Application of degradation kinetics to the rheology of poly(hydroxyalkanoates)

The time‐dependent rheological behavior of a series of 3‐hydroxybuytrate‐based semicrystalline copolymers is employed to determine the expected rheological curves that would be generated in the absence of any polymer degradation. Both dynamic frequency sweep and shear rate sweep experiments were analyzed. A model for the degradation kinetics, coupled with standard rheological relationships, was employed to extrapolate the measured sweeps to predicted curves at time zero, prior to degradation. The model is broadly applicable over a wide range of frequencies or shear rates, and generates a single degradation rate constant k for each polymer studied. A similar, although ad hoc, procedure was applied to the dynamic storage and loss moduli. The model provides a method for determining the rheological behavior of degrading polymers over a time interval, typically found in processing applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1794–1802, 2006     

Modeling of the degradation kinetics of biodegradable scaffolds: The effects of the environmental conditions

The rate of hydrolytic degradation of tissue‐engineered scaffolds made from bioresorbable polyesters is dependent on several factors. Some are related to the properties of the degrading polymeric material, but others are related to the geometry of the porous structure and the operating environment. It is well known that the rate of hydrolytic degradation of a given object, porous or nonporous, is lower when it is exposed to dynamic conditions, a flowing medium, than when it operates in static conditions. The most likely reason is the more efficient removal of the acidic degradation products from the vicinity of the polymeric material when it is operating in a flowing medium. In this article, we present a new phenomenological reaction–diffusion model of aliphatic polymer degradation. The model can be used to predict the significance of various factors in in vitro degradation tests, with particular reference to the flow of the degradation medium, and the frequency of medium replacement in the case of static conditions. The developed model was used to simulate the degradation of poly(dl ‐lactide‐co‐glycolide) scaffolds with different porosities subjected to static and dynamic testing conditions. The results confirm that the porosity of the scaffold had a significant influence on the degradation rate. It was shown that the combination of dynamic conditions and high porosity effectively reduced the mass loss and molecular weight loss of the degrading polymer. However, the effect of changes in the velocity of the flowing medium had a negligible effect on the rate of degradation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40280.     

Current application of controlled degradation processes in polymer modification and functionalization

Ecological concerns over the accumulation of polymeric waste material and the demand for functionalized polymers in specialty applications have promoted extensive research on different controlled degradation processes and their use. The production of functionalized or modified polymers by conventional synthetic routes is expensive and time consuming. However, advances in degradation technology have become an enabling factor in the production of modified polymers and their functionalization. Mild irradiation, ozonization, and enzymatic routes are among the processes that have been explored for polymer modification. Biopolymers, such as chitosan, hyaluronic acids, and polyhydroxyalkanoates, are known to be suitable for a diverse number of applications, ranging from biomedical to organic‐electronics. At the same time, their high molecular weight, crystallinity, and shelf degradability limit their utility. Controlled degradation processes can be used to prepare these types of polymers with reasonably low molecular weights and to generate radical species that help to stabilize these polymers or to initiate further beneficial reactions. In this article, we review the application of controlled degradation processes for polymer modification and functionalization. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Remote inhibition of polymer degradation

Polymer degradation has been explored on the basis of synergistic infectious and inhibitive interaction between separate materials. A dual stage chemiluminescence detection system with individually controlled hot stages was applied to probe for interaction effects during polymer degradation in an oxidizing environment. Experimental confirmation was obtained that volatile antioxidants can be transferred over a relatively large distance. The thermal degradation of a polypropylene (PP) sample receiving traces of inhibitive antioxidants from a remote source is delayed. Similarly, volatiles from two stabilized elastomers were also capable of retarding a degradation process remotely. This observation demonstrates inhibitive cross-talk as a novel interactive phenomenon between different polymers and is consequential for understanding general polymer interactions, fundamental degradation processes and long-term aging effects of multiple materials in a single environment.     

