Development of potentially degradable materials for marine applications. III. Polyethylene-polyethylene oxide blends

The effect of a simulated marine environment on unstabilized polyethylene-polyethylene oxide blends, having varying polyethylene oxide content (up to 40% by weight), with or without a metal catalyst (e.g., cobalt (III) acetylacetonate) and a metal containing plasticizer (e.g., aluminum stearate), has been studied for 10 weeks exposure time. In the absence of metal catalyst and plasticizer, phase separation of polyethylene oxide was quite evident visually after melt mixing and subsequent regular compression molding of polyethylene-polyethylene oxide blends. However, these blends rendered better and uniform mixing in the presence of metal catalyst and plasticizer. Since polyethylene oxide is a water soluble component of the system, % weight loss increased significantly with increase in its content after exposure to brine. These blends have been further characterized by tensile properties, optical and scanning electron microscopy, and thermal analysis in order to monitor mechanical as well as morphological changes.     

Photodegradable vinyl plastics. III. Comparison of ultraviolet light and sunlight exposure

Polystyrene (PS), polypropylene (PP), and polyethylene (PE) films, blended with additives to enhance photodegradability, were irradiated with UV light and sunlight. In almost every case, photodegradation was greater with outdoor exposure than under laboratory conditions. Explanations for the differences in degradation obtained by the two methods of irradiation are discussed. Based on IR measurements and molecular weight determinations, photo-oxidative changes that occur in PS induced by UV light appear similar to those induced by sunlight. In addition to the additives previously reported, several new classes of photoinitiators were evaluated. These include selected halocarbonyl compounds, haloalkyl sulfur compounds, and halogen compounds containing certain electron-withdrawing groups. The performance of the additives in vinyl polymer blends is discussed.     

Degradability in a natural compost medium of (linear low‐density polyethylene)/(soya powder) blends compatibilized with epoxidized natural rubber

The objective of this study was to investigate the degradability of linear low‐density polyethylene (LLDPE)/(soya powder) blends. The blends were compatibilized by epoxidized natural rubber with 50 mol% of epoxidation. They were exposed to a natural compost medium located in northern Malaysia. The degradability was evaluated by using tensile tests, a morphological study, carbonyl indices, crystallinity measurements, weight loss, and molecular‐weight changes. The tensile strength and elongation at break of the compatibilized blends decreased during one year of exposure. The colonization of fungus and the formation of pores were observed in micrographs. The carbonyl indices, crystallinity, and weight loss increased during exposure, thereby indicating the degradation of the blends. The reduction in molecular weight revealed the degradation of the LLDPE upon composting. Surprisingly, after composting, the compatibilized blends showed more degradation than the uncompatibilized ones. J. VINYL ADDIT. TECHNOL., 20:42–48, 2014. © 2014 Society of Plastics Engineers     

Thermo-oxidative and photo-oxidative aging of polypropylene under simultaneous tensile stress

The effect of uniaxial tensile stress at constant load in the range of 0 to 6.86 MN/m² upon the behavior of stabilized and unstabilized types of isotactic polypropylene was investigated in the course of thermo-oxidative aging at 80° to 130°C and of photo-oxidative aging in the Xenotest 450 apparatus at 45° and relative humidity of 65%. From kinetic evaluation of the temperature dependence of weight changes of unstabilized polypropylene during thermo-oxidative aging, it was found that the weight losses of unstressed and tension-stressed specimens obey the kinetic equations for a reaction of the first order. The degradation of stressed specimens, however, proceeds at a considerably higher rate as compared with the unstressed state and is marked by a decrease in apparent activation energy as well as by an increased rate of crack development. The cracks develop in the direction perpendicular to the tensile stress and have the shape of hollow funnels widening outward. The tensile stressing of stabilized types of polypropylene in thermo-oxidative and photo-oxidative environments causes an accelerated embrittlement of the polymer, manifested particularly by a marked decrease of elongation at break. This accelerated embrittlement goes on under the action of tensile stresses exceeding the so-called safe stress, i.e., the stress below which no acceleration of aging (as measured by the relative decrease in the elongation at break of the stressed and unstressed specimens), can be detected. The values of this safe tensile stress decrease with the temperature and lie well below the tensile strength of the polymer. In the range of tensile stresses exceeding the safe stress, the dependence of the logarithm of time of a 50% decrease of the elongation at break on the applied tensile stress was found to be linear. The findings are in agreement with Zhurkov's kinetic concept of mechanical deterioration of polymers, where the effect of the applied mechanical stress is superimposed on the thermal fluctuation and leads to the scission of chemical bonds and to the formation of cracks in the polymer.     

