Compatibility of HDPE/postconsumer HDPE blends using compatibilizing agents

Mechanical properties, molecular weight, X‐ray diffraction, and differential scanning calorimetry (DSC) characterization of blends of virgin high‐density polyethylene (HDPE) with two types of recycled material were investigated. The recycled came from urban plastic waste; one kind was only washed and grounded and the other was extruded and pelletized to remove most of contaminant particles. Starting with the 30/70 virgin/grounded recycled and 50/50 virgin/pelletized recycled blends the recycled content was increased in both blends and compatibilizing agents were used to increase the blend performance. A mixture of phenolic antioxidants and phosphite costabilizers under the name of Recycloblend?, ethylene vinyl acetate (EVA) copolymer, low‐density polyethylene (LDPE), and linear low density polyethylene (LLDPE) were used as compatibilizers. The effect of these additives and the recycled content on the performance of extrusion blow‐molded bottles was determined. The results suggest that blends of virgin/grounded recycled and virgin/pelletized recycled HDPE, in general, were not significantly different among each other and both had a quite similar behavior than the virgin HDPE when compatibilizing agents were used. The addition of compatibilizing agents yielded a material with properties similar to those for the virgin HDPE, helping to reduce the effect of polymers degradation on the rheological and mechanical behavior, with Recycloblend and LLDPE being the most effective for the blends with grounded recycled material, and LLDPE y EVA, for the blends with pelletized recycled. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3696–3706, 2006     

Crystallization and chemi-crystallization of recycled photo-degraded polypropylene

Injection moulded bars have been made from virgin polypropylene and from blends containing recycled photo-degraded polypropylene, then subjected to further ultraviolet (UV) exposure. Crystallinity measurements have been made at different depths from the exposed surface using X-ray diffraction and differential scanning calorimetry. Strong evidence for chemi-crystallization is provided for the photo-degraded samples. The crystallinity results are interpreted in terms of molecular scission and photo-initiated molecular defects. Scission leads to greater crystallizability and accounts for the observed chemi-crystallization. Molecular defects inhibit crystallization and eventually limit chemi-crystallization, as observed with a blend containing 75% virgin material and 25% recycled photo-degraded polymer after further UV exposure.     

Recycling PET beverage bottles and improving properties

Recycling PET from bottles has been carried out by three different extrusion methods. Under optimized processing conditions, a virgin poly(ethylene terephthalate (PET), recycled PET and a mixture of virgin and recycled PET, with and without the modifier polypropylene functionalized with maleic anhydride [PP‐graft‐MA]), were processed. Different methods were used to characterize the processed products. The results showed that the intrinsic viscosity and molecular weight decreased as the blend ratio of recycled PET was increased. This was due to thermal exposure as well as shear degradation of recycled PET. Thermal cycles of the processes used for recycling PET and its blending specimens with virgin PET show the importance of the thermal treatment in the improvement of mechanical strength and increased crystallinity. Nevertheless, the properties of the functionalized blends were improved. This behaviour is attributed to a series of chemical and physico‐chemical interactions taking place between the two components. Copyright © 2004 Society of Chemical Industry     

Headspace solid‐phase microextraction with gas chromatography/mass spectrometry reveals a correlation between the degradation product pattern and changes in the mechanical properties during the thermooxidation of in‐plant recycled polyamide 6,6

