Thermally reversible and self‐healing novolac epoxy resins based on Diels–Alder chemistry

The modified novolac epoxy resins with furan pendant groups were prepared by novolac epoxy resin and furfuryl alcohol and then crosslinked by bifunctional maleimide via Diels–Alder (DA) chemistry to obtain the thermally reversible and self‐healing novolac epoxy resins. The as‐prepared crosslinked novolac epoxy resins were characterized by FT‐IR, NMR, TGA, and DMA. The results indicate that the novel crosslinked novolac epoxy resins present higher storage modulus (2.37 GPa at 30°C) and excellent thermal stability (348°C at 5% mass loss). Furthermore, the thermal reversible and self‐healing properties were studied in detail by DSC, SEM, thermal re‐solution, and gel–solution–gel transition experiments. All the results reveal that the crosslinked novolac epoxy resins based on DA reaction can be used as smart material for the practical application of electronic packaging and structural materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42167.     

高固含量聚合物乳液黏度的影响因素

综述了乳液粒径及分布、乳化剂、引发剂、单体配比、反应温度、功能单体、pH值等对聚合物黏度的影响，确定了实现高固含量低黏度乳液的最佳条件。     

室内模拟硫化氢对聚合物粘度影响研究方法的建立

针对配注污水中因硫化氢气体的存在导致所配聚合物溶液粘度损失严重,其含硫化氢污水取样后室内很难存储问题,开展室内合成硫化氢,建立室内研究硫化氢对聚合物粘度影响实验方法。该研究方法为:盐酸与硫化钠反应后生成一定量的硫化氢,以氮气为载气通入聚合物溶液中,考察硫化氢对聚合物溶液粘度的影响。通过控制载气流量、吹脱温度、酸滴加速度确定硫化氢的最佳生成条件,从而确定硫化氢对聚合物粘度影响的最佳室内模拟条件。通过实验研究最终确定反应温度为80℃、氮气流量为0.1L/min、盐酸在5min内滴加完成,在该反应条件下可以准确评价硫化氢对聚合物溶液粘度影响。     

Electrospinning of linear homopolymers of poly(methyl methacrylate): exploring relationships between fiber formation, viscosity, molecular weight and concentration in a good solvent

A series of seven linear homopolymers of poly(methylmethacrylate) ranging from 12,470 to 365,700 g/mol M_w, were utilized to further explore scaling relationships between viscosity and concentration in a good solvent at 25 °C and to investigate the impact of these relationships on fiber formation during electrospinning. For each of the polymers investigated, chain dimensions (hydrodynamic radius and radius of gyration) were measured by dynamic light scattering to determine the critical chain overlap concentration, c^*. The experimentally determined c^*, was found to be in good agreement with the theoretically determined value that was calculated by the criteria c^*∼1/[η], where the intrinsic viscosity was estimated from the Mark-Houwink parameters, K and a (at 25 °C in dimethyl formamide) obtained from the literature. The plot of the zero shear viscosity vs. c/c^* distinctly separated into different solution regimes, viz. dilute (c/c^*<1), semidilute unentangled (1<c/c^*<3) and semidilute entangled (c/c^*>3). The crossover between semidilute unentangled and semidilute entangled regimes in the present investigation occurred at c/c^*∼3, which, therefore, marked the onset of the critical chain entanglement concentration, c_e, according to the procedure utilized by Colby and co-workers [Colby RH, Rubinstein M, Daoud M. J de Phys II 1994;4(8):1299-310. [52]]. Electrospinning of all solutions was carried out at identical conditions to ascertain the effects of solution concentration, molecular weight, molecular weight distribution and viscosity on fiber formation and morphological features of the electrospun material. Only polymer droplets were observed to form from electrospinning of solutions in the dilute concentration regime due to insufficient chain overlap. As the concentration was increased, droplets and beaded fibers were observed in the semidilute unentangled regime; and beaded as well as uniform fibers were observed in the semidilute entangled regime. Uniform fiber formation was observed at c/c^*∼6 for all the narrow MWD polymers (M_w of 12,470-205,800 g/mol) but for the relatively broad MWD polymers (M_w of 34,070 and 95,800 g/mol), uniform fibers were not formed until higher concentrations, c/c^*∼10, were utilized. Dependence of fiber diameter on concentration and viscosity was also determined, viz. fiber dia∼(c/c^*)^3.1 and respectively. These scaling relationships were in general agreement with that observed by Mckee et al. [McKee MG, Wilkes GL, Colby RH, Long TE. Macromolecules 2004;37(5):1760-67. [33]].     

