Closed‐loop recycling of postused garden chairs based on PP using the restabilization technique. I. Evaluation of processing parameters

A remelting–restabilization technique was applied to evaluate the closed‐loop recycling of postused, white pigmented, garden chairs made from CaCO₃‐filled polypropylene (PP). Analysis of the randomly collected postused chairs showed only an insufficient quantity of residual active stabilizers. Different stabilization systems in selected concentrations were employed to investigate the optimum restabilization recipe for eliminating degradation effects during reprocessing. For monitoring the processing stability of the restabilized and nonrestabilized material a multiple extrusion procedure at two different reprocessing temperatures was performed. Furthermore, a repigmentation step was applied to investigate the role of the additional pigment on the processing stability of the recycled product. Finally, mechanical tests were carried out, for studying further the effect of restabilization on the mechanical performance of the recycled material. The results lead to the conclusion that restabilization for quality improvement of postused filled PP chair material during reprocessing is permitting its reuse in the original application. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2472–2485, 2002     

Mechanical recycling of postused high-density polyethylene crates using the restabilization technique. I. Influence of reprocessing

A remelting–restabilization technique was applied for the recycling of postused, yellow-pigmented high-density polyethylene (HDPE) bottle crates. Multiple extrusion cycles procedure, at different reprocessing temperatures, was performed for monitoring the processing stability of the restabilized and nonrestabilized material as reference. In addition, mechanical properties measurements were carried out, to study further the effect of restabilization on the performance of the recycled material. Finally, repigmentation was used to investigate the role of new pigments on the final recycled product. The results illustrate that restabilization of postused crates leads to careful reprocessing without severe degradation, which is an essential prerequisite for reuse in the original application. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1775–1785, 1999     

Mechanical recycling of post‐used HDPE crates using the restabilization technique. II: Influence of artificial weathering

Artificial weathering was applied for about 8000 h to evaluate the light stability of postconsumer high‐density polyethylene (HDPE) material recycled from bottle crates. For recycling the remelting‐restabilization technique was applied. To study the effect of the restabilization, the tensile impact strength was monitored during the artificial weathering exposure. The data were compared with microphotographs of the specimens' surface. Repigmentation was used to evaluate the role of new pigments on the final performance of the recycled material. The repigmented grades were further studied by colorimetric determinations of the color difference (ΔE) during artificial weathering. The results illustrate that the restabilization is mandatory for improving the light stability of the postconsumer crate material, ensuring its re‐use in the original application. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1118–1127, 2000     

Reactive‐extrusion route for the closed‐loop recycling of poly(ethylene terephthalate)

The effectiveness of the reactive extrusion technique was investigated for poly(ethylene terephthalate) to promote the concept of closed‐loop recycling, that is, the reuse of waste material in the initial application. More specifically, a chain‐extender system, consisting of pyromellitic dianhydride, polyol, and a catalyst, was employed, and its efficiency regarding the improvement of the recyclate quality was evaluated. Accordingly, rheological and thermal characterizations were performed and used as criteria of the modification induced in the polymer molecular structure during processing due to the counteracting degradation and chain‐extension reactions. In particular, the molecular weight, related to intrinsic viscosity and melt flow rate measurements, of modified poly(ethylene terephthalate) samples was found to increase with the additive content. Simultaneously, a decrease in the crystallinity was observed, attributed to the branching effect of the chain extender, which restricted the ability of the macromolecules to organize in the crystal structure. Beyond a critical concentration of the additive system, the molecular weight of the treated samples started to decrease again, and this was accompanied by a small increase in the crystallinity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1671–1678, 2007     

Effect of nano‐TiO2 surface modification on polarization characteristics and corona aging performance of polyimide nano‐composites

Using coupling agent isocyanatopropyltriethoxysilane (ICTOS) to modified nano‐TiO_2, the polyimide (PI) with different titanium dioxide (TiO₂) contents (0, 1, 2, 3, 4, and 5 wt %) doped nano‐composites were prepared by sol–gel method (PI/TiO_{2 ICTOS} composites). The effect of ICTOS modification on polarization and time‐to‐breakdown properties of composites were investigated by thermally stimulated depolarization current (TSDC) method, dielectric, and Corona aging measurements. The TSDC spectra show that ICTOS modification enhanced α‐peak intensity and make β‐peak disappear in composites. Relevant trap parameters were calculated by an approximate model, and the results indicate that introduction of ICTOS is effective for the charge carrier traps, activation energy distribution in composites. Corona aging measurement show corona resistance was also sufficient improved in PI/TiO_{2 ICTOS} composites. The changes of activation energy and intensity of traps in composites may be responsible for the corona resistance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45101.     

