Thermal stability of poly(vinyl chloride)/layered double hydroxide nanocomposites

Effects of nanoscale dispersed layered double hydroxides (LDHs) on thermal stability of poly(vinyl chloride) (PVC) in thermal and thermooxidative degradation processes are investigated by dynamic and isothermal thermogravimetric analysis (TGA), discoloration test, fourier transform infrared (FTIR), and ultraviolet‐visible (UV‐vis) spectroscopic techniques. During both stages of thermal degradation, the degradation temperatures, including onset degradation temperature and temperature of the maximum degradation rate, increase, and the final residue yield of the PVC/LDH nanocomposites reaches 14.7 wt %, more than double that for neat PVC. The thermooxidative degradation process is more complex. During the first two stages, the presence of nanoscale dispersed LDH particles enhances the thermal stability, whereas in the last stage accelerates the thermal degradation possibly due to the accumulation of heat released. Additionally, the studies of the isothermal thermooxidative degradation process by FTIR and UV‐vis spectra indicate that both polyene backbone formation and some carbonyl groups are simultaneously developed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

热氧处理聚丙烯粉料DSC结晶参数研究

给出了一种采用DSC结晶参数评估聚丙烯回收料降解程度的方法。实验结果表明,随着热氧处理时间的增加,结晶峰温（Tpc）、外推结晶起始温度（Teic）、结晶起始温度（Tic）和结晶热焓（ΔHc）都逐渐下降,且呈现出较好的规律性。可以利用这种规律对聚丙烯回收料的降解程度做定量评估。     

Preparation and Characterization of Partially Degraded High-Density Polyethylene in an Internal Mixer

The partial degradation of high-density polyethylene was done in an internal mixer for different residence time. The oxidative thermomechanical degradation resulted in the formation of carbonyl groups in the polymer. The carbonyl index values estimated from the FTIR studies indicate the increase of carbonyl groups without any induction time. The common phenomenon during oxidative degradation of polyethylene is the increase in trans-vinylene groups and decrease in vinyl groups and these phenomena are observed in the current investigation. Owing to the chain scission occurring during the mixing at processing temperature, the change in morphology was studied by the amount of crystallinity estimated through DSC. The variation in the molar mass of the material was followed by SEC method.     

Thermal Degradation of Polyoxymethylene Evaluated with FTIR and Spectrophotometry

Thermooxidative degradation at and beyond processing temperatures of a polyoxymethylene copolymer has been progressively accelerated to carbonisation through oven-storage aging. The quantification of such degradation was carried out through FTIR spectrography and colour spectrophotometry methods. The state of thermo-oxidation was monitored through the FTIR spectra corresponding to the carbonyl aldehyde group (O=CH) and methylene bending (–CH₂), as well as the chromaticity changes experienced on the sample surface. The results showed that the FTIR bands suggested are a reliable indicator during the initial conditions of degradation, however, the spectrophotometry becomes more appropriate method for more aggressive conditions leading to carbonisation.     

热氧处理聚丙烯粉料DSC熔融参数研究

通过对热氧处理聚丙烯粉料的DSC熔融参数的系统考察,给出了一种采用DSC方法评估聚丙烯回收料降解程度的方法。实验结果表明,随着热氧处理时间的增加,熔融峰温（Tpm）、外推熔融起始温度（Teim）、外推熔融终止温度（Tefm）和熔融终止温度（Tfm）都逐渐下降,且呈现出好的规律性。可以利用这种规律对聚丙烯回收料的降解程度做定量评估。     

红外光谱法定性和定量分析聚烯烃中抗氧剂3114

研究了用红外光谱（IR）法定性和定量分析聚烯烃（聚乙烯、聚丙烯）中的抗氧剂3114的方法和准确度。分析了抗氧剂3114和PE、PP粉料的FTIR图,确定了抗氧剂3114在聚烯烃中的特征吸收峰为1695cm^-1,详细分析了不同含量抗氧剂3114的PE、PP样品的红外谱图和测试的准确度,同时根据抗氧剂3114的标准曲线可知,抗氧剂3114的含量与其特征峰的吸收强度呈良好的线性关系,相关系数达0．97以上,相对百分偏差最大为9．524％。表明红外光谱法可定性和定量分析聚乙烯、聚丙烯中的抗氧剂3114。     