The effect of coal properties on the viscosity of coal-water slurries

Studies on coal-water slurries (CWSs) have been conducted for many years to replace fuel oil. In this research project, the effect of coal properties on CWSs have been investigated using two Turkish coals of different ranks and a Siberian bituminous coal. Physical, chemical and surface properties of coal samples were determined. Furthermore, adsorption tests were carried out in order to put forward the effect of additive adsorption on the viscosity of CWSs. Viscosity measurements were realized for CWSs of various solid ratios by weight that were prepared using coal samples having mean particle sizes of 19, 35 and 50 μm.     

Rate acceleration of Diels–Alder reactions utilizing a fluorous micellar system in water

A fluorous micellar system in water has been created to produce a large interfacial area between these media that retains substrates, effectively facilitating intermolecular Diels–Alder reactions due to repulsion effects from both media. Because LiFOS functioned not only as a surfactant but also as a supporting electrolyte, an electrochemical approach could be introduced to evaluate the rate acceleration effects. The measurement of the particle size distribution of the fluorous micelles clearly supported these evaluations.     

The effect of alkali metal oxide on the properties of borosilicate fireproof glass: Structure,thermal properties,viscosity, chemical stability

The purpose of the current work was to research the effect of alkali metal oxide on the structure, thermal properties, viscosity and chemical stability in the glass system (R₂O–CaO–B₂O₃–SiO₂) systematically. Because the glass would emulsify when Li₂O was added to the glass batch, this article did not discuss Li₂O. The results showed that when the amount of Na₂O was less than 4 mol.%, there was a higher interconnectivity of borate and silicate sub-networks in glass, as more mixed Si–O–B bonds were present in glass. The glass samples exhibited excellent thermal properties and chemical stabilities. As the amount of Na₂O exceeded 4 mol.%, the interconnectivity of borate and silicate sub-networks was weakened. The thermal properties and chemical stabilities of the glass samples were reduced. The connectivity of the silicate sub-network was weakened slightly as the Na/K ratio varied, and the coefficient of thermal expansion (CTE) of the glass samples gradually increased, and the resistance to thermal shock (RTS) value gradually decreased. Moreover, the viscosity of the glass samples decreased with the ratio of Na/Si and Na/K increased.     

金属阳离子对部分水解聚丙烯酰胺溶液黏度影响的研究进展

综述了金属阳离子对部分水解聚丙烯酰胺溶液（HPAM）黏度影响的研究现状,解释了不同价态金属阳离子对HPAM的降黏作用机理,介绍了采油污水处理中金属离子的脱除技术。对目前金属离子与HPAM作用研究中存在的问题以及未来的发展方向进行了总结。     

功能高分子的增粘与乳化性能研究

用胶束聚合法将丙烯酰胺、丙烯酸与自制两亲功能单体进行共聚,合成了三元共聚物,考察了其流变学性质及乳化性能,并通过荧光光谱、扫描电子显微镜对两种功能高分子体系的聚集体结构和溶液中的分子聚集行为进行了研究,并对相应机理进行了分析探讨。研究结果发现,45℃下1500 mg/L的自制功能高分子在矿化度为4 756 mg/L的模拟水溶液中,粘度仍可以达到200 mPa.s。另外,自制功能高分子对模拟水与原油的混合体系具有很强的乳化能力。     

The effect of CO2 on the viscosity of polystyrene/limonene solutions

We demonstrate the use of a quartz crystal viscometer to determine the viscosity of solutions of polystyrene in limonene in the presence of high pressure carbon dioxide. These measurements were determined up to 50 bar in the range of temperature from 20 to 40 °C and at 0.025, 0.05, 0.1, 0.2, 0.3 and 0.4 g PS per ml of limonene. The selected variables of study (pressure, temperature and concentration) were statistically significant over the range of viscosity studied. The viscosities of the solutions at all loadings were found to decrease with increasing temperature and pressure while the plastising effect of CO₂ prevailing over the hydrostatic pressure applied by the gas. The flow activation energies of the system were obtained from an Arrhenius fitting of the experimental data reaching a maximum of 40 kJ/mol. An empirical model correlating the viscosity of the mixtures to pressure and temperature was developed in order to interpolate and extrapolate in the study region or in a range close to the working limits. Finally, the viscosity data were used to determine the solvent quality and to quantify the demixing points of the mixtures.     

