Viscosity properties of acrylonitrile-sodium methallylsulfonate copolymer solutions

Conclusions To obtain structurally uniform solutions of the acrylonitrile-sodium methallylsulfonate copolymer, it is advisable to prepare them at elevated temperatures.An effect of structural homogenization of concentrated solutions of the copolymer has been detected in the process of temperature treatment at 60–80°C.Translated from Khimicheskie Volokna, No. 2, pp. 27–28, March–April, 1986.     

Effect of glass transition temperature and saturation temperature on the solid‐state microcellular foaming of cyclic olefin copolymer

Effect of glass transition temperature and saturation temperature on the solid‐state microcellular foaming of cyclic olefin copolymer (COC)—including CO₂ solubility, diffusivity, cell nucleation, and foam morphology—were investigated in this article. COCs of low T_g (78°C) and high T_g (158°C) were studied. Solubilities are 20–50% higher in high T_g COC than in the low T_g COC across the saturation temperature range. Diffusivities are about 15% higher on average in high T_g COC for temperatures up to 50°C. A much faster increase of diffusivity beyond 50°C is observed in low T_g COC due to it being in the rubbery state. Under similar gas concentration, high T_g COC starts foaming at a higher temperature. And the foam density decreases faster in low T_g COC with foaming temperature. Also, high T_g COC foams show about two orders of magnitude higher cell nucleation density than the low T_g COC foams. The effect of saturation temperature on microcellular foaming can be viewed as the effect of CO₂ concentration. Nucleation density increases and cell size decreases exponentially with increasing CO₂ concentration. Uniform ultramicrocellular structure with an average cell size of 380 nm was created in high‐T_g COC. A novel hierarchical structure composed of microcells (2.5 μm) and nanocells (cell size 80 nm) on the cell wall was discovered in the very low‐density high‐T_g COC foams. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42226.     

Effect of the resin/hardener ratio on curing,structure and glass transition temperature of nanofilled epoxies

The curing reaction, structure, and glass transition behavior of epoxy‐clay nanocomposites prepared using several different resin/hardener ratios were investigated. Nonisothermal DSC experiments evidenced that the incorporation of the organoclay did not induce appreciable changes in the curing enthalpy, but determined a slight acceleration of the curing reaction, without modifying the activation energy. TEM and SEM analyses of the nanocomposite resins showed the presence of micrometric aggregates for all the resin/hardener ratios investigated, even though these materials showed good optical clarity and their WAXD analyses did not evidence any organoclay peak. In addition, the higher the hardener content, the lower the tendency toward exfoliation and the broader the distribution of the interlamellar distances. The degree of cross‐linking of cured resins was evaluated both from measurements of the elastic modulus in the rubbery plateau and from solvent sorption experiments. A maximum in cross‐link density was observed near the stoichiometric composition. Both modulus and sorption experiments suggested that filler‐matrix adhesion increased with increasing the resin/hardener ratio, a trend that was confirmed also by glass transition temperature data. An analysis of ethyl acetate sorption curves evidenced that a gradual transition from Fickian to Case II diffusion occurred as the resin/hardener ratio was raised and that the organoclay promoted deviation from the Fickian behavior. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Thickness and composition dependence of the glass transition temperature in thin random copolymer films

Glass transition temperatures (T_g) of thin poly(styrene-co-methyl methacrylate) and poly(2-vinyl pyridine-co-styrene) films coated on a native oxide surface of Si wafer (100) were measured by ellipsometry. The thickness dependence of T_g can be properly fitted by previously suggested equation developed for homopolymers, based upon a continuous multi-layer model, although one component in thin random copolymer films demonstrates a slightly favorable interaction between a substrate and thin film, and another demonstrates a strongly favorable interaction. Surface and interface have a strong influence on T_g of thin film coated on substrate: the surface has the effect of reducing T_g, whereas the interface increases the T_g according to the degree of interaction between a substrate and thin film. This degree of interaction can be quantified as an interaction parameter (k), and is dependent on the composition of random copolymers. For the estimation of k values of thin random copolymer films, we proposed a parallel type additive function (1/k_ran=w₁/k₁+w₂/k₂) where w is a weight fraction of component.     

