Control of shrinkage and final conversion of vinyl ester resins cured in low‐temperature molding processes

Vinyl ester resin is a major thermoset polymer used in low‐temperature composite manufacturing processes such as the Seemann composite resin infusion‐molding process (SCRIMP). Volume shrinkage and residual styrene are important concerns for composites produced in such processes. A low‐shrinkage additive (LSA) is a typical agent added to control the volume shrinkage of vinyl ester resins during molding. In this study, the effects of LSA content and the temperature profile (the temperature gradient and peak temperature) on the volume shrinkage control of a vinyl ester resin were investigated. The reaction kinetics of the resin system were also studied. We achieved good volume shrinkage control if we raised the curing temperature slowly to allow sufficient time for phase separation and if the curing temperature reached a high value after phase separation to allow microvoid formation. On the basis of experimental results, we designed an improved SCRIMP to increase resin conversion, reduce resin shrinkage, and produce composites with better properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1486–1496, 2003     

不饱和聚酯树脂微乳液的研究(Ⅰ)不饱和聚酯树脂的微乳化

合成了不同磺酸盐含量的三种不饱和聚酯，通过拟三元相图分析磺酸盐含量、苯乙烯、不同正构醇和水组成的体系对微乳区域的影响。研究结果表明，磺酸盐不饱和聚酯同苯乙烯互溶的前提下，磺酸盐含量越大，其微乳液增溶的水量越大；磺酸盐含量一定时，苯乙烯含量越小，其微乳液增溶的水量越大；正构醇质量分数为在2％～10％范围内，其微乳液增溶的水量最多；三种醇相比较，正丁醇体系的微乳区是W／O型向O／W型过渡的连续区域，正丙醇体系的O／W型微乳液区明显不同于正丁醇体系，正戊醇体系不能形成水包油型的微乳区。     

Toughening of thermoset/thermoplastic composites via reaction‐induced phase separation: Epoxy/phenoxy blends

Phase morphology and phase separation behavior of amine‐cured bisphenol‐A diglycidyl ether epoxy and phenoxy mixtures have been investigated by means of time‐resolved small angle light scattering, optical microscopy, and scanning electron microscopy. The starting reactant mixtures composed of epoxy, phenoxy, and curing agents such as diaminodiphenyl sulfone (DDS) and methylene dianiline (MDA) were found to be completely miscible. Upon curing with DDS at 180°C, phase separation took place in various epoxy/phenoxy blends (compositions ranging from 10–40% phenoxy), whereas the MDA curing showed no indication of phase separation. The mechanical and physical properties of single‐phase and two‐phase networks were examined, in that the DDS‐cured epoxy/phenoxy blends having a two‐phase morphology showed improved ductility and toughness without significantly losing other mechanical and thermal properties such as modulus, tensile strength, glass transition and heat deflection temperatures. The energy absorbed to failure during the drop weight impact event was also found to improve relative to those of the single‐phase MDA‐cured blend as well as of the neat epoxy. Such property enhancement of the DDS‐cured blends has been discussed in relation to the two‐phase morphology obtained via scanning electron microscopy micrographs of fractured surfaces. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1257–1268, 2000     

Study of the porous network developed during curing of thermoset blends containing low molar weight saturated polyester

Polymerisation of unsaturated polyester/styrene blend added with a thermoplastic additive leads to the formation of a porous biphasic polymer network. In this paper, the porous medium was specifically studied by TEM associated with images analysis by chord length distribution and small angle X-ray scattering (SAXS). When the molar weight and/or the amount of low profile additive (LPA) are sufficient to ensure porosity higher than 2%, chord length distribution can be performed and is characteristic of a Debye random medium and Porod's law was observed in SAXS. The lengths deduced from Porod's law are similar to those observed for Debye random regime and are lower than 50 nm. These characteristics are closely related to the processes happening during curing and especially to the phase separation. For less porous samples, deviation from Porod's law was observed and could be attributed to additional scattering intensity coming from concentration fluctuations within polymer matrix. For nonporous samples, scattering intensity was only due to concentration fluctuations.     