The increased susceptibility of in‐plant recycled polyamide 6,6 toward thermooxidation was shown by headspace solid‐phase microextraction with gas chromatography/mass spectrometry (HS‐SPME/GC‐MS), tensile testing, differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR). A correlation between the deterioration in mechanical properties and the formation of degradation products due to thermooxidation was found, and the most prominent decrease in mechanical properties coincided with the largest increase in the abundance of degradation products. The recycled materials had a shorter induction period toward oxidation, and their mechanical properties deteriorated faster than the mechanical properties of virgin material. The same trend was observed with HS‐SPME/GC‐MS because degradation products were found for recycled materials after oxidation times shorter than those for virgin material. Furthermore, larger amounts of degradation products were formed in the recycled materials. The high sensitivity of HS‐SPME/GC‐MS as an analytical tool was demonstrated because it was able to detect changes caused by oxidation considerably earlier than the other methods. Unlike DSC and FTIR, it could also show differences between samples recycled for different times. Four groups of degradation products—cyclic imides, pyridines, chain fragments, and cyclopentanones—were identified in thermooxidized polyamide 6,6. After 1200 h of thermooxidation, 1‐pentyl‐2,5‐pyrrolidinedione was the most abundant degradation product. Approximately four times more 1‐pentyl‐2,5‐pyrrolidinedione was formed in polyamide recycled three times than in virgin polyamide. Pyridines and chain fragments behaved toward oxidation and repeated processing like cyclic imides; that is, their amounts increased during oxidation, and larger amounts were formed in recycled materials than in virgin material. The cyclopentanone derivatives were present already in unaged material, and their amounts decreased during oxidation. Cyclopentanones were not formed because of the thermooxidation of polyamide 6,6. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3396–3407, 2002     

Polymeric alloys of poly(vinylpyrrolidone) with a macrocyclic polyether–polyamide

High molecular weight polyamide (PC-6) with macrocyclic polyetheral rings incorporated into the polymeric backbone was synthesized by a modified interfacial polycondensation of isophthaloyl chloride with diamino-dibenzo-18-crown-6. The high molecular weight polymer is a good film-forming material and forms homogeneous blends with poly(vinylpyrrolidone) (PVP). Scanning electron microscopy did not reveal any heterogeneity in such blends. The water-soluble PVP is not leached out from the blends even after a prolonged storage in water. Excellent mechanical properties of PC-6 were not adversely affected by blending it with PVP. The thermomechanical analysis and differential scanning calorimetry of the blends showed a single transition in lieu of those of the two components. PVP was also found to exert a stabilizing effect on the polyamide. The blends have been found to be thermally more stable than their components.     

Reprocessing of thermoplastics. II. Polycarbonate

The effect of recycling on the properties of injection molded polycarbonate was investigated. One unreinforced and two glass-reinforced grades were studied. Fiber degradation was distinguished from molecular scission by spiral flow measurements and molecular weight analysis. During the first cycles the average fiber length was significantly reduced, but at later stages it approached an equilibrium. The number of scission per original polymer molecule increased linearly with the number of recycles for all systems studied, but the degradation reaction did not follow random scission kinetics. The glass reinforced grades exhibited degradation rates which were at least twice as high as that of an unreinforced polymer. This discrepancy was most probably the result of a more extensive viscous heating in the glass-reinforced systems. The decrease in molecular weight as well as in fiber length greatly affected the impact strength of the material. The effect of processing temperature on polymer degradation during recycling was evaluated. The fraction of virgin material that has to be added to the regrind to maintain a certain property level was determined. On a 90 percent property level, an icrease in melt temperature by 1°C corresponded to an increase of 1 percent in the required amount of virgin material. Aging tests indicated that there was no significant difference in degradation rate between recycled and virgin material, although the former certainly exhibited lower absolute values of the measured property (impact strength).     

Selected physical characteristics of polystyrene/high density polyethylene composites prepared from virgin and recycled materials

Mixtures of polystyrene and high density polyethylene were injection molded from recycled and virgin polymers to generate cocontinuous structures. The mechanical properties of these blends were evaluated to assess their conformance to rule of mixtures behavior in general and to identify areas of synergy or incompatibility in specific. Flexural and tensile data for recycled blends showed that generally the properties are not additive, except in a cocontinuous region of composition near 35/65 PS/HDPE that has been identified previously for recycled materials. Analysis of crystallinity in the HDPE phase of these blends by differential scanning calorimetry indicates a marked reduction in the level of HDPE crystallinity at the 35/65 PS/HDPE composition. Similar blends of virgin PS/HDPE polymer do not show the differing regions of incompatibility and synergy illustrated by the recycled materials, but rather show approximate conformance to the rule of mixtures. Furthermore, the virgin blends show virtually no crystallinity suppression and a more pronounced T_g shift in the polystyrene compared to recycled materials. Detailed characterization of the recycled materials in terms of polymer and particulate impurities should improve understanding of these differences and perhaps provide direction for obtaining enhanced synergistic behavior in virgin polymer blends. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Blends of poly(ethylene oxide) samples of different molecular weights: thermal and mechanical properties