Primary processes of the thermal degradation of HET acid containing unsaturated polyester cured with styrene

The primary processes of thermal degradation of 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic (HET) group containing unsturated polyesters cured with styrene were investigated. DTA traces in nitrogen atmosphere showed a much more pronounced endothermic reaction as the chlorine content in the unsaturated polyester resin decreased. This could be associated to the unzipping of the polystyrene units which is interfered by hexachlorocyclopentadiene ejected during degradation. Actually the styrene formation is prevented in a certain range of temperature due to the interaction with hexachlorocyclopentadiene. This was proved by on-line mass spectroscopic analysis of the degrading polymer.     

Mechanochemical degradation of an EPDM polymer

A mill-mastication study of an EPDM polymer (DuPont, Nordel 1070) was conducted in the mill-roll temperature range of 68–480°F. The extent of degradation was determined by dilute-solution viscosity measurements. The role of oxygen in the polymer mastication was followed by infrared spectroscopy. The breakdown of the EPDM polymer on the mill is minimum in the temperature range of 185–315°F. Up to 315°F. the increase in temperature leads to a decreased amount of degradation. During cold mastication mechanical breakdown occurs. The use of a free-radical acceptor shows that this type of breakdown is caused by the mechanical rupture of C? C bonds in the polymer chain. At and above 350°F. thermooxidative degradation becomes dominant, the polymer degrading drastically, and the higher the temperature, the greater the extent of degradation for the same period of mastication. Infrared spectroscopy shows that hot mastication results in decreased double-bond concentration and increased amounts of carbonyl and, possibly, anhydride and lactone groups. Of the carbonyl groups formed 30% are due to the oxidation of double bonds in terpolymer and 70% to the oxidation of the main chain. A mechanism is proposed to account for these observations.     

Shear degradation of polymer solutions

Shear degradation of polyisobutylene solutions was studied in laminar flow through capillaries. A special apparatus was designed with a view to a controlled shear history. The various effects of initial molecular weight, concentration, temperature, and shear stress at the wall on the final degradation product are combined in a single parameter representing the minimum force required for degrading a polymer sample to its final state. This work is based on the M.Sc. Thesis of A. Kadim, submitted at the Department of Chemical Engineering, Technion—Israel Institute of Technolog, Haifa, Israel.     

Physicochemical Processes in Pyrolysis and Combustion of Fireproof Polyacrylonitrile and Viscose Fibres

The characteristics of thermooxidative degradation of fibres in the presence of flame retardants, manifested by predominance of cross-linking processes which favors formation of CR over degradation processes, are established. Modification with flame retardants decreases the yield and toxicity of combustible volatile products, the rate of thermolysis, the activation energy of dehydration (for VF) and cyclization (for PAN fibres), and the exothermic effects and reverse heat flow to the polymer. The fibres obtained have OI of 32 vol. % and are resistant to wet treatments with a fireproofing effect.     

Preparation and photocatalytic activity of chitosan‐supported cobalt phthalocyanine membrane

A chitosan‐supported cobalt phthalocyanine membrane was prepared by deposition for use as a new environmentally friendly and economical photocatalyst. The structure and surface morphology of the polymer catalyst were analysed by Fourier Transform‐infrared spectroscopy, ultraviolet‐visible spectroscopy, X‐ray diffraction, and scanning electron microscopy. The polymer photocatalyst was used for degradation of Rhodamine B, a stable dye material. Rhodamine B degradation reached 99% in aqueous solution at room temperature under ultraviolet irradiation. The influence of pH, the initial concentration of Rhodamine B, and the catalyst concentrations were investigated. The results revealed that the chitosan‐supported membrane is an attractive photocatalyst for Rhodamine B degradation. It retained 60% of its initial catalytic activity after being reused five times.     