红外光谱法定性和定量分析聚烯烃中微量抗氧剂168

研究了用红外光谱法快速测定（聚乙烯、聚丙烯）中微量亚磷酸酯类抗氧剂168的含量，确定了其与固体粉料的混合方式为溶剂混合；分析了抗氧剂168与PE、PP粉料共混的FTIR图，确定了抗氧剂168在PE、PP中的特征吸收峰分别为854cm^-1、1082cm^-1，详细分析了抗氧剂168分别与特定组成的PE、PP、主抗氧剂1010及硬脂酸钙所制样品对所测谱图和所制曲线的影响。根据抗氧剂168的标准曲线可知。抗氧剂168的含量与其特征峰的吸收强度呈良好的线性关系，相关系数达0．96以上，样品中抗氧荆168的回收率高于94．7％。该方法已用于快速定性和定量分析实际样品。     

Comparison of dynamic and static degradation of poly(vinyl chloride)

The thermal degradation of PVC was measured under dynamic and static conditions. The UV and IR spectra, as well as the molecular weight distribution of the PVC samples, taken after different time intervals were measured. It was established that during the dynamic PVC degradation, performed in a mixing chamber, two stages with different degradation rates can be distinguished both in extinction and torque vs. time curves. While oxygen does not, dissolved HCl does play an important role in the dynamic degradation: HCl steps into reaction with the formed polyenes and has a catalytic action. The chemical degradation, particularly the crosslinking, produces the changes in the rheological behavior of the material. Results were compared with those obtained under static conditions in argon, air, and HCl atmosphere.     

Mechanical,Chemical and Morphological Investigations on the Degradation of Low-Density Polyethylene Films Under Soil-Burial Conditions

Commercial formulations of low-density polyethylene (LDPE) films were subjected to an outdoor soil burial test to investigate the environmental degradation under natural conditions. Samples periodically retrieved from soil were examined for changes in physical character, tensile properties, dielectric behavior, X-ray diffraction pattern and FTIR spectra. Irrespective of thickness and color, load-extension curves of all samples reflect complete or partial destruction of plastic and elastic regions after 15 to 17 months of soil exposure. IR spectra after 17 months revealed major absorption of the region from 1400–1800 cm^?1, characteristic of carbonyl peak in polyethylene. Upon exposure, the power factor increased remarkably and fairly intense transition peaks were found in dielectric loss curves. XRD graphs reflected possible damage in the amorphous region of the polymer matrix. Disrupted holes under scanning electron microscope further revealed degradation of LDPE films under natural soil conditions.     

废旧PU硬泡的降解及其与PP共混物的性能研究

采用二乙醇胺为降解剂对废旧聚氨酯(PU)硬泡进行降解处理,制备了降解PU/聚丙烯(PP)共混材料;研究了不同降解程度的PU硬泡对PU/PP/PP-g-MA共混材料性能的影响。结果表明:随着降解时间的增加,PU硬泡的凝胶的质量分数由91.4%下降到3.6%,降解产物的玻璃化转变温度由75℃下降到36℃;FTIR证明了降解产生了带有氨基和羟基基团的PU,这些基团成为反应增容的活性点;PU/PP/PP-g-MA复合材料的断裂伸长率由100%上升到1800%,SEM表明复合材料具有有良好的均匀性和相互作用。     

Rigid poly(vinyl chloride) (PVC) gelation in the brabender measuring mixer. I. Equilibrium state between sliding,breaking, and gelation of PVC