Thermal behavior and specific interaction in high glass transition temperature PMMA copolymer

A series of high glass transition temperature copolymers based on poly(methyl methacrylate) (PMMA) were prepared by free radical copolymerization of methacrylamide and methyl methacrylate monomers in dioxane solvent. The thermal properties and hydrogen-bonding interactions of these poly(methacrylamide-co-methyl methacrylate) (PMAAM-co-PMMA) copolymers with various compositions were investigated by differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, and solid-state nuclear magnetic resonance (NMR) spectroscopy. A large positive deviation in the behavior of T_g, based on the Kwei equation from DSC analyses, indicates that strong hydrogen bonding exists between these two monomer segments. The FTIR and solid-state NMR spectroscopic analyses give positive evidence for the hydrogen-bonding interaction between the carbonyl group of PMMA and the amide group of PMAAM (e.g. by displaying significant changes in chemical shifts). Furthermore, the proton spin-lattice relaxation time in the rotating frame (T_1ρ(H)) has one single value over the entire range of compositions of copolymers, and gives a value shorter than the average predicted. The proton relaxation behavior indicates the rigid nature of the copolymer.     

Effect of water on the glass transition temperature of hydrophilic polyurethanes

The depression of the glass transition temperature by water was studied in a set of polyurethanes in which the soft segment consisted of polyethylene oxide (sample I) or a block copolymer of poly(propylene oxide) terminated with poly(ethylene oxide) in various proportions (sample set II). DSC measurements were made at two added water contents for each type of sample and at various temperatures. The T_g reduction appeared to be governed solely by the nonfreezing bound water and was much larger in sample I than in samples of set II. The more limited effect on the T_g of set II samples is attributed to restricted mobility arising from coupling of the short terminal poly(ethylene oxide) to rigid hard-segment units. Therefore, the data for sample I are preferred as a test of the predictive relations for the T_g depression. On this basis, it appears that the simple Fox mixing equation is more reliable than is the available free volume approach, which required unrealistically high values of the thermal expansion coefficient for water to fit the data for sample I. © 1993 John Wiley & Sons, Inc.     

氮官能化多锂引发合成星形苯乙烯-异戊二烯-丁二烯共聚物的微观结构和玻璃化转变温度

以六亚甲基亚胺锂(LHMI)与二乙烯基苯(DVB)合成的氮官能化多锂(简称Li)为引发剂,N,N,N′,N′-四甲基乙二胺(TMEDA)为极性调节剂,环己烷为溶剂,制备了带有氮官能化基团的星形无规苯乙烯-异戊二烯-丁二烯共聚物(SIBR),用核磁共振法进行了表征,并分析了TMEDA用量、聚合温度、引发剂浓度及DVB/Li(摩尔比)对SIBR微观结构和玻璃化转变温度(Tg)的影响。结果表明,在DVB/LHMI(摩尔比)为0.8的条件下,SIBR中有C—N存在,并且为臂数不等的星形聚合物;随着TMEDA用量的增加和聚合温度的降低,SIBR中非1,4-结构含量增加,Tg提高;在实验范围内引发剂浓度和DVB/Li对SIBR中非1,4-结构含量和其Tg影响不大。     

无铅玻璃粉粘合剂对温度的影响

本次实验的目的是将无铅玻璃粉经细化后制备成浆料,在浆料中通过添加有机粘合剂PVA、HEC、CMC纤维素浆料配方体系,通过喷雾干燥考察其对无铅玻璃粉造粒料的颗粒强度、粒径分布以及颗粒微观形貌的影响,然后静电喷涂使用,从而进一步考察其对釉料的玻化温度.     

Effect of added homopolymer on the microphase separation transition temperature of block copolymer

Summary The change in the microphase separation transition temperature (T_mst) of a diblock copolymer (AB), induced by the addition of homopolymer (HA), is theoretically studied. The calculations based on the modified Meier's theory show that T_mst is dependent on both the volume fraction of added homopolymer and the molecular volume ratio of HA to AB, which is the same as the previous theoretical results and qualitatively in agreement with the experimental results. This theory also predicts that the molecular weight ratio at the crossover of T_mst from elevation to depression is affected by the molecular weight of AB.     