Influence of the processing parameters and composition on the thermal stability of PLA/nanoclay bio‐nanocomposites

Poly(lactic acid) (PLA) is one the most promising bio‐based and biodegradable polymer. However, its low thermal stability limits the range of applications and complicates its transformation via the most industrial common processes. The novelty of this work is studying the thermal stability of PLA and PLA/clay nanocomposites during use, as a function of the composition and using a wide range of extrusion and injection moulding processing parameters. To improve the thermal stability of the PLA, laminar silicates containing different organomodifications have been added (Cloisite 20A and Cloisite 30B). The results show that the processing conditions and composition define the morphology of the bio‐nanocomposites, which plays key role in defining final thermal properties of the material. In general, clays improve the thermal stability of the processed material, increasing the degradation temperature and decreasing the degradation rate under a wide range of processing conditions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40747.     

不同酶对PBS基共聚酯/淀粉复合材料降解性能的影响

采用L_9(3~3)正交试验对α–淀粉酶降解聚丁二酸丁二酯(PBS)基共聚酯/热塑性淀粉(TPS)复合材料的条件进行了优化,得出α–淀粉酶的最优降解条件为:温度65℃,磷酸盐缓冲液p H=6.8,α–淀粉酶浓度3.5 g/L。利用α–淀粉酶和南极假丝酵母脂肪酶N435对PBS/TPS、聚(丁二酸丁二醇-co-丁二酸二甘醇)酯(PBS-co-DEG)/TPS、聚(丁二酸丁二醇-co-丁二酸乙二醇-co-丁二酸聚乙二醇200)酯(PBES-co-PEG200)/TPS、聚(丁二酸丁二醇-co-丁二酸乙二醇-co-丁二酸聚乙二醇400)酯(PBES-co-PEG400)/TPS复合材料分别进行降解实验,研究了两种酶对这4种复合材料降解性能的影响。结果表明,α–淀粉酶和N435脂肪酶对复合材料均有较好的降解能力,当降解时间较短(6 h)时,α–淀粉酶对复合材料的降解效果优于脂肪酶N435,但当降解时间超过60 h后,后者的降解效果略优于前者;(PBES-co-PEG200)/TPS和(PBES-co-PEG400)/TPS复合材料的降解性能总体上优于(PBS-coDEG)/TPS及PBS/TPS复合材料;随PEG200和PEG400在共聚酯中的含量增加,即醚链含量的增加,相应复合材料的质量损失率呈升高趋势,但当醚链含量较高时,复合材料的质量损失率反而有所下降。     

Applicability and limitations of current lifetime prediction models for thermoplastics pipes under internal pressure

Engineering thermoplastics, in particular polyolefins such as special grades of poly(ethylene), are gaining importance in pipe applications such as gas and water supply systems. To ensure proper performance of such pipes over the required lifetime, polymer physics and mechanics concepts are needed to adequately account for the effects of time, temperature, and environmental conditions as well as the occurrence of pipe defects and imperfections on relevant polymer properties and pipe performance. This article provides a critical overview of the scientific background of current methodologies to describe the long-term behavior of thermoplastic pressure pipes. In particular, the merits and limitations of two different approaches-namely, the standard extrapolation method (SEM) described in ISO/TR 9080 and the linear elastic fracture mechanics (LEFM) approach-are compared. Special attention is given to effects associated with material ageing and degradation.     

高铁酸盐和臭氧氧化法降解水中双酚A的研究

通过烧杯试验,对比研究了不同因素对高铁酸盐和臭氧氧化降解双酚A的影响,并对试验过程中的生物毒性进行了对比分析。试验结果表明:针对质量浓度为1 mg/L的双酚A模拟废水,在高铁酸盐和臭氧的投加量分别为5.0和1.20 mg/L的条件下,高铁酸盐降解双酚A的能力更强,去除率达到91.6%,而臭氧氧化法仅为80.9%;同时,高铁酸盐法具有更广的pH值(3~11)和温度(10~50℃)适应性。不同的干扰离子对氧化体系的影响不同,HCO3-对2个氧化体系均具有一定的促进作用;Fe3+的存在具有催化作用,有利于臭氧氧化降解双酚A,但是不利于高铁酸盐的稳定性从而不利于双酚A的脱除。2种方法处理后水的生物毒性均随反应时间的延长呈先升高后降低的趋势,相对而言,高铁酸盐法对处理后水的毒性控制效果更佳。     