Performance and structure changes of the aromatic co‐polysulfonamide fibers during thermal‐oxidative aging process

The changes in performance during thermal‐oxidative aging process of the aromatic co‐polysulfonamide (co‐PSA) fibers over a broad temperature range from 250 °C to 320 °C have been investigated. In addition, the mechanism of thermal‐oxidative aging process has been studied by using structural information obtained from the fibers at varying length scales. The results showed that a significant reduction in tensile strength was observed compared with that of initial modulus during aging process. Macroscopically, thermal‐oxidative aging mainly causes color changes of fibers and thermally induced macro defects begin to appear only at 320 °C for 100 h. On a micro level, the crystal structure of fibers remained stable and did not show significant changes expect that aging at 320 °C. In addition, thermo‐degradation as well as crosslinking has been observed primarily in amorphous region. With the increase of temperature and time duration, the crosslinking became more dominant and crosslinking density increases. Correspondingly, the fibril length decreases due to degradation and then increases due to the formation of crosslinked structures within the fibers. The results suggest that molecular degradation is the main cause of strength loss and the formation of crosslinking structure within the fibers contributes to the retention of modulus and improvement of creep resistance. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44078.     

Modeling the role of stabilizing additives during melt recycling of high‐density polyethylene

Post‐use high‐density polyethylene, almost devoid of any stabilizing agents, was restabilized in various degrees and subjected to multiple extrusion cycles at different reprocessing temperatures for assessing its chemical stability. The process‐induced material degradation was attributed primarily to long‐chain branching caused by crosslinking. It was monitored by an increase in viscosity and evaluated on the basis of an approximate expression derived using fundamental principles of macromolecular rheology. It was determined that long‐chain branching increases with temperature and the extent of processing, while decreasing with the amount of restabilizing agent added. A simple model was developed to quantitatively describe the progress of the chemical change by relating it to key material and operational variables. Besides constituting a useful method of monitoring and controlling polymer modification during processing, this model suggests ways of optimizing stabilization according to the particular processing and product requirements. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2207–2217, 2001     

Cure characteristics and physical properties of ground‐rubber‐filled natural rubber vulcanizates: Effects of the curing systems of the ground rubber and rubber matrix

Recycling discarded rubber is important for both environmental and economic reasons. One of the most attractive methods of recycling rubber waste is to use ground rubber (GR) as a compounding ingredient or as a replacement for raw polymers. In this study, ground natural rubber was prepared with different curing systems and compounded into the parent compounds. The cure behaviors and physical properties of the GR‐filled vulcanizates were investigated, and they were largely affected by the curing systems of the rubber matrix and GR. GR‐filled vulcanizates with GR and the rubber matrix, having a conventional curing system, showed the largest changes in the cure characteristics. The greatest decrease in the physical properties was observed for peroxide‐cured‐GR‐filled vulcanizates. The addition of GR decreased the crosslink density of the GR‐filled vulcanizates. This was thought to be the main reason for the reduction of the mechanical properties of the GR‐filled vulcanizates. However, the adhesion between the GR and rubber matrix may also have caused the differences in the physical properties of the GR‐filled vulcanizates with respect to the curing systems of the rubber matrix and GR. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Smart polymer recycling: Synthesis of novel rigid polyurethanes using phosphorus‐containing oligomers formed by controlled degradation of microporous polyurethane elastomer

This article describes a new approach for the recycling of microporous polyurethane elastomers by Tris(1‐methyl‐2‐chloroethyl) phosphate‐induced degradation. The phosphorus‐containing degradation products formed are transformed into reactive intermediates by reaction with propylene oxide and are used for the preparation of rigid polyurethane foams. These new phosphorus‐containing materials have higher density and better mechanical properties compared to the standard rigid polyurethane foams. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Miniemulsions using static mixers: Part 2. Co‐emulsification and composite materials using SMX static mixers

A 50:50 mixture of methylmethacrylate (MMA) and butyl acrylate was emulsified, then polymerised using different static mixers. It was shown that the emulsification behaviour was very different from that observed for MMA alone under similar conditions. It was shown that the hydrophobicity of the monomers had a strong influence on the droplet size and stability. It was also shown that the amount of work done on the emulsion is important for obtaining polymerisable droplets, and that monomer systems that are difficult to miniemulsify with a low energy system can in fact be made to form stable emulsions simply by changing the emulsification conditions. Finally, it was shown that when the miniemulsification conditions are correctly chosen, it is possible to generate miniemulsion dispersions containing silica that can be successfully polymerised to produce silica/polyacrylic nanocomposites.     