Differential scanning calorimetry and mechanical measurements have been performed on binary poly(ethylene oxide) blends of different molecular weight samples. Some thermodynamic and mechanical properties, such as the melting point and the ultimate stress and strain are strongly affected by blend composition. The enthalpy of fusion and the Young's modulus, however, vary only slightly over the entire range of composition. Also the time for dissolution in water, at two different temperatures, has been measured on blends made from the lowest and the highest molecular weight components.The results indicate that by blending two different molecular weight samples, even of the same polymer, it is possible to influence the physical properties of the relative blends, so obtaining improvements of technological importance.     

Blends of thermoplastic polyurethanes and polyamide 12: Structure,molecular interactions,relaxation, and mechanical properties

Studies were done to understand the effects of polyamide 12 (PA 12) incorporation on microphase separation (microsegregation) in thermoplastic polyurethanes (TPU) based on oligoether (polytetramethylene oxide, molecular weight, 1000) and oligoester (polyethylene butylene glycol adipate, molecular weight, 2000), and relaxation transitions, compatibility, and molecular interaction energy in polymer blends. It was learned that the addition of PA 12 caused partial degradation of the domain structure in the oligoester‐containing polyurethane, whereas interaction of hard blocks in the oligoether‐containing polyurethane increased. Analyzing compatibility and interphase interactions in blends is possible in the frame of the quantum theory of relaxation processes. Also, interferences of the components on characteristic temperatures of relaxation transitions were studied. Partial compatibility was detected between PA 12 and the soft block of oligoether‐based TPU over the whole range of components concentrations tested. For oligoester‐based TPU, partial compatibility was observed only at low polyamide concentrations (up to 20 wt %). Effects of a polyurethane phase on PA 12 crystallization in the blends along with the pattern of concentration—mechanical properties dependencies are discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1054–1070, 1999     

Ultraviolet stability of polyimides and polyamide–imides

The ultraviolet stability of polyimides and polyamide–imides was determined in both a wet and dry environment. Films have been exposed to these environments for 3000 and 6000 hr, respectively. The polymers are not stable to UV radiation (2900–4000 Å); serious deterioration of the mechanical properties occurs under both wet and dry conditions with the former giving rise to greater damage. The polyamide–imide polymer is more unstable to UV radiation than the two polyimides evaluated; however, it is more resistant to hydrolysis as indicated from rate data obtained from a kinetic analysis of the mechanical property degradation curves. The electrical properties of the polymers are relatively unaffected in the dry environment but begin to deteriorate as the polymer becomes brittle. In the wet environment these properties begin to deteriorate more rapidly. Dissipation factor and dielectric strength are the properties most affected.     

Influence of Recycled ABS Added to Virgin Polymers on the Physical,Mechanical Properties and Molding Characteristics

Reuse of recycled polymers is steadily increasing. In this study, two different ABS virgin materials are considered. Then, blends of varying proportions of ABS recycled resins (0–50%), obtained from the gate and runner materials of products, was added to virgin resin to investigate the effect of various compositions of virgin ABS and recycled polymers on the physical and mechanical properties of the final blend. Three different rib and closure organization of boss of the reinforcement structures were designed and injection molded under blends of varying proportions of the ABS recycled resins to do the torsion test by Air-Torsion tools. In addition, molding characteristics were also examined. The results show that there is no obvious effect of recycled ABS percentage (by weight) on the tensile strength, elongation at yield, flexural strength, flexural modulus, and impact strength. However, the torsion strength for rib and closure organization of boss of the reinforcement structures decrease with increasing recycled ABS weight percentage. On the other hand, hardness, glass transition temperature, and melting flow index of recycled ABS increase with as the percentage (by weight) of recycled material increase. The impact strength was found to vary with the recycled ABS loading. The injection pressure decreases with increasing the content of recycled resin under some specified molding conditions.     