Process behavior of compatible polymer blends

It is a common industrial practice to blend virgin polymer with the same polymer recycled from scrap plastic that, in general, has not undergone relevant degradation. In this article, the influence that incorporating recycled material has on injection processes, especially on the rheological behavior of the material was studied. With this aim in mind, a mixture of two materials with the same nature or composition and similar viscosity was used, which is the system that is most commonly seen in industry. The mixture studied is composed of virgin PP (polypropylene) typically found in injection processes, and recycled copolymer PP from scrap plastic. A complete characterization of the materials and applied existing models was carried out to predict the mechanical behavior of the mixtures. A model to predict the behavior of the mixtures during processing, based on the rheological characteristics of the materials used was developed. This predictive model has been experimentally validated using filling tests in injection molding machines, as well as by specific simulation software. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

油田含聚污水处理技术研究进展

随着含聚污水量的逐年增加,越来越多的聚丙烯酰胺降解技术应用到含聚污水处理领域.聚丙烯酰胺降解技术包括机械降解、化学降解、热降解和生物降解,其中生物降解技术成熟、无二次污染.因此,利用高效降解聚丙烯酰胺的菌株处理含聚污水将成为解决这一问题的有效手段.对聚丙烯酰胺降解技术、微生物固定化技术进行了介绍,着重阐述了生物降解技术...     

Comparative study of complex mechanisms of various polystyrene degradations and oxidations

Comparative investigations of the polymeric residues remained after degrading polystyrene by heat or by UV irradiation reveal numerous profound changes of the structural and molecular parameters of the polymer when subjecting it to either of these main types of degradation. The polymeric residues of the commercial and of the prepared polystyrene samples were investigated in view of the following characteristics: discolouration, IR, UV and ¹³C NMR spectra, DSC-analysis, GPC-elution curves and X-ray patterns. The results show pronounced heterogeneity of the degradative reactions occuring in the framework of the thermal and photochemical degradation of polystyrene, including the existence of crosslinking processes and producing thus very inhomogeneous polymeric material. The presumption of the existence of different mechanism paths occuring in various polystyrene structural fractions was confirmed and further promoted, especially from the standpoint that the lower-molecular fractions of the polymer should behave more sensitively against the degradative attacks. Many-sided meanings of the informations obtained by analysing degraded polystyrene samples allow to postulate the present degradative mechanism by comparing among them various types of de gradative processes. The gained informations about the locations and ranges of absorption bands in UV, IR and ¹³C NMR spectra, as well as the complementary evidence from other determinations enabled the claim that polystyrene thermo-oxidative degradation would preferentially take place in the way to produce acetophenone structures near the chain ends. In the initial degradation periods this would be related with substantial lowering of the molecular mass. The photo-oxidative degradation mechanisms cause the build-up ketone and aldehyde structures and ring-opening reactions concurrent with chain crosslinking reactions. Comparing long-wave and short-wave UV irradiations of polystyrene does not only show the existence of inequal induction times, but additionally the presence of two sets of similar reactions leading to the production of many oxidized structures. The investigations would show that oxidative polystyrene degradation is a very complex phenomenon in which the prefered courses of chemical reactions are in the relations to the initial reaction steps, namely they do depend on structures formed in the early stages of the thermal and photo-degradative processes.     