Silica‐Supported Zirconium Complexes and their Polyoligosilsesquioxane Analogues in the Transesterification of Acrylates: Part 2. Activity,Recycling and Regeneration

The catalytic activity of both supported and soluble molecular zirconium complexes was studied in the transesterification reaction of ethyl acrylate by butanol. Two series of catalysts were employed: three well defined silica‐supported acetylacetonate and n‐butoxy zirconium(IV) complexes linked to the surface by one or three siloxane bonds, (SiO)Zr(acac)₃ ( 1 ) (SiO)₃Zr(acac) ( 2 ) and (SiO)₃Zr(O‐n‐Bu) ( 3 ), and their soluble polyoligosilsesquioxy analogues (c‐C₅H₉)₇Si₈O₁₂(CH₃)₂Zr(acac)₃ ( 1′ ), (c‐C₅H₉)₇Si₇O₁₂Zr(acac) ( 2′ ), and (c‐C₅H₉)₇Si₇O₁₂Zr(O‐n‐Bu) (3′ ). The reactivity of these complexes were compared to relevant molecular catalysts [zirconium tetraacetylacetonate, Zr(acac)₄ and zirconium tetra‐n‐butoxide, Zr(O‐n‐Bu)₄]. Strong activity relationships between the silica‐supported complexes and their polyoligosilsesquioxane analogues were established. Acetylacetonate complexes were found to be far superior to alkoxide complexes. The monopodal complexes 1 and 1′ were found to be the most active in their respective series. Studies on the recycling of the heterogeneous catalysts showed significant degradation of activity for the acetylacetonate complexes ( 1 and 2 ) but not for the less active tripodal alkoxide catalyst, 3 . Two factors are thought to contribute to the deactivation of catalyst: the lixivation of zirconium by cleavage of surface siloxide bonds and exchange reactions between acetylacetonate ligands and alcohols in the substrate/product solution. It was shown that the addition of acetylacetone to the low activity catalyst Zr(O‐n‐Bu)₄ produced a system that was as active as Zr(acac)₄. The applicability of ligand addition to heterogeneous systems was then studied. The addition of acetylacetone to the low activity solid catalyst 3 produced a highly active catalyst and the addition of a stoichiometric quantity of acetylacetone at each successive batch catalytic run greatly reduced catalyst deactivation for the highly active catalyst 1 .     

Research on the tribological performance of Cr2O3 filled with bronze‐based PTFE composites

Enhancement of the wear resistance of bronze‐filled polytetrafluoroethylene (PTFE) composites has been achieved using various fillers, for example, chromic oxide (Cr₂O₃), molybdenum disulfide (MoS₂), graphite, and nanometer aluminum oxide (n‐Al₂O₃), in the present study. The wear resistance was evaluated by a block‐on‐ring wear tester, and the effects of fillers on the wear resistance as well as the mechanism were investigated. The wear rate for the composite where the recipe containing 59% PTFE + 40% bronze + 1% Cr₂O₃ was 0.5 × 10^?5 mm^?3/N m and for the composite in the recipe containing 60% PTFE + 40% bronze was 4.2 × 10^?5 mm^?3/N m, which meant that that Cr₂O₃ increased the wear resistance by approximately 10 times. The differential scanning calorimetry measure analysis showed that Cr₂O₃ had a positive effect on the crystallization of PTFE; the crystallinity of PTFE composites increased from 45% to 52%, which exhibited improved wear resistance. Wear testing and scanning electron microscope analysis had shown that Cr₂O₃ had a positive effect on the formation of transfer film and keeping it stable to exhibit improved wear resistance. X‐ray photoelectron spectroscopy results also showed that Cr₂O₃ was effective in tribochemical reactions during sliding against stainless ring; these maybe responsible for forming transfer film and lowering wear rate of composite. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41117.     

