 126-mediated hepatotoxicity that warrants further attention.

  2. Diacyltransferase Activity and Chain Length Specificity of Mycobacterium tuberculosis PapA5 in the Synthesis of Alkyl β-Diol Lipids.

    Touchette, Megan H; Bommineni, Gopal R; Delle Bovi, Richard J; Gadbery, John E; Nicora, Carrie D; Shukla, Anil K; Kyle, Jennifer E; Metz, Thomas O; Martin, Dwight W; Sampson, Nicole S; Miller, W Todd; Tonge, Peter J; Seeliger, Jessica C


    Although they are classified as Gram-positive bacteria, Corynebacterineae possess an asymmetric outer membrane that imparts structural and thereby physiological similarity to more distantly related Gram-negative bacteria. Like lipopolysaccharide in Gram-negative bacteria, lipids in the outer membrane of Corynebacterineae have been associated with the virulence of pathogenic species such as Mycobacterium tuberculosis (Mtb). For example, Mtb strains that lack long, branched-chain alkyl esters known as dimycocerosates (DIMs) are significantly attenuated in model infections. The resultant interest in the biosynthetic pathway of these unusual virulence factors has led to the elucidation of many of the steps leading to the final esterification of the alkyl β-diol, phthiocerol, with branched-chain fatty acids known as mycocerosates. PapA5 is an acyltransferase implicated in these final reactions. Here, we show that PapA5 is indeed the terminal enzyme in DIM biosynthesis by demonstrating its dual esterification activity and chain-length preference using synthetic alkyl β-diol substrate analogues. By applying these analogues to a series of PapA5 mutants, we also revise a model for the substrate binding within PapA5. Finally, we demonstrate that the Mtb Ser/Thr kinases PknB and PknE modify PapA5 on three overlapping Thr residues and that a fourth Thr is unique to PknE phosphorylation. These results clarify the DIM biosynthetic pathway and indicate post-translational modifications that warrant further elucidation for their roles in the regulation of DIM biosynthesis.

  3. Novel Repair Concept for Composite Materials by Repetitive Geometrical Interlock Elements

    David Zaremba


    Full Text Available Material adapted repair technologies for fiber-reinforced polymers with thermosetting matrix systems are currently characterized by requiring major efforts for repair preparation and accomplishment in all industrial areas of application. In order to allow for a uniform distribution of material and geometrical parameters over the repair zone, a novel composite interlock repair concept is introduced, which is based on a repair zone with undercuts prepared by water-jet technology. The presented numerical and experimental sensitivity analyses make a contribution to the systematic development of the interlock repair technology with respect to material and geometrical factors of influence. The results show the ability of the novel concept for a reproducible and automatable composite repair.

  4. A High T(sub g) PMR Polyimide Composites (DMBZ-15)

    Chuang, Kathy C.; Bowles, Kenneth J.; Papadopoulos, Demitrios S.; Hardy-Green, DeNise; Mccorkle, Linda


    A high T(sub g) thermosetting PMR-type polyimide, designated as DMBZ-15, was developed by replacing methylene dianline (MDA) in PMR-15 with 2,2'-dimethylbenzidine. Polyimide/carbon fiber (T650-35) composites were fabricated from a formulation of 3,3', 4,4'-benzophenonetetracarboxylic acid dimethyl ester (BTDE) and 2,2'-dimethylbenzidine (DMBZ), along with nadic ester (NE) as the endcap. DMBZ-15 displays a higher glass transition temperature (T(sub g) = 414 C) than PMR-15 (T(sub g) = 345 C), and thus retains better mechanical properties for brief exposure above 400 C. The physical properties and longterm thermo-oxidative stability of the DMBZ-15 polyimide/carbon fiber composites are also compared to that of PMR-15.

