FTIR Study of the Thermal Degradation of Poly(vinyl Alcohol)

The degradation of poly(vinyl alcohol) was investigated using TG analysis and Fourier transform infrared spectroscopy to determine the effect of atmosphere on the process of degradation. In the spectra, four vibrational modes were identified that characterised the major steps of the degradation process. These were the O-H, C-H, C=O and C=C stretching modes. The mechanism observed for degradation in an inert atmosphere was in accordance with the accepted mechanism of elimination followed by pyrolisation. Evidence of conjugated polyenes, however, was not observed. For the air atmosphere, oxidation in both steps of the degradation process was observed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal Degradation and Kinetics of Poly(3-hydroxybutyrate)/Organoclay Nanocomposites

Poly(3-hydroxybutyrate)/Cloisite30B (PHB/30B) nanocomposites were prepared by solution-intercalation method. The influence of 30B content on the thermal stability of PHB was investigated. With the addition of 3 wt. % of 30B the highest thermal stability of PHB was achieved. The kinetic analysis of the non-isothermal degradation was performed using the isoconversional Friedman method and invariant kinetic parameters method.     

苯乙烯/聚氯乙烯接枝膜的热稳定性研究

用自由基悬浮聚合法合成了苯乙烯 /聚氯乙烯接枝膜 ,并对产物热处理 ,然后进行紫外 -可见光谱 ,红外光谱 ,热失重分析。结果表明接枝苯乙烯后的聚氯乙烯膜热稳定性得到了提高。同时 ,讨论了热稳定性机理。     

Al(OH)3和Mg(OH)2对PVC热解特性的影响研究

利用热重分析仪并借助电导率测定法探讨了Al(OH)3和Mg(OH)2对PVC热解特性的影响,简要分析了其机理。结果表明:加入Al(OH)3和Mg(OH)2后均能增加PVC体系在第一阶段的最大热解速率和残炭量,最大热解速率增加约1倍,残炭量增加约4倍。并且分解产生的结晶水吸收大量的热量,惰性金属氧化物也有利于成核、炭层生长和凝聚,有着明显的阻燃和抑烟作用。HCl毒性气体的释放主要集中在体系的第一阶段,Al(OH)3能促使HCl提前释放,HCl的释放总量增加,Mg(OH)2也能促使HCl提前释放,但HCl的释放总量却是减少的。     

A study of the thermodynamic properties and dehydration reaction kinetics of some salt-hydrates

Correlations were determined between heat capacity and temperature and phase change enthalpy of Ba(OH)₂·8H₂O. The phase diagram and DSC curve of the binary system Na₂CO₃·10H₂O?Na₂HPO₄·12H₂O were determined The kinetics of the dehydrating reaction of Ba(OH)₂·8H₂O, Na₂CO₃·10H₂O and Na₂HPO₄·12H₂O were measured and theoretically analyzed by TG.     

Thermal degradation of copolymers from vinyl acetate and vinyl alcohol

The thermal degradation of poly(vinyl acetate) (PVA), poly(vinyl alcohol) (PVAL), vinyl acetate-vinyl alcohol (VAVAL), vinyl acetate-vinyl-3,5-dinitrobenzoate (VAVDNB) and vinyl alcohol-3,5-dinitrobenzoate (VALVDNB) copolymers have been studied using differential thermal analysis (DTA) and thermogravimetry (TG) under isothermal and dynamic conditions in nitrogen. Thermal analysis indicates that PVA and PVAL are thermally more stable than VAVAL copolymers, being PVAL the most stable polymer. The presence of small amounts of vinyl-3,5-dinitrobenzoate (VDNB) in PVA or PVAL produces a marked decrease in the thermal stability of both homopolymers, being VALVDNB copolymers the less stable materials. The apparent activation energy of the degradative process was determined by the Kissinger and Flynn-Wall methods which agree well.     