Ultrasonication and microwave assisted extraction of degradation products from degradable polyolefin blends aged in soil

Two nonconventional extraction techniques, microwave assisted extraction (MAE) and ultrasonication, were used to extract degradation products from polyolefins with enhanced degradability. High‐density polyethylene/polypropylene blends with two different biodegradable additives (a granular starch/iron oxide mixture and Mater‐Bi AF05H) were subjected to outdoor soil burial tests and removed at different periods of time between 0 and 21 months. The extracted products were analyzed by gas chromatography mass spectrometry (GC‐MS). Ultrasonication was found to be a more suitable technique than MAE because of better reproducibility. In addition, higher amounts of certain products (e.g., carboxylic acids) were extracted by ultrasonication than by MAE. The degradation products extracted from the two blends were basically a homologous series of alkanes, alkenes, carboxylic acids, and alcohols. The amount of hydrocarbons (saturated and unsaturated) and alcohols remained basically the same as the degradation times increased. However, carboxylic acids tended to decrease slightly with the exposure time. Their concentration remained practically unchanged until 12 months of soil burial when a more significant decrease was noted. The quantitative analysis of the degradation products revealed for both samples a decrease in the amount of carboxylic acids with the exposure time, although the trend was different according to the additive used in each sample. For blends with Mater‐Bi the amount of carboxylic acids was at a minimum after 12‐month exposure in soil, which coincided with a minimum in the molecular weight distribution. After blends with granular starch/iron oxide were exposed to 3 months in soil, tetradecanoic acid was no longer detectable and the amount of hexadecanoic and octadecanoic acids decreased significantly. Solid‐phase microextraction, a solvent‐free extraction technique, was used to extract the degradation products that could have migrated to the soil from blends with Mater‐Bi. Small amounts of tetradecanoic acid and dodecanol were identified by GC‐MS in the soil surrounding the sample. The degradation patterns observed here correlate with our previous results from mechanical and morphological characterization of these samples. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1101–1112, 2001     

Investigation of tensile properties and dyeing behavior of various polypropylene/amine modifier blends

Polypropylene is utilized in manifold applications due to its unique properties. However, its use has been limited in the textile industry because conventional dyestuffs have no affinity for this polymer. Amine modifiers, generally improve the dye‐ability of polypropylene. Polyamide 6 (PA6) is a traditional amine modifier which improves the dyeing ability of polypropylene with disperse dyes. In this investigation, polyetheramine (PEA) is introduced as a novel amine modifier which improves the dye‐ability of polypropylene with disperse and acid dyestuffs. To this end, the dyeing behavior as well as possible impairments of tensile properties of PEA modified polypropylene were studied and compared to PA6 modified polypropylene. As with the PA6 containing blends, the tensile properties of the incompatible PP/PEA blends decreased due to weak interfacial adhesions between the components of the blends. However, the incorporation of a compatibilizer into such blends led to better dispersions of modifiers in the matrix as well as formation of amide or imide linkages which in turn reincreased the tensile properties almost to their initial values. Both PEA and PA6 modifiers improved the disperse dye uptake of the blends. However, Only Jeffamine ED‐2003 (i.e., PEA) was capable of enhance the acid dye uptake of modified polypropylene. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Plastic waste minimization: Compatibilization of polypropylene/polyamide 6 blends by polyalkenyl‐poly‐maleic‐anhydride‐based agents