Hydrogenation of low‐molar‐mass,OH‐telechelic polybutadienes. I. Methods based on diimide

Low‐molar‐mass, OH‐telechelic polybutadienes were hydrogenated (1) by diimide alone and (2) by using a novel method, consisting of the following two steps: up to some 95% degree of conversion by gaseous hydrogen with conventional Ziegler–Natta catalysts, and, only then, up to almost full saturation by diimide. The two‐step method, which has been found to be equally efficient, enables one to decrease substantially the necessary feed of p‐toluenesulfonylhydrazide, by the thermal decomposition of which diimide is generated. The crude saturated products, which could not be purified by a conventional (re)precipitation technique due to their low molar mass, contained a relatively large amount of a side‐product, bis(p‐tolyl)disulfide (TDS). It was found that free TDS can be converted quantitatively by reduction cleavage into p‐tolyl mercaptan (TM) without changing the structure of the polymeric product, and TM can then be removed from the mixture by alkaline extraction. Alternatively, the crude product can be freed from TDS by chromatography. With the two‐step hydrogenation method, only a small amount of the fragments and/or precursors of TDS add to the 5% residual CC double bonds of the partially hydrogenated polybutadiene chains. After any of the two purification procedures, the fully saturated products usually contained less than 1 wt % of such undesirable substituents only, which is comparable with the reported single‐step diimide hydrogenation of the initial, fully unsaturated polybutadiene in the presence of a proton scavenger (tri‐n‐propylamine). © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3203–3213, 1999     

Study of unsaturated polyester and vinylester morphologies using excimer laser surface treatment

A technique based on the use of an ArF excimer laser (193 nm) to analyze the morphology of the unsaturated polyester and vinylester networks has been developed. This method is based on the use of the differences between the thresholds at which ablation of the various constituent phases of the materials occurs. After having determined the ablation threshold of a polystyrene, various surface treatments using excimer lasers fluence around this threshold were applied to unsaturated polyesters and vinylester. In the latter case, a two-phase structure consisting of microgels in a polystyrene phase was shown by scanning electron microscopy observations, allowing us to conclude that the mechanisms by which vinylester and unsaturated polyester networks are formed are similar. We also observed that the two-phase structure of the vinylester matrixes, unlike that of the unsaturated polyesters, is organized rather than random-structured, which could represent a major parameter contributing to the very good hydrolysis stability of these materials. In the event of degradation by osmotic mechanisms, the organized structure network would enable limiting of the development of the osmotic pressures by distributing the forces within the material, thus avoiding crazing. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1703–1714, 1997     

Effects of molecular weight of polysulfone on phase separation behavior for cyanate ester/polysulfone blends

The effects of molecular weight of polysulfone (PSF) on the morphology of bisphenol‐A dicyanate (BADCy)/PSF blends were studied. Because the viscosity of the blend increased and the miscibility between BADCy and PSF decreased with the increase of PSF molecular weight, these two competing effects on the phase‐separation were investigated. It was observed that the effect of viscosity was predominant: the viscosity of the blends at the onset point of phase separation increased with the increase of PSF molecular weight. The phase separation mechanism depends on the viscosity of the blends at the onset point of phase separation and determines the morphology of the blends. Because the increasing viscosity with increasing the molecular weight of PSF suppressed the nucleation and growth even with 10 phr of PSF content, phase separation occurred through spinodal decomposition to form the combined morphology having both PSF particle structure and BADCy particle structure. The combined morphology and the BADCy particle structure were obtained with a smaller amount of high molecular weight PSF content. This indicates that the viscosity of the blends at the onset point of phase separation is the critical parameter that determines the morphology of the blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 921–927, 2000     

DSC curing study of catalytically synthesized maleic‐acid‐based unsaturated polyesters