Thermal evolution of microporous nitroprussides on their dehydration process

Divalent transition metal nitroprussides form a family of microporous materials which lose their crystallization water (coordinated and zeolitic) below 100°C and then remain stable up to above 150°C. The dehydration process of representative samples in their stable phases was studied by thermo-gravimetry (TG) and differential scanning calorimetry (DSC). The copper complex dehydrates in a single step through a practically irreversible process. For cadmium and cobalt complexes the water evolution on heating takes place in two stages. The first one, where only zeolitic waters are removed, is dominated by a diffusion mechanism while, during the loss of the strongly bonded waters (second stage) the material framework effect is added. The involved activation energy and its dependence on the conversion degree were estimated evaluating the thermo-gravimetric data according to an isoconversion model.     

Thermal and dynamic mechanical analysis of cross-linked poly(esterurethanes)

New cross-linked poly(esterurethanes) (PEU) based on unsaturated olygo(alkyleneester)diol (OAE), 4,4’-diphenylmethane diisocyanate (MDI) and styrene or methyl methacrylate as curing monomers were prepared. The synthesis of PEU was performed in two steps. In the first step OAE was obtained from adipic acid, maleic anhydride and ethylene glycol. In the second step a prepolymer was obtained in a reaction of OAE with different amounts of 4,4’-diphenylmethane diisocyanate followed by crosslinking using previously mentioned curing monomers. The influence of structure of the poly(esterurethanes) on thermal and dynamic mechanical properties is studied. Thermogravimetric analysis shows that cross-linked poly(esterurethanes) demonstrate high thermal stability. Moreover the dynamic mechanical thermal analysis shows that the presence of styrene cross-linking chains in polymers lead to the phase separation in cross-linked poly(esterurethanes).     

几种热塑性特种工程塑料的热分析研究

聚芳醚和聚芳硫醚两类聚合物都为热塑性的耐高温特种高分子材料 ,由于它们的加工性好、加工成型效率高 ,受到了世界各国的高度重视。这两类聚合物在结构上有许多相似之处 ,如它们的主链都含苯环、酮基或砜基 ,而聚芳醚类聚合物的柔性基团为醚键 ,聚芳硫醚类聚合物的柔性基团为硫醚键 ,但由于氧和硫在元素周期表中属于同一族元素 ,原子结构仍然相似 ,因而在某些方面具有一定的可比性。研究它们的性能差异对于改进聚合物性能以及进行进一步的结构设计将有一定的帮助。在这两类聚合物中 ,国内已商品化生产的品种有ＰＥＥＫ、ＰＥＳ和ＰＰＳ ,有…     

Kinetics of the complex process of thermo-oxidative degradation of poly(vinyl alcohol)

The thermo-oxidative degradation of poly(vinyl alcohol) (PVA) has been investigated by TG+DTG+DTA simultaneous analysis performed in static air atmosphere, at four heating rates, namely 3, 5, 10 and 15 K min⁻¹. TG, DTG and DTA curves showed that, in the temperature range 25–700°C, four successive processes occur. The first process consisting in the loss of physical adsorbed water is followed by three processes of thermal and/or thermo-oxidative degradations. The processing of the non-isothermal data corresponding to the second process (the first process of thermo-oxidation) was performed by using Netzsch Thermokinetics — A Software Module for Kinetic Analysis. The dependence of the activation energy evaluated by Friedman’s isoconversional method on the conversion degree shows that the investigated process is complex one. The mechanism of this process and the corresponding kinetic parameters were determined by Multivariate Non-linear Regression Program and checked for quasi-isothermal experimental data. It was pointed out that the first process of thermo-oxidation of PVA consists in three consecutive steps having Avrami-Erofeev kinetic model. The obtained results can be used for prediction of the thermal lifetime of PVA corresponding to a certain temperature of use and an endpoint criterion.     