Synthesis of a copolymer of acrylonitrile with sodium methallylsulfonate in dimethyl sulfoxide and the preparation of a chemisorptive fibre based on it

Conclusions Conditions have been developed for the synthesis of a copolymer of acrylonitrile and sodium methallylsulfonate in dimethyl sulfoxide containing up to 2–1/2% water by wt., using a redox initiating system.Fibres spun from the indicated copolymer have satisfactory physico-mechanical properties, and their static exchange capacity is as much as 1.1 meq/g.Translated from Khimicheskie Volokna, No. 4, pp. 16–18, July–August, 1990.     

氮官能化多锂引发合成星形苯乙烯-戊二烯-二烯共聚物的微观结构和玻璃化转变温度

以六亚甲基亚胺锂（LHMI）与二乙烯基苯（DVB）合成的氮官能化多锂（简称Li）为引发剂，N，N，N’，N’-四甲基乙二胺（TMEDA）为极性调节剂，环己烷为溶剂，制备了带有氮官能化基团的星形无规苯乙烯-异戊二烯-丁二烯共聚物（SIBR），用核磁共振法进行了表征，并分析了TMEDA用量、聚合温度、引发剂浓度及DVB/Li（摩尔比）对SIBR微观结构和玻璃化转变温度（Tg）的影响。结果表明，在DVB/LHMI（摩尔比）为0．8的条件下，SIBR中有C-N存在，并且为臂数不等的星形聚合物；随着TMEDA用量的增加和聚合温度的降低，SIBR中非l，4-结构含量增加，Tg提高；在实验范围内引发剂浓度和DVB/Li对SIBR中非1，4-结构含量和其，Tg影响不大。     

Effect of the degree of branching on the glass transition temperature of polyesters

Glass transition temperature dependence on the branching degree can be empirically estimated by excluding additional effects on this parameter as molecular weight distribution, end group interactions or crystallization. In this communication aliphatic–aromatic polyesters with a well defined degree of branching between 0% (linear) and 50% (hyperbranched) are investigated by differential scanning calorimetry. The hydrogen bonding effect of the OH-terminal groups was successfully extracted from the pure branching effect by protection of the end-functionalities. Fractionation of samples with variation of the branching degree and end-functionalities led to series of narrowly distributed molar masses. The dependence of the molecular weight on the glass transition temperature for different branching degrees was calculated and compared for polar and non-polar end groups.     

Effect of Ar/O2 ratio on double-sided electrochromic glass performance

This paper reports the qualities of WO₃ film and NiO film added to a counter electrode and their use in a double-sided electrochromic glass device. A mixture of argon and oxygen gasses with ratios of Ar/O₂ of 1.5, 2, 3, and 5 were used for the deposition of the working electrode of WO₃ film for EC glass. The structure of double-side EC glass consists of glass/ITO/NiO/electrolyte/WO₃/ITO/glass/ITO/WO₃/electrolyte/NiO/ITO/glass layers. The working electrode of WO₃ film controls the color presented, the applied voltage controls the color depth, and the counter electrode controls the transparency in the bleached state. The double-sided EC glass with double WO₃ films and double NiO films have faster coloration/bleaching rates than do single-sided EC glass. A mixture of Ar/O₂ ratio of 3.0 has the best coloration/bleaching property of the ratios tested. Compared to the single-sided EC glass, the double-sided EC glass has lower transmittance of about 72% and 6% than the 78% and 12% during coloration and bleaching states in the visible light region with +1.5 V and ?3.5 V applied.     