Unsaturated polyesters were synthesized based on ethylene glycol and maleic acid as unsaturated dicarboxylic acid, using a variety of saturated acids in the initial acid mixture, without or with different catalysts. The curing of the polyesters produced with styrene was studied using differential scanning calorimetry (DSC) under dynamic‐ and isothermal‐heating conditions. The FTIR spectra of the initial polyesters and cured polyesters were also determined. Curing is not complete at the end of DSC scan and the unreacted bonds were quantitatively determined from the FTIR spectra and by estimation based on literature data. The value of the mean degree of conversion (α) of all double bonds (styrene unit and maleate unit) was approximately α = 0.40. Using an appropriate kinetic model for the curing exotherm of polyesters, the activation energy (E_a), the reaction order (x) and the frequency factor (k_o) were determined. Because the kinetic parameters (ie E_a, k, x) affect the kinetics in various different ways, the curves of degree of conversion versus time at various isothermal conditions are more useful to compare and characterize the curing of polyesters. The kinetic parameters are mainly influenced by the proportion of maleic acid in the polyesterification reaction mixture and secondarily by the residual polyesterification catalyst. The degree of conversion of already crosslinked polyesters is greatly increased by post‐curing them at elevated temperature and for a prolonged time. © 2002 Society of Chemical Industry     

Crystallization of low‐density polyethylene‐ and linear low‐density polyethylene‐rich blends

The crystallization of a series of low‐density polyethylene (LDPE)‐ and linear low‐density polyethylene (LLDPE)‐rich blends was examined using differential scanning calorimetry (DSC). DSC analysis after continuous slow cooling showed a broadening of the LLDPE melt peak and subsequent increase in the area of a second lower‐temperature peak with increasing concentration of LDPE. Melt endotherms following stepwise crystallization (thermal fractionation) detailed the effect of the addition of LDPE to LLDPE, showing a nonlinear broadening in the melting distribution of lamellae, across the temperature range 80–140°C, with increasing concentration of LDPE. An increase in the population of crystallites melting in the region between 110 and 120°C, a region where as a pure component LDPE does not melt, was observed. A decrease in the crystallite population over the temperature range where LDPE exhibits its primary melting peaks (90–110°C) was noted, indicating that a proportion of the lamellae in this temperature range (attributed to either LDPE or LLDPE) were shifted to a higher melt temperature. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1009–1016, 2000     

Preparation and characterization of bismaleimide (N,N′‐bismaleimido‐4,4′‐diphenyl methane)–unsaturated polyester modified epoxy intercrosslinked matrices

An intercrosslinked network of unsaturated polyester–bismaleimide modified epoxy matrix systems was developed. Epoxy systems modified with 10, 20, and 30% (by weight) of unsaturated polyester were made by using epoxy resin and unsaturated polyester with benzoyl peroxide and diaminodiphenylmethane as curing agents. The reaction between unsaturated polyester and epoxy resin was confirmed by IR spectral studies. The unsaturated polyester toughened epoxy systems were further modified with 5, 10, and 15% (by weightt) of bismaleimide (BMI). The matrices, in the form of castings, were characterized for their mechanical properties. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) of the matrix samples were performed to determine the glass transition temperature (T_g) and thermal degradation temperature of the systems, respectively. Mechanical properties, viz: tensile strength, flexural strength, and plain strain fracture toughness of intercrosslinked epoxy systems, were studied by ASTM methods. Data obtained from mechanical and thermal studies indicated that the introduction of unsaturated polyester into epoxy resin improves toughness but with a reduction in glass transition, whereas the incorporation of bismaleimide into epoxy resin improved both mechanical strength and thermal behavior of epoxy resin. The introduction of bismaleimide into unsaturated polyester‐modified epoxy resin altered thermomechanical properties according to their percentage concentration. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2853–2861, 2002     

Phase separation in blends of homopolymer and graft copolymer based on styrene and butadiene

A series of blends of homopolystyrene and styrene-g-butadiene copolymer with different combinations of molecular weights of the copolymer and graft polystyrene segments have been prepared. Phase separation behaviour of the blends has been examined by electron microscopy. The results reveal a regular change of morphology of the blends with the relative molecular weights of the free and graft polystyrene chains. The observed relationships between compatibility of the homopolymer and copolymer and the relative molecular weight are generally in agreement with that observed previously in homopolymer-block copolymer blends. Taking the inherent polydispersity of the molecular weight of the component polymers into account, some peculiarities of the morphologies of the blends have been explained.     