  5. Gravity Effects of Curing Angle on Laminated Composite Structures: A Review on Novel Study

    T. T. T. Jennise


    Full Text Available Composites manufactured by small and medium industries/entrepreneurs (SMI/E are conventionally cured in the horizontal position. Hence, the confined space restricts optimum productivity. Besides, SMI/E is unable to allocate high budget for high-end technology such as autoclave and vacuum mechanical oven which limits the development of SMI/E as a result of high capital cost. Through a series of literature review, the review confirmed that there is no similar scientific study has been conducted. Consequently, the review is carried out to facilitate the investigation of the feasibility of a gravity cured glass fiber laminated thermosetting composites via vacuum bagging at angle position from horizontal (0° to vertical (90° to enhance the curing space required.

  6. An improved processible acetylene-terminated polyimide for composites

    Landis, A. L.; Naselow, A. B.


    The newest member of a family of thermosetting acetylene-substituted polyimide oligomers is HR600P. This oligomer is the isoimide version of the oligomer known as HR600P and Thermid 600. Although both types of material yield the same heat resistant end products after cure, HR600P has much superior processing characteristics. This attributed to its lower melting temperature (160 + or - 10 C, 320 + or - 20 F) in contrast to 202 C (396 F) for Thermid MC-600, its longer gel time at its processing temperature (16 to 30 minutes bvs 3 minutes), and its excellent solubility in low boiling solvents such as tetrahydrofuran, glymes, or 4:1 methyl ethyl ketone/toluene mixtures. These advantages provide more acceptable coating and impregnation procedures, allow for more complete removal at lower temperatures, provide a longer pot life or working time, and allow composite structure fabrication in conventional autoclaves used for epoxy composite curing. The excellent processing characteristics of HR600P allow its use in large area laminated structures, structural composites, and molding compositions.

  7. 带金属嵌件的热固性塑料手柄注射模设计%Design of Injection Mold for the Thermosetting Plastic Handle with Metal Insert



    Insert the metal with a thermosetting plastic injection mold for the slider with spring structure of stainless steel metal insert,reliable positioning,effectively ensure the forming process is carried out smoothly. The products in large quantities of production testing,production efficiency is high,products of quality is good.%带金属嵌件的热固性塑料手柄注射模采用滑块加弹簧的结构使不锈钢金属嵌件能够可靠地定位,有效地保证了成型工艺的顺利进行。手柄经大批量的生产检验,生产效率高,质量好。

  8. Isolation and identification of dieldrin-degrading Pseudonocardia sp. strain KSF27 using a soil-charcoal perfusion method with aldrin trans-diol as a structural analog of dieldrin.

    Sakakibara, Futa; Takagi, Kazuhiro; Kataoka, Ryota; Kiyota, Hiromasa; Sato, Yuuki; Okada, Sanae


    We isolated a novel aerobic dieldrin-degrading bacterium from an enrichment culture in a soil-charcoal perfusion system. Enrichment culture using a soil-charcoal perfusion system was an effective way to obtain microorganisms that degrade recalcitrant compounds. The soil-charcoal perfusion was performed using aldrin trans-diol, which was a metabolite of dieldrin. Aldrin trans-diol had higher bioavailability (2.5 mg/l) than dieldrin (0.1-0.25 mg/l), therefore it is possible for microorganisms to utilize it as a substrate in soil. After 100 days of circulation and three exchanges of the medium, the enriched charcoal was harvested and a bacterium isolated. The isolate was designated as strain KSF27 and was found to be closely related to Pseudonocardia spp. as determined by 16S rRNA sequencing analysis. Strain KSF27 degraded aldrin trans-diol by 0.05 μmol/l from an initial concentration of 25.5 μmol/l. The metabolite of aldrin trans-diol was detected by HPLC/MS and determined to be aldrindicarboxylic acid based on retention time and the MS fragment. Moreover, strain KSF27 degraded dieldrin from 14.06 μmol/l to 2.01 μmol/l over a 10-day incubation at 30°C. This strain degraded dieldrin and other persistent organochlorine pesticides, such as α-endosulfan, β-endosulfan, endosulfan sulfate, heptachlor, heptachlor epoxide and chlordecone. Copyright © 2011 Elsevier Inc. All rights reserved.