纳米LDH作为热稳定剂在PMMA中的应用

水滑石;;聚甲基丙烯酸甲酯;热稳定性;纳米LDH作为热稳定剂在PMMA中的应用     

Radiation effects on the thermal degradation of poly(vinyl chloride) and poly(vinyl alcohol)

Radiation effects on the formation of conjugated double bonds in the thermal degradation of poly(vinyl chloride) (PVC) and poly(vinyl alcohol) (PVA) were investigated. Thin films of PVC and PVA were either irradiated with γ-rays at ambient temperature (pre-irradiation) and then subjected to thermal treatment, or irradiated at elevated temperatures (in situ irradiation). An extensive enhancement of the thermal degradation was observed for the pre-irradiation of the PVC films, which was more effective than the effect of the in situ irradiation at the same absorption dose. For the PVA degradation, however, the effect of the in situ irradiation was larger than that of the pre-irradiation. The results were explained and related mechanisms were discussed based on radiation-induced chemical reactions and their individual contributions to the thermal degradation behaviors of the two polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3089–3095, 1998     

Thermal and photochemical stability of poly(methyl methacrylate) and its blends with poly(vinyl acetate)

An investigation of the thermal stability of poly(methyl methacrylate) (PMMA) blends with poly(vinyl acetate) (PVAc) revealed that PVAc acts as a stabilizer as concerns thermal and photochemical degradation when the processes take place in air. The temperatures of decomposition of these blends are higher than that of pure PMMA. The efficiency of photodegradation and photooxidation in the blends is lower than that of pure PMMA.     

Thermal weight loss of silica-poly(vinyl acetate) (PVAc) sol-gel composites

Thermogravimetric analyses of sol-gel derived silica and silica-poly(vinyl acetate) (PVAc) materials show that the loss in weight between 35 and 900°C can be attributed to three distinct reactions. Samples were prepared by dissolving the reactants tetraethyl orthosilicate (TEOS), poly(vinyl acetate) (PVAc), and water in mixtures of ethanol and formamide. The lowest temperature weight loss is due to the decomposition/removal of the solvents, while the intermediate weight loss corresponds to decomposition of the PVAc. The highest temperature weight loss is related to the dehydroxylation of the silica surface. The relative amounts of ethanol and formamide have a considerable effect on processing time, drying behavior, and the resulting thermal behavior of the gels.The financial support of the Center for Ceramic Research, a New Jersey Commission on Science and Technology Center, is greatly appreciated.     

Electrochemical synthesis of poly(3‐methylthiophene): A kinetic study

Poly(3‐methylthiophene) (P3MT) films were electrogenerated on both platinum and carbon‐felt working electrodes. The kinetic equation was determined by the monomer and electrolyte concentrations being changed for different reaction times. For each sample, the weight of the polymer obtained was measured along with the polymerization charge, the oxidation charge, the ratio (R) between the two magnitudes, the charge storage efficiency (SE), and the doping level. The results obtained from the kinetic study indicate significant electrolyte participation in the electropolymerization process. The SE and the doping level decreased inversely proportionately to both the reaction time and the concentrations of the monomer and electrolyte. The ratio R increased with reaction time as well as with monomer or electrolyte concentrations for all P3MTs generated on the carbon‐felt electrodes, whereas for those films generated on platinum electrodes, the highest values were obtained for the lowest monomer and electrolyte concentrations. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1258–1266, 2000     

Improvement of Structural and Thermal Stabilities of PVC and Wood/PVC Composite by Zn and Pb Stearates,and Zeolite

Three different chemical stabilizers were introduced into neat PVC and a wood/PVC composite (containing 50 phr wood flour) to improve their thermal and structural stabilities. The changes in CIE yellowness index, polyene index, %wt loss, and decomposition temperature (T_d) were monitored. The effects of type and content of thermal stabilizers, thermal ageing time, and the presence of wood flour were our main interests. The experimental results suggested that the additions of Zn and Pb stearates into PVC and wood/PVC composite could improve the thermal stability of the PVC. At the test temperature of 177°C, the additions of Zn and Pb stearates could improve the thermal stabilities of PVC by retarding the upzipped reaction and by reducing the conjugated double bonds in PVC, Pb stearate being the most suitable for thermally stabilizing the PVC. Around the T_d range (～264°C), the addition of Zn stearate reduced the T_d value of PVC whereas that of Pb stearate had no effect on the change in T_d value. Zeolite loading could shift the T_d value of the PVC from 264 to 280°C. The addition of wood particles increased the polyene content and decreased the decomposition temperature of the PVC. The effect of wood flour on the thermal and structural changes of PVC overruled that of thermal stabilizer loading.     