This article discusses the first part of the Brabender typical torque process curves. Rigid poly(vinyl chloride) (PVC; Polanwil S‐61) was processed at various temperatures between 160 and 200°C with blade speeds in the range of 5–40 min^?1. The morphological changes of the processed compound was characterized by scanning electron microscopy and optical microscopy, and the degree of gelation was estimated on the basis of DSC thermograms. The values of torque minimum strongly depends on temperature. Shear rate affects mainly the time of reaching the minimum torque. The grains are disintegrated into the nonuniform particles and aggregates of the dimensions between 20 and 4 μm. The significant variation of the gelation degree was found for the sample produced in the same conditions and unloaded from Brabender chamber at minimum of torque. It was found that the value of the minimum of torque described momentary equilibrium state between sliding of breaking grains and increasing degree of PVC gelation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 966–971, 2004     

Torque rheometry and rheological analysis of powder–polymer mixture for aluminum powder injection molding

Selection of desired powder–polymer mixture (feedstock) formulation is a key factor in manufacturing perfect parts via powder injection molding. In the present study, feedstock characteristics of an aluminum-based powder were investigated by torque rheometry and rheological analyses. Several binders containing various amounts of polypropylene (PP), paraffin wax (PW), and stearic acid (SA) were selected for torque mixing and viscosity evaluation. Then, feedstocks consisting of 54, 58, 62, and 66 vol. % solid contents were prepared with modified binder. Feedstock flow behaviors were investigated regarding the rheological parameters such as mixing torque, viscosity, flow behavior index, flow activation energy and moldability index. It was found that increasing solid loading from 54 to 62 vol. % led to improved rheological behavior. This improvement was not observed in high solid contents, i.e., 66 vol. %. Based on experimental results, the optimized binder composition (60PW,35PP,5SA vol. %) and the optimum powder loading (62 vol. %) were selected as the best formulations for injection of aluminum powder. These values are supported by critical powder volume concentration measurements deduced from the oil absorption method. The resulting aluminum molded green parts with no defects exhibited the straightforward injection molding process of selected feedstock.     

Polypropylene/polypropylene‐grafted acrylic acid blends for multilayer films: Preparation and characterization

Polypropylene (PP) was functionalized with acrylic acid (AA) and styrene (st) as a comonomer by means of a radical‐initiated melt‐grafting reaction. FTIR, ESCA, and ¹H‐NMR spectroscopies were used to characterize the formation of polypropylene grafted with acrylic acid (PP‐g‐AA) and polypropylene grafted with acrylic acid and styrene (PP‐g‐AAst). The content of AA grafted onto PP was determined by using volumetric titration. Blends of PP with 0–100 wt % of PP‐g‐AA were prepared by melt mixing. The effect of the modified polymer content on the surfaces of cast films was characterized through FTIR–ATR and ESCA analysis as well as contact‐angle, wetting‐tension, and ink‐adhesion measurements. The influence of the content of AA on the melting and crystallization temperature of PP was investigated by DSC. The contact angles of water on cast‐film surfaces of PP/PP‐g‐AA blends decreases with increasing modified polymer content and decreasing PP‐g‐AA molecular weight. A notorious improvement on wetting tension was observed with increasing modified polymer content and decreasing PP‐g‐AA molecular weight. From FTIR–ATR and ESCA spectra of the blends, a calculation was made of the carbonyl index on the films' surfaces. It was found that the higher the carbonyl index, the lower the contact‐angle value for the polypropylene blends. An increase in crystallization temperature of PP was observed when AA monomers were grafted into PP and with increasing PP‐g‐AA content in the blend, probably caused by a nucleation effect of AA monomers that would improve the crystallization capability of PP. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1497–1505, 2001     

Thermal stability and decomposition mechanism of poly(p‐acryloyloxybenzoic acid and poly (p‐methacryloyloxybenzoic acid) and their graft copolymers with polypropylene,Part II

