Recycling of roofing membrane rubber by ultrasonic devulcanization

The recycling of vulcanizates based on EPDM roofing membrane rubber using a new ultrasonic devulcanization reactor with a grooved barrel was carried out. This reactor provided continuous devulcanization at an output as high as 2.52 g/s. Die pressure and ultrasonic power consumption were measured as a function of processing conditions. The mechanical properties of virgin vulcanized and revulcanized roofing membranes were measured. Tensile strength of the revulcanized rubber was found to be similar to that of the virgin vulcanizate. Gel fraction, crosslink density, and dynamic properties of the virgin vulcanizate, the ultrasonically devulcanized rubber, and the revulcanized rubber were determined. Also, dynamic properties and the cure behavior of the virgin compound and of the devulcanized roofing membrane were investigated. All these properties were found to be dependent on processing conditions during devulcanization. The thermal stability of the virgin compound, virgin vulcanizate, and devulcanized and revulcanized rubbers were studied by means of TGA. It was found that the thermal stability of all the vulcanizates in air and nitrogen environments remained practically intact, while that of devulcanized rubber in air environment was a function of processing conditions.     

Continuous ultrasonic devulcanization of carbon black‐filled NR vulcanizates

The continuous ultrasonic devulcanization of natural rubber (NR) filled with various concentrations of carbon black (CB) indicated a minimum of crosslink density and gel fraction at an intermediate amplitude, which is independent of CB content. An attempt was made to improve the efficiency of devulcanization by use of various chemicals (1,3 Diphenylguanidine, 2‐Mercaptobenzothiazole, Thianaphthene). However, these experiments did not indicate any improvement in comparison with devulcanization without chemicals. An idea of adding fresh CB into devulcanized compound, which has been shown to improve mechanical properties in the case of styrene–butadiene rubber (SBR), was tested in the present study for CB filled NR compound. The obtained result indicated that an addition of fresh CB to devulcanized CB‐filled NR did not lead to an improvement in mechanical properties upon revulcanization. The revulcanization recipe was optimized to improve the mechanical properties of revulcanized CB‐filled NR vulcanizates. It was found that CB‐filled NR upon revulcanization retained its strain‐induced cystallizability with the tensile strength and elongation at break at about 50 and 70% level of the virgin vulcanizates. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2340–2348, 2001     

Continuous ultrasonic devulcanization of unfilled butyl rubber

The devulcanization of resin‐cured unfilled butyl rubber with a grooved‐barrel ultrasonic reactor under various processing conditions was carried out. The experiments indicated that, because of the lower unsaturation and good thermal stability of butyl rubber, its devulcanization could be successfully accomplished only under severe ultrasonic‐treatment conditions. Gel permeation chromatography measurements were carried out for the virgin gum and sol part of devulcanized samples to study the changes in the rubber network during the devulcanization process. The obtained data showed a significant molecular weight reduction and a broadening of the molecular weight distribution upon devulcanization, which indicated that the devulcanization and degradation of butyl rubber occurred simultaneously. The rheological properties showed that devulcanized butyl rubber was more elastic than the virgin gum. The vulcanizates of the devulcanized butyl rubber showed mechanical properties comparable to those of the virgin vulcanizate. The thermal behaviors of the virgin and devulcanized butyl rubber were different and were correlated to the double‐bond content. The structural characteristics of the devulcanized butyl rubber were simulated with the Dobson–Gordon theory of rubber network statistics. A fairly good agreement between the experimental data and theoretical prediction was achieved. The simulation of devulcanized butyl rubber indicated that the rate of crosslink rupture was much higher than that of the main chain. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1316–1325, 2004     

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     

Continuous ultrasonic devulcanization of unfilled NR vulcanizates

Sulfur-cured unfilled natural rubber (NR) is successfully devulcanized in a continuous extrusion process under the application of high-power ultrasonic energy. The die characteristics and ultrasonic power consumption are measured. A unique correlation is found between the crosslink density and gel fraction of the devulcanized NR. This correlation is independent of the processing parameters, such as barrel temperature, die gap, flow rate, and amplitude of ultrasound. However, these parameters do influence the degree of devulcanization. In most cases, the degree of devulcanization is found to pass through a maximum at an intermediate level of ultrasonic energy. It is hypothesized that simultaneous breakup and reformation of crosslinks occur during the devulcanization of NR, with the relative contribution of each being determined by the process parameters. The cure curves and mechanical properties of the revulcanized NR are studied. The mechanical properties are found to depend on the revulcanization recipe. On optimizing it, tensile strength as high as 14.2 MPa is achieved, which is about 70% of that of the virgin NR vulcanizate. Ultimate elongation as high as 670% is obtained, which is the same as that of the virgin NR vulcanizate. Such stress–strain behavior is an indication that the devulcanized NR maintains the strain-induced crystallization characteristics inherent to the virgin NR vulcanizates. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2007–2019, 1998     