  9. Process Optimization of Bismaleimide (BMI) Resin Infused Carbon Fiber Composite

    Ehrlich, Joshua W.; Tate, LaNetra C.; Cox, Sarah B.; Taylor, Brian J.; Wright, M. Clara; Faughnan, Patrick D.; Batterson, Lawrence M.; Caraccio, Anne J.; Sampson, Jeffery W.


    Engineers today are presented with the opportunity to design and build the next generation of space vehicles out of the lightest, strongest, and most durable materials available. Composites offer excellent structural characteristics and outstanding reliability in many forms that will be utilized in future aerospace applications including the Commercial Crew and Cargo Program and the Orion space capsule. NASA's Composites for Exploration (CoEx) project researches the various methods of manufacturing composite materials of different fiber characteristics while using proven infusion methods of different resin compositions. Development and testing on these different material combinations will provide engineers the opportunity to produce optimal material compounds for multidisciplinary applications. Through the CoEx project, engineers pursue the opportunity to research and develop repair patch procedures for damaged spacecraft. Working in conjunction with Raptor Resins Inc., NASA engineers are utilizing high flow liquid infusion molding practices to manufacture high-temperature composite parts comprised of intermediate modulus 7 (IM7) carbon fiber material. IM7 is a continuous, high-tensile strength composite with outstanding structural qualities such as high shear strength, tensile strength and modulus as well as excellent corrosion, creep, and fatigue resistance. IM7 carbon fiber, combined with existing thermoset and thermoplastic resin systems, can provide improvements in material strength reinforcement and deformation-resistant properties for high-temperature applications. Void analysis of the different layups of the IM7 material discovered the largest total void composition within the [ +45 , 90 , 90 , -45 ] composite panel. Tensile and compressional testing proved the highest mechanical strength was found in the [0 4] layup. This paper further investigates the infusion procedure of a low-cost/high-performance BMI resin into an IM7 carbon fiber material and the

  10. 酯交换法合成聚碳酸酯二元醇研究的进展%The Progress of the Synthesis Method for Polycarbonate Diol by Transesterification

    魏亚波; 韩生


    The polycarbonate diol usage, advantage and synthetic methods were introduced. The development of synthesizing polycarbonate diol using different kinds of homogeneous catalysts( alkali metal compounds catalyst, alkaline earth metal compound catalyst, an organic metal compound catalyst, an organic amine catalyst, the hydro-talcite-type catalyst) and heterogeneous catalysts ( the supported catalyst and enzyme catalyst) were described. The problem of the polycarbonate diol synthesis and the ways of solving were summarised.%介绍了聚碳酸酯二元醇的用途、优点及合成方法。综述了使用均相催化剂(碱金属化合物催化剂、碱土金属化合物催化剂、有机金属化合物催化剂、有机胺类催化剂)和多相作化剂(水滑石类催化剂、负载型催化剂、酶催化剂)合成聚碳酸酯二元醇的研究进展。总结了合成聚碳酸酯二元醇过程中遇到的问题并提出了解决方法。

  11. Biomechanics of Natural Fiber Green Composites as Internal Bone Plate rafted

    Hashim Ahmed M.


    Full Text Available The main purpose of this paper was to introduce a new series of green composites as a plate for bone fracture applications. These green composites offer many advantages over traditional composites and biocomposites based on synthetic polymers. In current work, the new green composites bone plate based on two types of biopolymers involves biopolymethylmethacrylate thermoplastic material and bioepoxy thermosetting material reinforced with randomly oriented corn natural fibers at different weight fractions (5, 10, 15, and 20% were fabricated by hand lay–up technique. Four forms of green composites ; treated and untreated corn biopolymethylmethacrylate groups A and B respectively, treated and untreated corn bioepoxy groups C and D respectively were investigated. The mechanical properties were tested (tensile, compression, and compact tension under a flow of phosphate buffered saline PBS at 37 °C has been reported. The experimental results showed that the green composites group A have the best mechanical properties than other groups under PBS condition while the green composites group D have the weak mechanical properties due to plastization by immersion in PBS solution. Also, the analysis of femur bone fracture plates carried out by applying finite element method FEM using the ANSYS 16 software package.