Evaluation of methods for verifying the performance of color‐measuring instruments. Part II: Inter‐instrument reproducibility

Part I described an experiment in which the repeatability of a number of common, commercially available spectrocolorimeters was compared using ASTM procedures. ASTM E2214‐02 Standard Practice for Specifying and Verifying the Performance of Color‐Measuring Instruments is intended to standardize the terminology and procedures used to evaluate color measuring instruments. In this article, we develop reproducibility results from a medium‐term study of 10 commercial spectrocolorimeters. The comparisons are presented so as to contrast between the traditional color difference based specifications found in the historical literature and in manufacturer's literature and the more complex multidimensional methods specified in E2214. Instrument to instrument contrasts are reported as well as tests of agreement across a set of instruments as a whole. The results confirm common understandings. Hemispherical diffuse instruments exhibit a higher level of inter‐instrument agreement than do bidirectional (45:0) instruments. The results also provide support for a surprising conclusion about the statistical significance of the minor differences in both inter‐instrument agreement and inter‐model agreement for a single manufacturer. Some speculations on the impact of these conclusions to the development of future comparisons of spectrocolorimeters are given. © 2007 Wiley Periodicals, Inc. Col Res Appl, 32, 176–294, 2007     

Evaluation of methods for verifying the performance of color‐measuring instruments. Part I: Repeatability

A recent ASTM specification (ASTM E2214‐02) was created to standardize the terminology and procedures used to evaluate color measuring instruments. This specification addresses the need for uniformity among the manufacturers of such instruments when quantifying the performance of their products. The scope of E2214 is necessarily large, covering the procedures required to compare instruments for a variety of metrics, all of which are important to their overall performance. In this work, we will focus on one aspect of the instrument evaluation: repeatability performance. We will present repeatability results from a long‐term study of twelve commercial spectrophotometers. Comparisons will be made between traditional color difference metrics and the more complex multidimensional methods specified in E2214. © 2007 Wiley Periodicals, Inc. Col Res Appl, 32, 166–175, 2007     

Effects of temperature and strain rate on the tensile behavior of unfilled and talc‐filled polypropylene. Part I: Experiments

The tensile behavior of unfilled and 40 w% talc‐filled polypropylene has been determined at four different temperatures (21.5, 50, 75 and 100°C) and three different strain rates (0.05, 0.5 and 5 min^?1). Experimental results showed that both unfilled and talc‐filled polypropylenes were sensitive to strain rate and temperature. Stressstrain curves of both materials were nonlinear even at relatively low strains. The addition of talc to polypropylene increased the elastic modulus, but the yield strength and yield strain were reduced. The temperature and strain rate sensitivities of these materials were also different. An energy‐activated, rate sensitive Eyring equation was used to predict the yield strength of both materials. It is shown that both activation volume and activation of energy increased with the addition of talc in polypropylene.     

Preparation of silica‐filled poly(2‐hydroxymethyl methacrylate) nanocomposites cured by photoirradiation during the sol–gel process

The sol–gel process was used to prepare a photosensitive inorganic–organic composite, silica/poly(2‐hydroxymethyl methacrylate). Its nanoscale morphology was observed with field emission scanning electron microscopy at high magnifications (e.g., 160,000×). The size of the particles in the nanocomposite synthesized under various preparation conditions fell in the range of 20–50 nm. The effects of the pH, reactant composition, and solvent content in the reaction mixture on the thermal and mechanical properties of the nanocomposite were studied with thermogravimetric analysis, dynamic mechanical analysis, and thermomechanical analysis. The thermal stability of the synthesized nanocomposite could generally be improved by an increase in the molar ratio of the inorganic component, a reduction in the reaction pH, or an increase in the solvent content. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1927–1935, 2004     

Effects of temperature and strain rate on the tensile behavior of unfilled and talc‐filled polypropylene. Part II: Constitutive equation

Based on the experimental results presented in Part I of this research, a three parameter nonlinear constitutive model has been proposed to describe the strain rate and temperature dependent tensile behaviors of unfilled and talc‐filled polypropylene. One of the parameters is the elastic modulus. The other two parameters in this model are a strain exponent, m, and a compliance factor, β. Their relationships to strain rate and temperature are obtained from the experimental results. The simulated stress‐strain curves from the model are in good agreement with the test data. The analysis of the model shows that the strain exponent m, which controls the strain softening (or hardening) effect of the material, is not only strain rate independent, but also temperature independent. The compliance parameter, β, which controls the flow stress level of the material, on the other hand, varies with both strain rate as well as temperature. Results also show that the addition of talc filler in polypropylene reduces the strain exponent m, and increase the compliance parameter, β, which reduces the flow stress level of talc‐filled polypropylene to lower than that of unfilled polypropylene.     