The present article discloses the properties improvement in PP/PA 6 blends by new type experimental coupling additives. By the experimental agents especially the tensile properties could be improved. For example, the tensile strength and the elongation were 16.5 MPa and 4.4% without additive, which increased to 25.5, 20.1, 46.8 MPa and 8.1, 6.4, 8.6% in specimens containing polyalkenyl‐poly‐maleic‐anhydride‐amide, polyalkenyl‐poly‐maleic‐anhydride‐ester, and MA‐grafted‐low‐polymer additives, respectively. DSC curves shows that compatibilizers influenced thermal properties of the polymer blends and reveal affecting of crystalline phase formation process in the blends due to the compatibilization step. Additives A and B rather leads to influencing of PA crystallinities. According to the SEM and FTIR analysis well separated polypropylene and polyamide phases was observed in case of specimens absence of additives but only one well distributed phase by the applying of the synthetized coupling agents. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Epoxidized linolenic acid salts as multifunctional additives for the thermal stability of plasticized PVC

Calcium and zinc salts of epoxidized linolenic acid were synthesized and used as multifunctional additives, to minimize or prevent the reaction of epoxidized soybean oil (ESO) with liberated hydrochloric acid (HCl) during the thermal degradation of poly(vinyl chloride) (PVC) in particular. These metal epoxy salts were incorporated as thermal stabilizers for both diisodecyl phthalate and ESO–plasticized PVC blends that underwent thermal degradation studies at 170°C. The overall performance of these metal epoxy salts was examined by thermal gravimetric analysis and visual color retention of the PVC blends. The weight loss profiles of the metal salt stabilized PVC were comparable to those of blends containing metal stearates. There were, however, vast improvements in color retention of the plasticized PVC using these novel additives. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41736.     

Chemical conversion of PET waste using ethanolamine to bis(2-hydroxyethyl) terephthalamide (BHETA) through aminolysis and a novel plasticizer for PVC

Poly(ethylene terephthalate) (PET) recycling has been carried out by various methods, e.g., mechanical recycling, chemical recycling and energy recovery method. In this study, chemical recycling of PET was carried out by aminolysis using ethanolamine and converted into bis(2-hydroxyethyl) terephthalamide (BHETA). The reaction was performed by varying the PET:ethanolamine ratio, reaction time and catalyst used for waste medical grade bottles of PET. Yield of about 81 % was obtained for PET:ethanolamine ratio of 1:4 (w/w), with 3 h reaction time, at 160 °C with zinc acetate as a catalyst. BHETA was characterized with FTIR, ¹H NMR, and DSC analysis. BHETA was further reacted with heptanoic acid at a molar ratio of 1:2.5. The product obtained was used as a plasticizer for PVC at 5, 10, 15 and 20 parts per hundred (phr) concentration. Thermal and mechanical tests were carried out and the result obtained was compared with the virgin PVC without plasticizer and with conventional plasticizer of PVC, i.e., dioctyl phthalate at 15 phr concentration since new plasticizer showed excellent properties at 15 phr concentration. This newly synthesized plasticizer was completely fused with PVC and in tensile testing helped in increasing the elongation, which was an indication of the plasticization effect shown by this developed material. Glass transition temperature also decreased with an incorporation of the new plasticizer as compared to virgin PVC.     