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     

Recycling of blends of acrylonitrile–butadiene–styrene (ABS) and polyamide

The aim of this work is to evaluate routes to upgrade recycled engineering plastics, especially mixed plastics with acrylonitrile–butadiene–styrene copolymers (ABS) as the major component. A core‐shell impact modifier was successfully used to improve the impact strength of blends of ABS and ABS/polycarbonate (PC) blends recycled from the automotive industry. However, the presence of other immiscible components like polyamide (PA), even in small amounts, can lead to a deterioration in the overall properties of the blends. A styrene–maleic anhydride (SMA) copolymer and other commercial polymer blends were used to promote the compatibilization of ABS and PA. The core‐shell impact modifier was again found to be an efficient additive with regard to the impact strength of the compatibilized ABS/PA blends. The results obtained with fresh material blends were quite promising. However, in blends of recycled ABS and glass‐fiber‐reinforced PA, the impact strength did not exhibit the desired behavior. The presence of poorly bonded glass fibers in the blend matrix was the probable reason for the poor impact strength compared with that of a blend of recycled ABS and mineral‐filled PA. Although functionalized triblock rubbers (SEBS–MA) can substantially enhance the impact strength of PA, they did not improve the impact strength of ABS/PA blends because the miscibility with ABS is poor. The possibilities of using commercial polymer blends to compatibilize otherwise incompatible polymer mixtures were also explored giving promising results. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2535–2543, 2002     

Continuous ultrasonic devulcanization of unfilled butadiene rubber

The devulcanization of sulfur‐cured unfilled butadiene rubber (BR) with a grooved‐barrel ultrasonic reactor under various processing conditions was carried out. The experiments indicated that BR had a narrow devulcanization window. Outside this window, significant degradation or no devulcanization occurred. Gel permeation chromatography (GPC) measurements were carried out with the sol part of virgin and devulcanized samples to study the breakdown of the polymeric chains. The GPC data showed a significant molecular weight reduction and a broadening of the molecular weight distribution upon devulcanization, indicating that the devulcanization and degradation of BR occurred simultaneously. The rheological properties showed that devulcanized BR was more elastic than the virgin gum. The vulcanizates of the blends of virgin and devulcanized BR showed a considerable enhancement of the mechanical properties. The thermal behaviors of the virgin and devulcanized BR were found to be different. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1166–1174, 2004     

Mechanical properties of composites from sawdust and recycled plastics

Mechanical properties of wood plastic composites (WPCs) manufactured from sawdust and virgin and/or recycled plastics, namely high density polyethylene (HDPE) and polypropylene (PP), were studied. Sawdust was prepared from beech industrial sawdust by screening to the desired particle size and was mixed with different virgin or recycled plastics at 50% by weight fiber loading. The mixed materials were then compression molded into panels. Flexural and tensile properties and impact strength of the manufactured WPCs were determined according to the relevant standard specifications. Although composites containing PP (virgin and recycled) exhibited higher stiffness and strength than those made from HDPE (virgin and recycled), they had lower unnotched impact strengths. Mechanical properties of specimens containing recycled plastics (HDPE and PP) were statistically similar and comparable to those of composites made from virgin plastics. This was considered as a possibility to expand the use of recycled plastics in the manufacture of WPCs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3641–3645, 2006     

Pure component recovery from polyamide 6/6 6 mixtures by selective dissolution and reprecipitation