Prediction of viscosity of mixed electrolyte solutions based on the Eyring's absolute rate theory and the semi-ideal hydration model

The mixing behavior of viscosities of electrolyte solutions under isopiestic equilibrium has been studied for the first time using the Eyring's absolute rate theory and the semi-ideal hydration model. The concentration dependence of the change in molar free energy of activation for flow has been formulated and discussed based on the concept of average hydration number and the structure-making or structure-breaking nature of the ion species. Coupling of the Erying's theory and the semi-ideal hydration model yields very simple mixing behavior of viscosities of electrolyte solutions under isopiestic conditions and thus yields new simple equations for viscosity, which can provide predictions for mixed solutions using only information on the single solute solutions. The new equations have been tested by comparisons with the experimental results for 15 systems and the existing equations reported in literature. The present equations improve the predictions considerably and the agreement with experimental results is in general quite good. The effect of different contributions accompanying the mixing process on the predicted results has been studied. The viscosities of the mixed electrolyte solutions can be well predicted only by using the additive contribution from the viscosities of binary solutions under isopiestic condition. The addition of the mixing term in this simple additive equation yields better predictions for mixed solutions mainly consisting of the structure-making ions. The inclusion of the density term has little effect on the predicted results.     

Cure kinetics, morphology and miscibility of modified DGEBA-based epoxy resin - Effects of a liquid rubber inclusion

Kinetics of the curic reaction and morphology of a diglycidyl ether of bisphenol-A based epoxy resin (DGEBA), using an anhydride hardener (nadic methyl anhydride) at different weight contents of carboxyl-terminated copolymer of butadiene and acrylonitrile liquid rubber (CTBN) was investigated using a differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), and scanning electron microscopy (SEM). The aim of the work is to understand the effects of inclusion of the liquid rubber phase in the transition phenomena that occur during the curing reaction. The curic reaction at three different curic temperatures and at varying rubber contents in the range of 5-20 wt% has been studied. The reaction rate and conversions that occurred at the curic temperatures were analyzed. The increase in the rate with the curic temperature showed this as a thermally catalyzed reaction. The rate of the reaction was found to decrease in liquid rubber-modified epoxies due to the effect of dilution and viscosity increase as obtained from the gelation times. The experimental data showed an autocatalytic behavior of the reaction, which is explained by the model predicted by Kamal. This model includes two reaction constants k₁ and k₂ and two reaction orders m and n. The order of the overall reaction was found to be approximately 2. The activation energies Ea₁ and Ea₂ were estimated at all curic temperatures for neat and all modified epoxies. The results obtained from the DSC data were also applied to diffusion controlled kinetic models. A schematic model to represent the curic reaction and phase separation was introduced and the molecular mechanism of this curing reaction was discussed. During the curic reaction, phase separation of the liquid rubber from the epoxy matrix took place and the modified epoxies showed phase separated morphology. The dispersed phase showed a homogenous particle size distribution. The size of the phase separated domains increased with increasing concentration of the CTBN and decreased with rise in curing temperature. The glass transition temperature (T_g) of the modified epoxies decreased with increase in curic temperature as studied from dynamic mechanical thermal analysis. Addition of the liquid rubber lowered the T_g of the network. This became prominent in the modification of the matrix with 15 and 20 wt% of the elastomer. This is attributed to flexibilization of the matrix. The dissolved rubber plasticizes the epoxy network. The T_g of the neat rubber in the low-temperature region was shifted to higher temperature upon addition of the elastomer. A higher shift was noted for 15 and 20 phr inclusion. This was due to dissolved epoxy in the rubber-rich phase that increased the modulus of the rubbery phase. The inclusion of a large wt% of carboxyl-terminated butadiene-co-acrylonitrile (CTBN) decreased the cross-linking density of the thermoset matrix.     

The effect of curing temperature on thermal,physical and mechanical characteristics of two types of adhesives for aerospace structures

The effects of cure temperatures on the thermal, physical and mechanical characteristics of two types of thermosetting structural epoxy film adhesives were determined in detail. The aim of this paper is to assess the effect of cure temperatures (82–121 °C) on the degree of cure of the two adhesives and the relevant void formations that need to be addressed in bonded part production and repair. Two thermal parameters were used to characterize the advancement of the reaction, such as degree of cure and glass transition temperature. The joint properties with respect to the cure temperatures were characterized by void content and bond-line thickness measurements and lap shear strength tests. Experimental results presented that all lap shear strengths were well within minimum shear strength (29 MPa) required by the specification of the film-type adhesive. However, the lap shear strength testing after aging at 82 °C and 95%R.H for 1000 h showed that the improved durability when the adhesive is cured at 121 °C did not occur for the 82 °C cure. Low curing conversion (75–77% degree of cure) combined with high voids (over 2 areal%) has a catastrophic effect on the bonding qualities at the metal-adhesive interface and due to lack of cohesion in the adhesive. The changes in the interface caused by the low temperature curing may contribute to an increased susceptibility of the bonded joint to moisture and consequent bond-line degradation.     