  12. Electromagnetic and Dynamic Mechanical Properties of Epoxy and Vinylester-Based Composites Filled with Graphene Nanoplatelets

    Fabrizio Marra


    Full Text Available Development of epoxy or epoxy-based vinyl ester composites with improved mechanical and electromagnetic properties, filled with carbon-based nanomaterials, is of crucial interest for use in aerospace applications as radar absorbing materials at radio frequency. Numerous studies have highlighted the fact that the effective functional properties of this class of polymer composites are strongly dependent on the production process, which affects the dispersion of the nanofiller in the polymer matrix and the formation of micro-sized aggregations, degrading the final properties of the composite. The assessment of the presence of nanofiller aggregation in a composite through microscopy investigations is quite inefficient in the case of large scale applications, and in general provides local information about the aggregation state of the nanofiller rather than an effective representation of the degradation of the functional properties of the composite due to the presence of the aggregates. In this paper, we investigate the mechanical, electrical, and electromagnetic properties of thermosetting polymer composites filled with graphene nanoplatelets (GNPs. Moreover, we propose a novel approach based on measurements of the dielectric permittivity of the composite in the 8–12 GHz range in order to assess the presence of nanofiller aggregates and to estimate their average size and dimensions.

  13. Transformações químicas do (+-10b,14-diol-allo-aromadendrano, isolado de duguetia glabriuscula r. e. fries (r. e. fries (annonaceae e avaliações biológicas de alguns derivados obtidos Chemical modifications of (+-allo-aromadendrane-10b,14-diol isolated from duguetia glabriuscula r. e. fries (r. e. fries (annonaceae and biological evaluation of some obtained derivatives

    Dênis Pires de Lima


    Full Text Available The sesquiterpene (+-allo-aromadendrane-10b-14-diol 1 was the lead compound to the preparation of several derivatives in order to test their biological activity against A. salina, C. sphaerospermum, E. coli and S. aureus. In this way the monoalcohols (+-viridiflorol 4, 9 and 11 were synthesized from 1 together with the acetal 6, the ketal 7, and the ketone 8. The oxirane 3 and nitrile 5 were also prepared using as an intermediate the tosylate derivative 2.

  14. Infrared thermography to impact damaging of composite materials

    Boccardi, Simone; Boffa, Natalino D.; Carlomagno, Giovanni M.; Meola, Carosena; Ricci, Fabrizio; Russo, Pietro; Simeoli, Giorgio


    Composite materials are becoming ever more popular and being used in an increasing number of applications. This because, to meet the users' demand, it is possible to create a new material of given characteristics in a quite simple way by changing either the type of matrix, or reinforcement. Of course, any new material requires characterization for its appropriate exploitation. In this context, infrared thermography (IRT) represents a viable means since it is non-contact, non-intrusive and can be used either for non-destructive evaluation to detect manufacturing defects, or fatigue induced degradation, or else for monitoring online the response to applied loads. In this work, IRT is used to investigate different types of composite materials which are based on either a thermoset, or a thermoplastic matrix, which may be neat, or modified by addition of a percentage of a specific compatibilizing agent, and reinforced with carbon, glass, or jute fibers. IRT is used with a twofold function. First, to non-destructively evaluate, with the lock-in technique, materials before and after impact to either assure absence of manufacturing defects, or discover the damage caused by the impact. Second, IRT is used to visualize thermal effects, which develop when the material is subjected to impact. The obtained results show that it is possible to follow the material bending, delamination and eventual failure under impact and get information, which may be valuable to deepen the complex impact damaging mechanisms of composites

  15. Viscoelastic properties of kenaf reinforced unsaturated polyester composites

    Osman, Ekhlas A.; Mutasher, Saad A.