Effect of pressure and temperature on viscosity of a borosilicate glass

During industrial glass production processes, the actual distribution of stress components in the glass during scribing remains, to date, poorly quantified, and thus continues to be challenging to model numerically. In this work, we experimentally quantified the effect of pressure and temperature on the viscosity of SCHOTT N‐BK7^® glass, by performing in situ deformation experiments at temperatures between 550 and 595°C and confining pressures between 100 and 300 MPa. Experiments were performed at constant displacement rates to produce almost constant strain rates between 9.70 × 10^?6 and 4.98 × 10^?5 s^?1. The resulting net axial stresses range from 81 to 802 MPa, and the finite strains range from 1.4% to 8.9%. The mechanical results show that the SCHOTT N‐BK7^® glass is viscoelastic near the glass transition temperature at 300 MPa of confining pressure. To elucidate the data, we incorporated both 1‐element and 2‐element generalized Maxwell viscoelastic models in an inversion approach, for which we provide MATLAB scrips. Results show that the 2‐element Maxwell model fits the experimental data well. The stress decreases with increasing temperature at 300 MPa and the temperature dependence yields a similar activation energy (601 ± 10 kJ mol^?1 or ?H/R = 7.2 × 10⁴ K) to a previously reported value at 1‐atm (615 kJ mol^?1 or ?H/R = 7.4 × 10⁴ K). The SCHOTT N‐BK7^® glass shows a limited linear increase in viscosity with increasing pressure of ~0.1 log₁₀ (Pa·s)/100 MPa, which is in agreement with the most recent 2‐internal‐parameter relaxation model (based on experiments).     

Effect of hybrid nanoparticles on glass transition temperature of polymer nanocomposites

Changes in the glass transition temperatures of composites based on polystyrene and nanosized macromolecular nanostructures (molecular silicasols, dendrimers) are reported. Silicasols are nanosized particles consisting of a silica core and an ethyl phenyl shell; dendrimers are formed using a carbosilane core with ethyl phenyl end groups. It has been observed that the glass transition temperatures of the composites (T_gc) may be either above or below the glass transition temperature of polystyrene, depending on the size of the filler particles. A theoretical model based on the relation between the glass transition temperature and the configurational entropy of the composite, which satisfactorily describes the experimental dependence, was developed. It is found that the effect of the size of the hybrid nanoparticles on T_gc was determined using two factors. First, the presence of an organic layer on the surface of nanoparticles increases the number of degrees of freedom and the entropy of the system, thereby reducing T_gc. Second, the particles present in the polymer reduce the number of configuration states of macromolecules, which reduces the disorientation entropy. This effect leads to an increase T_gc. The competition between these two main factors determines the sign of the glass transition temperature deviation. The size of the particles and their organic surface layer play the key roles in the thermodynamic properties of the composites. POLYM. COMPOS., 37:1978–1990, 2016. © 2015 Society of Plastics Engineers     

Significant glass transition temperature increase based on polyhedral oligomeric silsequioxane (POSS) copolymer through hydrogen bonding

Summary A series of poly(vinylphenol-co-vinylpyrrolidone-co-isobutylstyryl polyhedral oligosilsesquioxane (PVPh-co-PVP-co-POSS) copolymers were prepared by free radical copolymerization of acetoxystyrene, vinylpyrrolidone with POSS (PAS-co-PVP-co-POSS) following by selective removal of the acetyl protective group, and results in significant glass transition temperature increase. The thermal properties and hydrogen bonding of these copolymers were investigated by differential scanning calorimetry and fourier transfer infrared spectroscopy and good correlation between thermal behaviors and infrared spectroscopy results were observed. Received: 5 April 2002 / Revised version: 16 May 2002 / Accepted: 22 May 2002     

Effect of graft ratio on the dynamic moduli of acrylonitrile‐butadiene‐styrene copolymer

The effect of graft ratio on the dynamic moduli of ABS (Acrylonitrile‐Butadiene‐Styrene Copolymer) has been investigated. Unlike previous papers, the storage modulus at low frequency shows both minimum and maximum as graft ratio increases, and the rubber particles do not agglomerate significantly at high graft ratios. The dependence of the rheological properties on the graft ratio is quite complicated. This arises from its morphological change that leads to different interactions between the rubbery phase and the matrix phase. The minimum has been reported previously, and is explained in terms of rubber dispersion. However, the maximum at high graft ratio has never been reported. The origin of maximum seems to come from the repulsive forces between the long graft chains of neighboring rubber particles. Analogy between our experimental results and simulation results has been discussed to deduce the mechanism of maximum storage modulus at high graft ratio.