DSC study on simultaneous interpenetrating polymer network formation of epoxy resin and unsaturated polyester

A kinetic study on simultaneous interpenetrating polymer network formation of epoxy resin based on diglycidyl ether of Bisphenol A (DGEBA) and unsaturated polyester (UP) was performed by means of differential scanning calorimetry (DSC). Isothermal DSC characterizations of neat resins and their mixture (in a weight ratio of 50/50) were performed at different temperatures. Dynamic DSC characterization of the systems were performed at three different heating rates. A lower total heat of reaction developed during simultaneous polymerization in dynamic DSC tests was found, compared to the total heats developed during pure resins network formation. This phenomenon can be interpreted as an effect of network interlock that could not be compensated for completely by an increase in curing temperature. The kinetics of the reactions was described by empirical models. The DGEBA, in a 50/50 UP/DGEBA blend, indicated a higher rate constant than the pure DGEBA. The obtained results suggests that the hydroxyl end group of UP in the blend provided a favorably catalytic environment for the DGEBA cure. The results are in good agreement with the literature data. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2689–2698, 2002     

Liquid/solid two‐phase carbonization of low‐molecular‐weight chloro‐/bromo‐hydrocarbons

A novel liquid/solid two‐phase reaction has been discovered that enables destruction of a series of low‐molecular‐weight chloro‐/bromo‐hydrocarbons to carbon‐based materials. The solid phase is anhydrous potassium hydroxide and the liquid phase is a benzene or tetrahydrofuran solution of halide and contains a certain amount of tetrabutyl ammonium bromide (TBAB) as phase transfer catalyst. The structure of the carbon‐based materials have been characterized by elemental analysis, Fourier transform infrared (FT‐IR), FT‐Raman, and X‐ray photoelectron spectroscopies, and their morphologies have been examined by wide‐angle X‐ray diffraction and transmission electron microscopy. The results indicate that the products are amorphous nanoparticles and contain mainly elemental carbon. They consist of sp, sp², and sp³ carbon atoms simultaneously and can be regarded as carbyne analogues. This work provides a convenient method for synthesizing new carbon‐based materials in relatively high yields. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1510–1515, 2000     

Phase separation mechanism during membrane formation by dry‐cast process

Phase separation mechanisms during the membrane formation by dry‐cast process were investigated by light scattering in the cellulose acetate/dimethylformamide (DMF)/2‐methyl‐2,4‐pentanediol system. Phase separation occurred by spinodal decomposition (SD) when paths of the composition changes due to the evaporation of DMF were close to the critical point in the phase diagram. Characteristic properties of the early stage of SD such as an apparent diffusion coefficient and an interface periodic distance were obtained from the Cahn theory. Phase separation occurred by nucleation and growth (NG) when paths of the composition changes were far from the critical point. SEM observation confirmed that the membrane formed by the SD mechanism had interconnected structure, whereas that by the NG mechanism had the closed cell porous structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 776–782, 2000     

Effect of polymer-filler surface interactions on the phase separation in polymer blends

For the blends of chlorinated polyethylene and copolymer of ethylene with vinyl acetate, the effect of the introducing filler (fumed silica) on the phase behavior of the blends was investigated. It was found that introducing filler in polymer blends depending on its amount lead either to the increase or to the decrease in the temperature of phase separation. At the filler concentration where both components transit into the state of a border layers, the phase separation temperature increases. This effect was explained by the change of the total thermodynamic interaction parameter in the ternary system polymer-polymer-filler. At lower concentration of a filler, the possible effect is the redistribution of the blend components according to their molecular masses between filler surface (in the border layer) and in the bulk that may diminish the phase separation temperature.Effect of the filler on the phase behavior was explained by the simultaneous action of two mechanisms: by changing the thermodynamics of interaction near the surface due to selective adsorption of one of the components and by the redistribution of components according to their molecular masses between the boundary region (near the surface) and in the matrix.The measurements of the kinetics of phase separation and calculation of the parameters of the activation energy are in agreement with proposed mechanisms.     