Thermal stability and decomposition mechanism of poly(p‐acryloyloxybenzoic) acid (PABA), p‐methacryloyloxybenzoic acid (PMBA), and their graft coproducts of PP were studied by differential scanning calorimetry, direct pyrolysis mass spectrometry, and TG/IR system, combined thermogravimetric analyzer, and FTIR spectrometer. The homopolymers and corresponding grafts were found to be stable in nitrogen atmosphere but started to decompose under atmospheric conditions when heated above 230°C. PABA and PAPA‐g‐PP showed a better thermal stability compared to the other polymer. The degradation proceeded predominantly by decomposition of side groups giving phenol, benzoic acid, hydroxybenzoic acid, carboxylic and carbonyl groups, and by decomposition of phenol into cyclodiene mainly. It was also seen that the degradation path did not greatly changed whether the PABA or PMBA were homopolymers or grafted onto PP but the induction temperature of grafted polymers was seen at some 10–20°C higher. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Kinetics of thermo-oxidative degradation of zinc borate/microcapsulated red phosphorus with magnesium hydroxide in flame retarded polypropylene composites

The flammability and the thermo-oxidative degradation kinetics of zinc borate (ZB) and microcapsulated red phosphorus (MRP) with magnesium hydroxide (MH) in flame-retardant polypropylene (PP) composites were studied by limiting oxygen index (LOI), TGA, and FTIR spectroscopy. The results show that ZB/MRP is a good synergist for improving the flame retardancy of the PP composites. The Kissinger and Flynn-Wall-Ozawa methods were used to determine the activation energy (E) for degradation of PP composites. The results from the TGA curves indicate that the thermal stability of PP/MH/ZB and PP/MH/ZB/MRP composites is better than that of PP/MH composites. The kinetic results show that the values of E for degradation of PP/MH/ZB/MRP composites is much higher than those of PP/MH and PP/MH/ZB composites. The FTIR spectra data show that the incorporation of MH improves the thermo-oxidative stability of PP, especially for PP/MH composites with suitable content of MRP at higher temperatures. These data indicate that the synergistic flame retardants used in this work have a great effect on the mechanisms of pyrolysis and combustion of PP/MH composites.     

A comparison of rheology and FTIR in the study of polypropylene and polystyrene photodegradation

Rheology and FTIR spectroscopy are compared as methods to study the degree of photodegradation in polypropylene (PP) and polystyrene (PS) sheets. The materials are hot pressed, artificially photo‐aged with fluorescent lights for 4–2048 h and then measured with a rotational rheometer and FTIR. Both materials show a tendency for chain scission which can be seen as a reduction in viscosity. Changes in PP can be observed with both methods after 256 h of irradiation. Changes in PS become significant in rheology after 64 h but in FTIR only after 1024 h of irradiation. Due to the different chemical nature of the materials, the degradation of PS is rather linear with exposure, whereas the degradation of PP is more exponential. Using the zero shear viscosities obtained through extrapolations of the Cole–Cole and Carreau–Yasuda models, relative molecular weights are estimated with the aid of the power–law relationship between these two. These results are compared with the carbonyl indices determined from the FTIR spectra. Rheology is found to be a viable alternative for FTIR in certain situations. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42246.     

Effect of zeolite filler on the thermal degradation kinetics of polypropylene

In this study, the thermal degradation behavior of polypropylene (PP) and PP–zeolite composites was investigated. Clinoptilolite, a natural zeolitic tuff, was used as the filler material in composites. The effects of both pure clinoptilolite and silver‐ion‐exchanged clinoptilolite on the thermal degradation kinetics of the PP composites was studied with differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Polymer degradation was evaluated with DSC at heating rates of 5, 10, and 20°C/min from room temperature to 500°C. The silver concentration (4.36, 27.85, and 183.8 mg of Ag/g of zeolite) was the selected parameter under consideration. From the DSC curves, we observed that the heat of degradation values of the composites containing 2–6% silver‐exchanged zeolite (321–390 kJ/kg) were larger than that of the pure PP (258 kJ/kg). From the DSC results, we confirmed that the PP–zeolite composites can be used at higher temperatures than the pure PP polymer because of its higher thermal stability. The thermal decomposition activation energies of the composites were calculated with both the Kissinger and Ozawa models. The values predicted from these two equations were in close agreement. From the TGA curves, we found that zeolite addition into the PP matrix slowed the decomposition reaction; however, silver‐exchanged zeolite addition into the matrix accelerated the reaction. The higher the silver concentration was, the lower were the thermal decomposition activation energies we obtained. As a result, PP was much more susceptible to thermal decomposition in the presence of silver‐exchanged zeolite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 143–148, 2006     