Effect of oven aging on polypropylene

Injection-molded tensile bars of unstabilized polypropylene were oven aged at 90°C. After an induction period, tensile elongation decreased catastrophically. During the induction period no evidence of oxidation was observed by infrared reflectance; however, a definite surface etching was noted by electron microscopy. Differential scanning calorimetry measurements indicated that, for samples aged beyond the induction time, oxidative degradation caused a decrease in the melting temperature of polypropylene. Toluene immersion was used to remove selectively material from the surface of tensile bars aged for various times. Using this technique, changes in melting behavior were observed for partially aged polypropylene even prior to the catastrophic decrease in tensile elongation. Similarly, oxidation products and a reduction in molecular weight were detected for the dissolved surface layer during the apparent induction time. Results indicate that molecular weight measurement is the most sensitive indicator of oxidative degradation during the induction period.     

Effect of the wine wastes on the thermal stability,mechanical properties,and biodegradation's rate of poly(3-hydroxybutyrate)

In this work, two different wine derived additives, seeds extracts (Sext) and wine lees (WL), have been tested within poly(3-hydroxybutyrate) (PHB) for different purposes. First, the effect of wine seed polyphenolic extracts (Sext) on the PHB thermal stability has been investigated considering the molecular weight decrease (gel permeation chromatography), the impact on the viscosity (mass flow rate), the thermogravimetric analysis (TGA) curves, and the oxidation induction times. Different stabilizers formulations have been tested and the results have been compared with unstabilized PHB. Subsequently, WL have been mixed in different concentration (10, 20, and 40 phr) within PHB by twin-screw extrusion and the obtained biocomposites have been characterized from a thermal (differential scanning calorimetry and TGA) and mechanical (dynamic mechanical analysis and tensile test) points of view exploiting also the micromechanics models of Voigt, Halpin-Tsai and Pukanszky. Finally, biodegradation tests in soil and in marine water have been carried out for each investigated PHB formulation in order to evaluate the effect of Sext and WL on the microbial degradation.     

Poly(ε-caprolactone)-based additives: Plasticization efficacy and migration resistance

A family of poly(caprolactone) (PCL)-based oligomeric additives was evaluated as plasticizers for poly(vinyl chloride) (PVC). We found that the entire family of additives, which consist of a PCL core, diester linker, and alkyl chain cap, were effective plasticizers that improve migration resistance. The elongation at break and tensile strength of the blends made with the PCL-based additives were comparable to blends prepared with diisononyl phthalate (DINP), a plasticizer typically used industrially, and diheptyl succinate (DHPS), an alternative biodegradable plasticizer. Increasing concentration was found to decrease glass transition temperature (T_g) and increase elongation at break, confirming their role as functional plasticizers. We found that all of the PCL-based plasticizers exhibited significantly reduced leaching into hexanes compared to DINP and DHPS. The PCL-based plasticizers with shorter carbon chain lengths reduced leaching more than those with longer carbon chain lengths.     

Metal‐exchanged clay and zeolite additives as smoke suppressants and fire retardants for poly(vinyl chloride)

Cone calorimetry studies showed that various metal‐exchanged clays and zeolites containing only 3–4% of Cu(II), Cu(I), Zn(II), or Al(III) were effective smoke suppressants and fire retardants for plasticized poly(vinyl chloride). Copper(II)‐Zn(II) and Cu(II)‐Al(III) synergism for smoke and heat reduction was observed with binary blends of the clays, and the effectiveness of the additives was usually improved considerably by heating plasticizer‐additive mixtures under very high shear before combining them with the polymer. Possible mechanisms of action of the additives are described. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Tensile properties,degradation behavior,and water absorption of sago starch plastic films

Sago starch plastic films were prepared by a blending and casting method using various amounts of additives. The additives were glycerol (GLY), polyethylene glycol (PEG), and glutaraldehyde (GLU). Results indicated that the films had an optimum tensile strength of about 2.6 MPa and an optimum elongation at break of 74%. Meanwhile, a GLU content of five parts by weight gave the best tensile properties. Elongation at break of the films increased while tensile strength decreased upon increasing the level of plasticizer (GLY and PEG). The addition of plasticizer also increased the water absorption and soil burial degradation rate. However, the addition of GLU gave opposite results. J. VINYL ADDIT. TECHNOL., 2012. © 2012 Society of Plastics Engineers     