A selective dissolution/reprecipitation technique was applied for the effective recovery of Polyamide 6 (PA 6) and Polyamide 6 6 (PA 6 6) from their mixtures. The proposed process comprises mainly selective polyamide dissolution in an appropriate solvent at a specific temperature, reprecipitation of the polymer from the solution by addition of a nonsolvent, washing, and drying. A model mixture of virgin PA 6 and PA 6 6 pellets was initially tried, whereas in a following stage the selective dissolution technique was applied for the recovery of a PA‐copolymer layer from a three‐layered bottle end product also containing HDPE and EVA. End‐group analysis, dilute solution viscometry, and differential scanning calorimetry were used to assess the molecular weight preservation and crystallizability of the recycled polyamides. The recycled materials demonstrated excellent retention of the properties studied, although in the copolymer case, due to hydrolysis, a molecular weight decrease was detected, accompanied with a slight compositional shift, favoring the PA6 6 presence in the final product. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1924–1930, 2002     

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     

Rheological and mechanical properties of recycled polypropylene

In order to verify the possibility of manufacturing good quality articles by recycled polypropylene (PP), a study on the effect of many recycling operations on the rheological and mechanical properties of PP was conducted. The amount of degradation occurring during the reprocessing was estimated in the melt state by means of rheological measurements and the results obtained were correlated with the weight average molecular weight M_w and the molecular weight distribution MWD. Since the properties in the solid state are strictly dependent upon the molecular structure parameters and the morphology, mechanical properties were checked on films produced from virgin and recycled PP with a cast technology. Moreover, in order to estimate the effect of film composition and of the number of reprocessings on the final properties of the manufactured articles, blend films having different percentages of PP recycled several times and virgin PP were prepared.     

On a contribution to study some mechanical properties of WEEE recycled polymer blends

This research deals with the study of acrylonitrile-butadiene-styrene/polycarbonate (ABS/PC) totally derived from wastes of electrical and electronic equipment (WEEE). The aim of this study is to investigate the macroscopic use properties of 100% recycled polymers and compare them with the virgin materials. First, a preliminary work of sorting and characterization of the wastes was necessary to identify the predominant polymer components in the lots. Then, four compositions of blends (ABS/PC) were performed at laboratory using the twin-screw extruder and injection techniques. Next, a series of experimental tests were carried out to investigate the morphology of the blends, their mechanical and thermo-mechanical behavior. The experimental results highlighted the synergistic effect by blending ABS and PC wastes. In addition, the comparison with the virgin mixtures has shown a decrease in the mechanical properties of the waste blends, however, the mechanical behavior is still ductile and the blends stiffness was enhanced.     

Processability,rheology, and thermal,mechanical, and morphological properties of postconsumer poly(vinyl chloride) bottles and cables

The processability, rheology, and thermal, mechanical, and morphological properties of three different commercial poly(vinyl chloride) (PVC) compounds blended with postconsumer PVC bottles and PVC cables were examined with respect to the recycled PVC content. The addition of PVC bottle recyclates [recycled bottles (RBs)] into virgin PVC bottle (VB) and virgin PVC pipe (VP) compounds caused a progressive reduction in the average torque. No thermal degradation or color change in the RB‐blended PVC compounds used was detected through carbonyl and polyene indices from IR analysis. The rheological properties for VP compounds were more sensitive to RB addition than those of VB compounds. The extrudate swell ratio did not change with the RB content. The decomposition temperature for the VB and VP compounds increased at 60–80% RB, whereas the glass‐transition temperature was unaffected by the RB loading. The 20 and 80 wt % RB loadings were recommended for the VB and VP compounds, respectively, for the optimum impact strength, the blends showing ductile fracture with a continuous phase. At the optimum impact and tensile properties, introducing RB recyclates into the VB compounds gave better results than the VP compounds. The hardness and density of the VB and VP compounds did not change with the RB content. The RB property change was comparatively faster than that of recycled PVC pipes. Adding the PVC cable recyclate [recycled cable (RC)] to virgin PVC cable (VC) had no obvious effect on the torque value of the RC/VC blends. The decomposition temperatures of the RC/VC blends stabilized at 20–60% RC and tended to decrease at 80% RC. The ultimate tensile stress was improved by the addition of the RC compounds, whereas the hardness and density of the VC compounds were unaffected by the RC content. It was concluded that the optimum concentrations of PVC recyclates to be added to virgin PVC compounds were different from one property to another and also depended on the type of virgin PVC grade used. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2738–2748, 2003