Heat‐shrinkable polymer blends based on grafted low‐density polyethylene and polyurethane elastomer. Part I

Blends prepared by melt‐mixing of thermoplastic material‐elastomer have gained considerable attention in recent years. Heat‐shrinkability of polymer, which is dependent on elastic memory, can be introduced into the system in the form of an elastomeric phase. The present study deals with the measurement of the heat‐shrinkability of the blend of grafted polyethylene and polyurethane elastomer. Interchain crosslinking between grafted polyethylene and elastomer improves shrinkability. High‐temperature performance of the sample depends on the degree of interchain crosslinking. Probable interactions between the rubber and plastic phase are confirmed by IR spectroscopy. Extraction of the elastomeric phase is restricted due to interchain crosslinking as confirmed by SEM study. © 2000 Society of Chemical Industry     

Study on phase behavior–impact strength relationship of unsaturated polyester/polyurethane hybrid polymer network

The phase behavior of a hybrid polymer network (HPN) composed of poly[(propylene glycol maleate)-co-(propylene glycol phthalate)] crosslinked with styrene and polyester–urethane crosslinked with methylene-bis-ortho-chloroaniline was examined. The correlation between phase separation and impact strength of the HPNs is discussed. The composition of HPNs has an effect on their properties.     

Rapid and large‐scale separation of magnetic nanoparticles by low‐field permanent magnet with gas assistance

Bubbles can be used to greatly improve the speed of magnetic separation (MS) and overcome the limitation of magnetic force on the capture distance, making low‐field MS highly efficient and easily scalable. This novel method leads to the development of a medium‐free continuous gas‐assisted magnetic separator on small pilot scale using low‐field permanent magnet. This separator is demonstrated highly efficient for recovery of proteins‐loaded magnetic nanoparticles from large volume biosuspension. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3101–3106, 2014     

Effects of the cure cycle and thermoplastic content on the final properties of dicyanate ester/polysulfone Semi‐IPNS

A bisphenol A dicyanate resin, BADCy, was toughened by incorporating polysulfone, PSU, at various compositions. The catalyst system used was a mixture of copper acetylacetonate and nonylphenol. Phase separation and rheokinetics were studied through curing. The blends seemed to have a LCST behavior, and the presence of PSU did not affect the polycyclotrimerization kinetics. The phase structure, thermal, and mechanical properties of the final network were investigated as a function of the PSU content and cure temperature. The toughness of the BADCy/PSU blends was closely related to their final morphology, increasing with the amount of phase inversion. The mechanical properties were not affected by the addition of the thermoplastic. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1799–1809, 2002     

Synthesis of trimellitic anhydride microcapsule toner by liquid‐phase separation

A microcapsule toner containing trimellitic anhydride for use as a foam inhibitor in printing applications was synthesized by liquid‐phase separation in organic solvents. It is possible to determine materials appropriate for the microencapsulation of trimellitic anhydride from solubility parameters calculated on the basis of the molecular structures of raw material candidates. Considering solubility parameters of various polymers, the polyethylene/methacrylic acid copolymer was selected for the microcapsule wall material. In addition, two kinds of solvents, toluene [solvent (a)] and isoparaffin [solvent (b)], were employed. It was necessary for the microcapsule materials to meet the following conditions: (1) the wall material must completely dissolve in solvent (a); (2) the core material must disperse well, but not dissolve in solvent (a); and (3) the wall and core materials must not dissolve in solvent (b). By using mixtures of either lecithin and basic barium petronate or lecithin and basic calcium petronate as charge control agents, the trimellitic anhydride microcapsules could be charged either positively and negatively, respectively. The microcapsule toner fabricated in this method was successfully applied in commercial printing machines, where it inhibited foaming effectively enough to satisfy product requirements in the printing industry. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3822–3826, 2003