Study on electron‐beam‐irradiated (linear low‐density polyethylene)/(soya powder) blends under outdoor exposure

Linear low‐density polyethylene was blended with soya powder, and the blends were compatibilized with epoxidized natural rubber having 50 mol% of epoxidation. The content of soya powder was varied from 0 to 40 wt%. The blends were irradiated at 30 kGy with an electron beam. Degradation of the irradiated blends was evaluated by exposing the samples to an outdoor environment according to ISO 877.2. The degradation was monitored by changes in the tensile, morphological, and thermal properties, as well as the molecular structure and weight loss. The tensile strength and elongation at break (Eb) of the exposed samples decreased as a function of exposure period. The irradiated blends exhibited higher retention of tensile strength and Eb than nonirradiated blends after 1 year of exposure. The crystallinity of the irradiated blends increased upon exposure, though the nonirradiated blends showed higher crystallinity indicating higher degradability. Weight loss of the irradiated blends showed less change after 6 months of outdoor exposure, but significant change was observed after 1‐year exposure. The molecular weight changes of the irradiated blends exhibited the same trend as weight loss. All the results confirmed that the degradability of the irradiated blends was comparable to that of the nonirradiated blends upon long‐term outdoor exposure. J. VINYL ADDIT. TECHNOL., 2012. © 2012 Society of Plastics Engineers     

Tensile failure of weathered polycarbonate

Weatherability of several UV stabilized and unstabilized grades of LEXAN® polycarbonate (PC) was studied by exposure in a xenon arc lamp weather-o-meter. The tensile properties of thin (0.2 to 0.3 mm) compression molded and thick (3.4 mm) injection molded samples were investigated as a function of exposure time and correlated with the changes in fracture morphology and molecular weight by scanning electron microscopy (SEM) and gel permeation chromatography (GPC). The elongation at failure was the essential mechanical property influenced by exposure. An initial decrease in elongation at failure, followed by a slight increase before the materials turned completely brittle (i.e.; failure without yielding), was correlated with a change in the fracture mechanism starting from the exposed surface of the samples. The initial decrease was caused by penetrating surface cracks, while the later increase in ultimate elongation resulted from the flaking off of the brittle surface layer. The UV stabilized grade remained more ductile, since its molecular weight remains fairly constant up to 1500 h of exposure, while the unstabilized grades decrease in molecular weight continuously from the start of exposure. The useful lifetime of the samples, defined by the complete loss of ductility, is approximately 1500-2000 h of accelerated exposure, which corresponds approximately to 1 year outdoor exposure under Israeli conditions.     

Terpolymers. II. Mechanical properties and transition temperatures of terpolymers of vinyl stearate,vinyl acetate,and vinyl chloride

Vinyl stearate was studied as a major internal plasticizer in terpolymers containing vinyl acetate and vinyl chloride. The terpolymers were prepared by systematically replacing vinyl acetate by close increments of vinyl stearate starting with combinations of vinyl acetate and vinyl chloride, in increments, over all compositions. For comparison of properties, a complete range of copolymers of vinyl stearate and vinyl chloride, as well as mixtures of poly(vinyl chloride) and di-2-ethylhexyl phthalate (DOP) were also made. The external plasticizer was more efficient in reducing the glass temperature than was vinyl stearate. The decline in T_g with weight fraction of plasticizer was linear for the copolymers and terpolymers but concave downward with the liquid diluent. The linear decline was shown to involve mere additivity of the free volume contributed by each side-chain methylene (or methyl) group in both vinyl esters to reducing T_g. The mechanism of the diluent system was more complex. However, the magnitude of the reduction of tensile modulus at a given weight fraction of DOP could be equaled or exceeded by the same amount of vinyl stearate, by increasing the vinyl acetate content of the base copolymer to 40 mole-% or more. Unfortunately, the ultimate strengths and elongations of internally plasticized systems were reduced more than those of the mixtures at comparable compositions. Vinyl stearate was found to markedly retard photolytic degradation compared to both vinyl acetate and the external plasticizer in unstabilized samples having nearly the same thermal treatment. The effect was greater than could be ascribed to dilution by the long alkyl group. The production of a stearoyl radical more stable than the radicals initiating dehydrochlorination is suggested as a possible mechanism.     