    In order to quantify the effect of temperature on the mechanical and dynamic properties of kenaf fiber unsaturated polyester composites, formulations containing 10 wt.% to 40 wt.% kenaf fiber were produced and tested at two representative temperatures of 30°C and 50°C. Dynamic mechanical analysis was performed, to obtain the strain and creep compliance for kenaf composites at various styrene concentrations. It is possible to obtain creep curves at different temperature levels which can be shifted along the time axis to generate a single curve known as a master curve. This technique is known as the time-temperature superposition principle. Shift factors conformed to a William-Landel-Ferry (WLF) equation. However, more long term creep data was needed in order to further validate the applicability of time-temperature superposition principle (TTSP) to this material. The primary creep strain model was fitted to 60 min creep data. The resulting equation was then extrapolated to 5.5 days; the creep strain model of power-law was successfully used to predict the long-term creep behavior of natural fiber/thermoset composites.

  16. ROMP-based polymer composites and biorenewable rubbers

    Jeong, Wonje [Iowa State Univ., Ames, IA (United States)


    This research is divided into two related topics. In the first topic, the synthesis and characterization of novel composite materials reinforced with MWCNTs by ring-opening metathesis polymerization (ROMP) is reported for two ROMP based monomers: dicyclopentadiene (DCPD) and 5-ethylidene-2-norbornene (ENB). Homogeneous dispersion of MWCNTs in the polymer matrices is achieved by grafting norbornene moieties onto the nanotube surface. For the DCPD-based system, the investigation of mechanical properties of the composites shows a remarkable increase of tensile toughness with just 0.4 wt % of functionalized MWCNTs (f-MWCNTs). To our knowledge, this represents the highest toughness enhancement efficiency in thermosetting composites ever reported. DMA results show that there is a general increase of thermal stability (rg) with the addition of f-MWCNTs, which means that covalently bonded f-MWCNTs can reduce the local chain mobility of the matrix by interfacial interactions. The ENB system also shows significant enhancement of the toughness using just 0.8 wt % f-MWCNTs. These results indicate that the ROMP approach for polyENB is also very effective. The second topic is an investigation of the biorenewable rubbers synthesized by the tandem ROMP and cationic polymerization. The resin consists of a norbornenyl-modified linseed oil and a norbornene diester. Characterization of the bio-based rubbers includes dynamic mechanical analysis, tensile testing, and thermogravimetric analysis. The experimental results show that there is a decrease in glass transition temperature and slight increase of elongation with increased diester loading.

  17. Use of microfasteners to produce damage tolerant composite structures.

    Partridge, Ivana K; Hallett, Stephen R


    The paper concerns the mechanical performance of continuous fibre/thermosetting polymer matrix composites reinforced in the through-thickness direction with fibrous or metallic rods or threads in order to mitigate against low delamination resistance. Specific illustrations of the effects of microfasteners in reducing delamination crack growth are made for Z-pinned and tufted composites. Response to loading in such 'structured materials' is subject to multiple parameters defining their in-plane and out-of-plane properties. Single microfastener mechanical tests are well suited to establish the crack bridging laws under a range of loading modes, from simple delamination crack opening to shear, and provide the basis for predicting the corresponding response of microfastener arrays, within a given material environment. The fundamental experiments on microfasteners can be used to derive analytical expressions to describe the crack bridging behaviour in a general sense, to cover all possible loadings. These expressions can be built into cohesive element constitutive laws in a finite-element framework for modelling the effects of microfastener arrays on the out-of-plane mechanical response of reinforced structural elements, including the effects of known manufacturing imperfections. Such predictive behaviour can then be used to assess structural integrity under complex loading, as part of the component design process. This article is part of the themed issue 'Multiscale modelling of the structural integrity of composite materials'.