Structure and thermal behaviors of poly(vinyl alcohol)/surfactant composites: Investigation of molecular interaction and mechanism

Poly(vinyl alcohol) (PVA) is a promising biocompatible polymer, whose applicability is limited by its narrow processing window. Here, we adopted a facile approach to broaden the processing windows of PVA based on phosphoric ester of poly(ethylene oxide) (10) nonylphenyl (NP‐10P). Thermal analysis shows that both the melting temperature (T_m) and the glass transition temperature (T_g) of PVA decrease noticeably as NP‐10P content increases, indicating good miscibility of NP‐10P with PVA. The thermal degradation kinetics suggests composites display excellent thermal stability compared with neat PVA. The pyrolysis mechanism of PVA before and after modification with NP‐10P varies from chain unzipping degradation followed by chain random scission to chain random scission. The processing window of PVA is broadened from 9°C to 98°C with low content NP‐10P (5 wt%). Moreover, the composites maintain significant mechanical performance and transparency. This work provides an environmentally friendly and economical method to improve the possibility of thermal melt processing for PVA.     

Thermal Analysis of the Poly(Siloxane)–Poly(Tetrafluoroethylene) Coating System

Thermal properties of poly(siloxane)–poly(tetrafluoroethylene) (SIL–PTFE) system were investigated, using Perkin Elmer DSC-7 differential scanning calorimeter and TGA-7 thermogravimetric analyzer. For SIL–PTFE compositions, one glass transition temperature T _g has been found, in accordance with the reciprocal rule up to about 40 mass% of PTFE. However, for higher PTFE contents, T _g values about –118 to –112°C were observed that can be ascribed to motions of cross-linked SIL structures. Endo- and exothermic transitions, found in the range from 70 to 290°C, not observed for pure SIL and PTFE components, are considered as specific ones for the SIL–PTFE semi-IPN structures. The SIL–PTFE system, as well as its components, is thermally stable, if degradation reactions are considered; the temperatures of decomposition at the maximum decomposition rate were above 530°C. It has been found that the thermal stability of the SIL–PTFE system is increasing with the increase of the PTFE content. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal lensing in poly(vinyl alcohol)/polyaniline blends

Nonlinear optical properties of poly(vinyl alcohol) (PVA)/polyaniline (PAni) blends were measured with the single‐beam Z‐scan technique with Fourier analysis. The results obtained with continuous wave (cw) excitation indicated that the self‐phase modulation had a thermal origin. Besides the Z‐scan technique, we also employed the time‐resolved mode‐mismatched thermal lens (TL) technique to obtain the temperature coefficient of the optical path length, ds/dT, and the thermal diffusivity coefficient, D, for the specific concentrations used in our blends. ds/dT varied between ?0.8 and ?1.0 × 10^?4 K^?1, whereas the thermal diffusivity varied between 1.0 and 1.3 × 10^?3 cm²/s. The TL technique was further used to study the aging of the blends as they were heated to 90 °C. Unlike the electrical conductivity of PAni films, which presented a strong dependence on the doping level, the thermooptic properties presented only a slight variation with doping. This feature indicated that the PVA/glutaraldehyde network made the main contribution to the thermooptic properties (D and ds/dT) in the PAni blends. Similarly, dimethyl sulfoxide as a solvent determined the thermooptic properties of PAni solutions. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1949–1956, 2002