Compatibilization of SBR/NBR blends using chemically modified styrene‐co‐butadiene rubber Part 2. Effect of compatibilizer loading

The present work focuses on the compatibization of styrene‐co‐butadiene rubber (SBR)/acrylonitrile‐co‐butadiene rubber (NBR) blends with dichlorocarbene modified styrene‐co‐butadiene rubber (DCSBR) as a function of concentration of compatibilizer and composition of the blend. FTIR studies, differential scanning calorimetry and dynamic mechanical analysis reveal molecular level miscibility in the blends in the presence of compatibilizer. The formation of interfacial bonding is assessed by analysis of swelling behaviour, cure characteristics, stress–strain data and mechanical properties. These studies show that the compatibilizing action of DCSBR becomes more prominent as the proportion of NBR in the blend increases. The resistance of the vulcanizate towards thermal and oil ageing improved with compatibilization. The change in technological properties is correlated with the crosslink density of the blends assessed from swelling and stress–strain data. © 2001 Society of Chemical Industry     

Reaction kinetics of 2‐((2‐aminoethyl) amino) ethanol in aqueous and non‐aqueous solutions using the stopped‐flow technique

Observed pseudo‐first‐order rate constants (k_o) for the reaction between CO₂ and 2‐((2‐aminoethyl) amino) ethanol (AEEA) were measured using the stopped‐flow technique in an aqueous system at 298, 303, 308 and 313 K, and in non‐aqueous systems of methanol and ethanol at 293, 298, 303 and 308 K. Alkanolamine concentrations ranged from 9.93 to 80.29 mol m^?3 for the aqueous system, 29.99–88.3 mol m^?3 for methanol and 44.17–99.28 mol m^?3 for ethanol. Experimentally obtained rate constants were correlated with two mechanisms. For both the aqueous‐ and non‐aqueous‐AEEA systems, the zwitterion mechanism with a fast deprotonation step correlated the data well as assessed by the reported statistical analysis. As expected, the reaction rate of CO₂ in the aqueous‐AEEA system was found to be much faster than in methanol or ethanol. Compared to other promising amines and diamines studied using the stopped‐flow apparatus, the pseudo‐first‐order reaction rate constants were found to obey the following order: PZ (cyclic‐diamine) > EDA (diamine) > AEEA (diamine) > 3‐AP (primary amine) > MEA (primary amine) > EEA (primary amine) > MO (cyclic‐amine). The reaction rate constant of CO₂ in aqueous‐AEEA was double that in aqueous‐MEA, and the difference increased with an increase in concentration. All reaction orders were practically unity. With a higher capacity for carbon dioxide and a higher reaction rate, AEEA could have been a good substitute to MEA if not for its high thermal degradation. AEEA kinetic behaviour is still of interest as a degradation product of MEA. © 2012 Canadian Society for Chemical Engineering     

Effect of carboxylic acids on 2‐bisbenzothiazole‐2,2′‐disulfide‐ and tetramethylthiuram disulfide‐accelerated sulfur vulcanization. II. Vulcanization of polyisoprene in the absence of ZnO

Polyisoprene was vulcanized by 2‐bisbenzothiazole‐2,2′‐disulfide (MBTS)/sulfur and tetramethylthiuram disulfide (TMTD)/sulfur in the absence and presence of benzoic and stearic acids. It was found that the crosslink density of MBTS vulcanizates is halved by the addition of carboxylic acids and this can be explained in terms of the attack of the acids on the accelerator polysulfides. TMTD polysulfides are more reactive toward polyisoprene than are MBTS polysulfides, and their addition to the polymer chain occurs before significant attack by the carboxylic acids can reduce the polysulfide concentration. Consequently, the acids have little effect on the crosslink density of TMTD vulcanizates. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1007–1012, 1999