Effect of Thermal Aging on the Optical Properties of ABS Plastics

Poly(acrylonitrile/butadiene/styrene) (ABS) is a two-phase material consisting of elastomer particles in a glassy polymer matric of styrene and acrylonitrile (SAN) [1]. The photooxidation of ABS was the subject of several studies [2, 3]. It was suggested that several processes will take place during photooxidation. These changes include the formation of hydroperoxide [4], chain breakage of the polystyrene, and the oxidation of the polymer as it was monitored by IR spectroscopy [4–6]. Also photooxidation affect the polybutadiene in ABS and oxidizes it, which results in the formation of hydroperoxide. There are no data available on the thermal degradation of ABS. In a previous study the thermal aging of recycled high-impact polystyrene was studied using UV-vis spectroscopy [7]. It was found that this method provided very useful information about the degradation of several industrial polymers [8–12]. In this paper thermal degradation of ABS is investigated by UV-vis and IR spectroscopy.     

Biological pretreatment of corn stover by solid state fermentation of Phanerochaete chrysosporium

Biological pretreatment is a promising way to overcome the biorecalcitrance of cleaving the supermolecular structure of lignocellulose by lignin degrading enzymes from microorganisms. Solid state fermentation of corn stover with the white-rot fungus Phanerochaete chrysosporium was carried out and the efficiency of this pretreatment was evaluated. The enzymatic hydrolysis yield reached a maximum when the corn stover was biologically pretreated for nine days, and the hydrolysis yield decreased sharply if the solid state fermentation was carried out for more than nine days. A possible explanation for this sharp decrease is that not only the lignin degrading enzymes (LiP and MnP) were secreted, but also other metabolites, which were toxic or fatal to the hydrolysis enzymes resulting in the lower hydrolysis yield were generated during the prolonged period of biopretreatment. These results are useful to help determine the optimal timing and to understand the lignin structure and degradation mechanism in biological pretreatment processes.     

Evaluation of degradation on Nylon-6 and Nylon-6/montmorillonite nanocomposite by color measurement

An evaluation of degraded level is an important subject for industrial products. Ordinarily, many kinds of polymer material changes its color through the degrading process by altering its chemical structure, and IR and UV are applicable to ensure the production of the functional groups. However, these methods are hardly applicable to measurements of product on site without the sample collection. A spectrophotometer is sufficiently lightweight, compact, and capable of measurements on site without the sample collection. With these backgrounds, the correlation of the color with the tensile strength and the molecular weight was studied by using the spectrophotometer. Through the thermal aging test at various temperatures, specimens became yellowish and the increase rate of color change was different between neat Nylon-6 and Nylon-6 nanocomposite. Such changes were closely related to the tensile strength and the molecular weight. As a method to evaluate the polymer degradation, the correlation of the difference of yellowness index (ΔYI) with the tensile strength and the molecular weight was sufficiently high and the ΔYI indicated a difference between neat Nylon-6 and Nylon-6 nanocomposite. From these results, it is found that the color measurement with the spectrophotometer is a practical method for evaluation of polymer degradation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Degradation of low density polyethylene during extrusion. I. Volatile compounds in smoke from extruded films

Many problems with odor and taste in food packaging can be traced to degradation of the packaging materials during processing. From this starting point, the degradation of polyethylene in a commercial extrusion coating process was studied by analyzing degradation products present in smoke sampled at the extruder die orifice. Two low‐density polyethylenes, A and B, with similar melt flow indexes and densities and obtained from different producers, were investigated. A third polymer, C, consisting of recycled material B, was also investigated. More than 40 aliphatic aldehydes and ketones, together with 14 different carboxylic acids, were identified in the smoke. The highest concentration was found for acetaldehyde, regardless of polymer and processing conditions. Increasing the extrusion temperatures in the range 280–325 °C increased the amounts of the oxidized products in the smoke. The extruded film thickness, 12 and 25 μm, influenced the concentrations of degradation products, with the thicker film giving higher amounts of product. The recycled polymer C generally gave lower concentrations of degradation products compared with the virgin polymer B. Differences in the product spectrum between the two virgin polymers may be related to differences in the manufacturing process. Many of the identified compounds have very characteristic taste and smell and are consequently of interest from an odor and taste point of view in food packaging applications. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1580–1586, 2002