Prediction of viscosity of mixed electrolyte solutions based on the Eyring's absolute rate theory and the equations of Patwardhan and Kumar

The mixing behavior of viscosities of electrolyte solutions at constant ionic strength has been studied for the first time using the Eyring's absolute rate theory and the equations of Patwardhan and Kumar. Coupling of the Eyring's theory with the equations of Patwardhan and Kumar yields simple mixing behavior of viscosities of electrolyte solutions at constant ionic strength, and thus permits the establishment of new simple equations for viscosity, which can provide predictions for mixed solutions using only information on the single solute solutions. The new equations have been compared with the experimental results for fifteen systems and the existing equations reported in literature. The present equations generally give the best predictions and the agreement with experimental results is in general quite good. The effect of different contributions accompanying the mixing process on the predicted results has been studied. The viscosities of the mixed electrolyte solutions can be well predicted only by using the additive contribution from the viscosities of binary solutions at constant ionic strength. The addition of the mixing term in this simple additive equation yields better predictions. The inclusion of the density term has little effect on the predicted results.     

新型聚合物降粘剂稠油降粘效果的研究

以丙烯酰胺与自制的表面活性单体进行无规共聚,合成了5种聚合物降粘剂(ICA),考察了5种ICA对渤海SZ36-1油田稠油的降粘效果。结果表明,具有良好降粘能力的ICA-2降粘剂在混合体系浓度为800 mg/L,接近地层温度60℃时,降粘率高达90%以上,对20~30℃的渤海稠油具有更为明显的降粘效果。     

Prediction of the density and viscosity in biodiesel blends at various temperatures

Biodiesel defined as mono-alkyl esters of vegetable oils and animal fats, has had a considerable development and great acceptance as an alternative fuel for diesel engines. Density and viscosity are two important physical properties to affect the utilization of biodiesel as fuel. In this work, mixtures of biodiesel and ultra low sulfur diesel (ULSD) were used to study the variation of density (ρ) and kinematic viscosity (η) as a function of percent volume (V) and temperature (T), experimental measurements were carried out for six biodiesel blends at nine temperatures in the range of 293.15-373.15 K. Both, density and viscosity increases because of the increase in the concentration of biodiesel in the blend, and both of them decrease as temperature increases. One empirical correlation was proposed to estimate the density: ρ = α·V + β·T + δ; and three empirical correlations were developed to predict the kinematic viscosity: η = exp[ln(γ) + ?·V + ω/T + λ·V/T²], η = exp[ln(γ) + ω/T + λ·V/T²] and η = exp[ln(γ) + ω/T + λ·V/T]. The corresponding parameters were optimized by the Levenberg-Marquardt method. The estimated values of density and viscosity are in good agreement with the experimental data because absolute average prediction errors of 0.02% and 2.10% were obtained in the Biodiesel(1) + ULSD(2) system studied in this work.     

Kinetics of polyurethane formation between glycidyl azide polymer and a triisocyanate

Kinetics of the polyurethane formation between glycidyl azide polymer (GAP) and a polyisocyanate, Desmodur N‐100, were studied in the bulk state by using quantitative FTIR spectroscopy. The reaction was followed by monitoring the change in intensity of the absorption band at 2270 cm^?1 for NCO stretching in the IR spectrum, and was shown to obey second‐order kinetics up to 50% conversion. The activation parameters were obtained from the evaluation of kinetic data at different temperatures in the range of 50–80°C. The enthalpy and entropy of activation were found to be ΔH^? = 44.1 ± 0.5 kJ · mol^?1 and ΔS^? = ?196 ± 2 J · mol^?1l · K^?1, respectively. Dibutyltin dilaurate (DBTDL) was used as the curing catalyst. The kinetic study of the polyurethane formation between GAP and Desmodur N‐100 showed that the reaction is enormously speeded up in the presence of the catalyst, and the reaction obeys second‐order kinetics, provided that the catalyst concentration is kept constant. An investigation on the rate of the catalysed reaction depending on the catalyst concentration provided the order of the reaction, with respect to the DBTDL catalyst concentration, and the rate constant for the catalytic pathway of the reaction. The rate constant for the catalytic pathway was established to be 4.37 at 60°C, while the uncatalyzed reaction has a rate constant of 3.88 × 10^?6 L · mol^?1 · s^?1 at the same temperature. A rate enhancement factor of 23 was achieved by using 50 ppm catalyst. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 918–923, 2001