  18. Structure - property relations of high-temperature composite polymer matrices

    Morgan, R.J.; Jurek, R.J.; Larive, D.E. [Michigan Molecular Institute, Midland, MI (United States); Tung, C.M. [Northrop Corp., Hawthorne, CA (United States); Donnellan, T. [Naval Air Development Center, Warminster, PA (United States)


    The structure-deformation-failure mode-mechanical property relations of high-temperature thermoplastic polyimide and thermoset bismaleimide (BMI) polymeric matrices and their composites will be discussed. In the case of polyimides, the effects of test temperature, thermal history, strain rate, type of filler, and filler volume fraction on structure - property relations will be discussed. For BMIs we report systematic Fourier transform infrared spectroscopy and differential scanning calorimetry studies of the cure reactions as a function of chemical composition and time - temperature cure conditions and then describe the resultant cross-linked network structure based on our understanding of the cure reactions. The optimization of the BMI matrix toughness will be considered in terms of network structure and process-induced matrix microcracking. We also describe optimization of composite prepreg, lamination and postcure conditions based on cure kinetics, and their relationship to the BMI viscosity-time-temperature profiles. The critical processing-performance limitations of high-temperature polymer matrices will be critically discussed, and toughening approaches to address these limitations, such as toughness over a wide temperature range, will be presented. 7 refs., 2 figs., 1 tab.

  19. Research Progress on Resin/Graphite Conductive Composites%树脂/石墨导电复合材料的研究进展

    王益群; 寇开昌; 吴广磊; 卓龙海


    阐述了国内外热固性及热塑性树脂/石墨导电复合材料制备方法的研究现状,以及石墨类型、制备工艺等因素对复合材料导电性能的影响,并对其发展前景进行了展望.%Research status of preparing methods for thermoplastic and thermosetting resin / graphite conductive composites and effects of graphite types,preparing technics on conductive properties of the composites were summarized.Then,the possible development direction about resin/graphite conductive composites was pointed out.

  20. 5-Androstene-3{beta},17{beta}-diol Promotes Recovery of Immature Hematopoietic Cells Following Myelosuppressive Radiation and Synergizes With Thrombopoietin

    Aerts-Kaya, Fatima S.F.; Visser, Trudi P.; Arshad, Shazia [Department of Hematology, Erasmus University Medical Center, Rotterdam (Netherlands); Frincke, James; Stickney, Dwight R.; Reading, Chris L. [Harbor Therapeutics, Inc, San Diego, California (United States); Wagemaker, Gerard, E-mail: [Department of Hematology, Erasmus University Medical Center, Rotterdam (Netherlands)


    Purpose: 5-Androstene-3{beta},17{beta}-diol (5-AED) stimulates recovery of hematopoiesis after exposure to radiation. To elucidate its cellular targets, the effects of 5-AED alone and in combination with (pegylated) granulocyte colony-stimulating factor and thrombopoietin (TPO) on immature hematopoietic progenitor cells were evaluated following total body irradiation. Methods and Materials: BALB/c mice were exposed to radiation delivered as a single or as a fractionated dose, and recovery of bone marrow progenitors and peripheral blood parameters was assessed. Results: BALB/c mice treated with 5-AED displayed accelerated multilineage blood cell recovery and elevated bone marrow (BM) cellularity and numbers of progenitor cells. The spleen colony-forming unit (CFU-S) assay, representing the life-saving short-term repopulating cells in BM of irradiated donor mice revealed that combined treatment with 5-AED plus TPO resulted in a 20.1-fold increase in CFU-S relative to that of placebo controls, and a 3.7 and 3.1-fold increase in comparison to 5-AED and TPO, whereas no effect was seen of Peg-G-CSF with or without 5-AED. Contrary to TPO, 5-AED also stimulated reconstitution of the more immature marrow repopulating (MRA) cells. Conclusions: 5-AED potently counteracts the hematopoietic effects of radiation-induced myelosuppression and promotes multilineage reconstitution by stimulating immature bone marrow cells in a pattern distinct from, but synergistic with TPO.