Microstructure evolution of ammonia‐catalyzed phenolic resin during thermooxidative aging

The thermooxidative aging of ammonia‐catalyzed phenolic resin for 30 days at 60–170°C was investigated in this article. The aging mechanism and thermal properties of the phenolic resin during thermooxidative aging were described by thermogravimetry (TG)–Fourier transform infrared (FTIR) spectroscopy, attenuated total reflectance (ATR)–FTIR spectroscopy, and dynamic mechanical thermal analysis. The results show that the C? N bond decomposed into ammonia and the dehydration condensation between the residual hydroxyl groups occurred during the thermooxidative aging. Because of the presence of oxygen, the methylene bridges were oxidized into carbonyl groups. After aging for 30 days, the mass loss ratio reached 4.50%. The results of weight change at high temperatures coincided with the results of TG–FTIR spectroscopy and ATR–FTIR spectroscopy. The glass‐transition temperature (T_g) increased from 240 to 312°C after thermooxidative aging for 30 days, which revealed the postcuring of phenolic resins. In addition, an empirical equation between the weight change ratio and T_g was obtained. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Investigation of degradation of polypropylene in soil using an enzymatic additive

Polypropylene (PP) has been widely used industrially in several sectors, mainly in the use of packaging of different products. Thus, this has been accumulated in our environment due to the incorrect disposal and its high resistance toward degradation, causing an array of environmental impacts. With this, one alternative that has been explored to minimize the problems intensified by these residues is the use of pro-degrading additives. Therefore, the aim of this work is to evaluate the degradation process of PP blends in soil using enzymatic additive. The soil degradation experiment was done for 6 months; monthly collected samples were checked for alterations on the material properties during that time. The extent of PP degradation with enzymatic additive was compared to an organic additive by techniques of FTIR, TGA, DSC, carbonyl index (CI), and crystallinity. From the obtained results it was observed that the additives influenced the degradation of PP. In addition, the enzymatic additive caused more significant changes in the CI (increase of 3693%), crystallinity (variation of 18.7%), and structural characteristics, indicating a greater influence on the degradation process in relation to the organic additive. In this way, this work has had an important role in the research and development of biodegradable materials with the aim of minimizing the effects induced by plastic waste in the environment.

     

Effect of hydroperoxide decomposer and slipping agent on recycling of polypropylene

Polypropylene (PP) recycling has always been challenging because the polymer is highly susceptible to thermooxidative degradation during extrusion. Recycled (degraded) PP is normally blended with virgin PP to achieve reasonable mechanical properties after reprocessing operations. However, impurities present in recycled PP tend to degrade even the virgin PP in this process. In this study, standard recycled PP was produced in a laboratory by repeated extrusion and pelletization operations of virgin PP. This material was blended with virgin PP in a ratio from 3 : 7 to 7 : 3. An attempt was made to stabilize the recycled blend by adding a peroxide decomposer (triphenylphosphite, TPP) and a slipping agent (zinc stearate) in contrast to radical scavengers normally used in reprocessing. It was found that by using 0.3–0.5 wt % of TPP and 2 wt % of zinc stearate, this degradation could be effectively attested. Compared to the tensile strength retention of 68% (based on strength of pure virgin PP) of a 60 : 40 (recycled : virgin) PP blend without any stabilizer, a value of 77% was obtained for the same blend with the above‐mentioned stabilizers. This stabilization effect was attributed to decomposition of unstable hydroperoxides to stable compounds in the recycled materials by TPP, and lower generation of new radicals in the presence of zinc stearate. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3247–3251, 2004