Biocomposites developed using water‐plasticized wheat gluten as matrix and jute fibers as reinforcement

Biocomposites developed from wheat gluten using water without any chemicals as plasticizer and jute fibers as reinforcement have much better flexural and tensile properties than similar polypropylene composites reinforced with jute fibers. Wheat gluten is an inexpensive and abundant co‐product derived from renewable resources and is biodegradable but non‐thermoplastic. Previous attempts at developing biocomposites from wheat gluten have used plasticizers such as glycerol or chemical modifications to make gluten thermoplastic. However, plasticizers have a considerably negative effect on the mechanical properties of the composites and chemical modifications make wheat gluten less biodegradable, expensive and/or environmentally unfriendly. In the research reported, we developed composites from wheat gluten using water as a plasticizer without any chemicals. Water plasticizes wheat gluten but evaporates during compression molding and therefore does not affect the mechanical properties of the composites. The effect of composite fabrication conditions on the flexural, tensile and acoustic properties was studied in comparison to polypropylene composites reinforced with jute fibers. Wheat gluten composites had flexural strength (20 MPa), tensile strength (69 MPa) and tensile modulus (7.7 GPa) values approximately twice those of polypropylene composites. Water is an effective plasticizer for wheat gluten and could be used to develop various types of inexpensive and biodegradable wheat gluten‐based thermoplastics. Copyright © 2011 Society of Chemical Industry     

Natural weathering studies of biobased thermoplastic starch from agricultural waste/polypropylene blends

Thermoplastic starch (TPS) obtained from agricultural waste was blended with polypropylene (PP) for natural weathering studies. The agricultural waste material was obtained from seeds and tubers with a starch content of approximately 50%. Commercial‐grade TPS and native tapioca‐based TPS were also prepared for comparison. The biobased TPS/PP extruded sheets were exposed to natural weathering for six months and their deterioration in weight, tensile properties, thermal properties, and relative molecular weight were monitored. SEM micrographs revealed the formation of surface cracking and the presence of microorganisms. FTIR spectrum indicated an increase in the carbonyl index over time as a result of the formation of degradation products. TPS/PP blends made from agricultural waste showed a better resistance to natural weathering compared to the other high starch formulation. The higher starch content in the blend system encouraged the rapid degradation process due to the combined effect of UV radiation with oxidation, moisture, temperature, and microbial attack. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Comparison of carboxylated and maleated polypropylene as reactive compatibilizers in polypropylene/polyamide‐6,6 blends

Using reactive extrusion, polypropylene is functionalized with maleic anhydride and compared on an equimolar basis to polypropylene that is functionalized with an asymmetric, carboxylic acid containing peroxide. The grafting efficiency for the asymmetric peroxide is double that obtained for the maleic anhydride system. Moreover, the asymmetric peroxide yields a functionalized material with minimal molecular weight degradation and desirable mechanical properties, relative to maleic anhydride‐grafted polypropylene. In compatibilized blends of polypropylene and nylon 6,6, the polypropylene that was functionalized with the asymmetric peroxide is found to be an improved compatibilizer compared to that of maleic anhydride‐grafted polypropylene. The differences in mechanical properties of the two different functionalized polypropylene materials and their respective blends are rationalized on the basis of the grafting efficiency, molecular weight degradation during reactive extrusion, and effect of free functional species on the ability to form graft copolymers in compatibilized blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2398–2407, 2001