The effect of devulcanization level on mechanical properties of reclaimed rubber by thermal‐mechanical shearing devulcanization

Ground tire rubber (GTR) with crosslinked structure has hardly any plasticity and processability, which makes its property very poor. Thermal‐mechanical shearing devulcanization method can effectively destroy the crosslinked structure and restore GTR a certain extent of plasticity and processability. This article investigated the characteristic and reprocessing performance of reclaimed rubber prepared through thermal‐mechanical shearing devulcanization. The relationship between the devulcanization level (indicated by gel fraction and crosslink density) and the mechanical property was analyzed by sufficient experiments. Fourier transform infrared spectroscopy and elemental analyzer studies revealed the chemical structure of GTR changed and many complex reactions occurred after devulcanization. The gel permeation chromatography indicated the specific changes of molecular weight and molecular weight distribution in devulcanization process. The differential scanning calorimetry revealed various vulcanized abilities and vulcanized structures of reclaimed rubber. The scanning electron microscope further confirmed the recovery of plasticity after devulcanization and the distinct vulcanized structures between revulcanizates. The determination of devulcanization level and mechanical properties verified that mechanical properties especially tensile strength reached to the optimum value only at an appropriate devulcanization level. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Continuous ultrasonic devulcanization of NR/SBR blends

The ultrasonic devulcanization of sulfur‐cured natural rubber (NR)/styrene–butadiene rubber (SBR) blends was studied with the goal of understanding the devulcanization of rubber vulcanizates in which two networks of different natures were present. Also, similarities and differences in the devulcanization behaviors of NR, SBR, and their blends were found. During the devulcanization of cured NR/SBR blends, we observed that, as for NR, the ultrasonic power consumption for 75/25 and 50/50 (w/w) NR/SBR blends passed through a maximum at 7.5 μm. For SBR and 25/75 (w/w) NR/SBR blends, the power consumption increased with increasing ultrasonic amplitude. The higher power consumption led to a higher degree of devulcanization. The crosslink densities of the devulcanized 25/75, 50/50, and 75/25 (w/w) NR/SBR blends were lower than those of the devulcanized NR and SBR, possibly because of the reduced degree of unsaturation. The tensile properties of the revulcanized blends were lower than those of the virgin vulcanized blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 160–168, 2002     

Complete devulcanization of sulfur‐cured butyl rubber by using supercritical carbon dioxide

Sulfur‐cured butyl rubber was devulcanized completely in supercritical CO₂ by using diphenyl disulfide (DD) as a devulcanizing reagent. The optimum devulcanizing conditions were studied and the sol fraction of the reclaimed rubber obtained was up to 98.5%. The possible devulcanizing mechanism was investigated. Then, the sol component of reclaimed rubber was characterized by gel permeation chromatography, ¹H‐NMR, and differential scanning calorimetry, and the reclaimed rubber was characterized by TGA. Because of the substitution of a large portion of allylic hydrogen by sulfurated functional groups during vulcanization, the signal of the olefinic proton shift. As a result of the numerous decreases in the active crosslinking sites and the remaining DD, reclaimed rubber could not be cured by sulfur. At last, the blends of virgin butyl rubber and different contents of reclaimed rubber were revulcanized and their mechanical properties investigated. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effects of the presence of water on ultrasonic devulcanization of polydimethylsiloxane

The effects of the presence of water on ultrasonic devulcanization of 30 phr silica‐filled polydimethylsiloxane (PMDS) were investigated at increasing feed rates and different die gap sizes. The results showed that the initial die entrance pressure without ultrasound for wet rubber was higher than in the case without water and then it decreased monotonously with applying ultrasound. The die pressure for wet rubber decreased significantly even at low ultrasonic amplitude, while that for dry rubber changed little at low amplitude. The power consumption at an amplitude of 10 μm, where devulcanization was most effectively achieved, was lower for wet rubber even though the pressure was lower. The crosslink density and gel fraction after the devulcanization of wet rubber were lower than those of dry rubber, indicating that the presence of water facilitates the devulcanization process under the same devulcanization conditions. The good mechanical properties of recycled silica‐filled PDMS were obtained at higher feed rates and at lower ultrasound amplitudes, which are directly related to the economics of a recycling process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2630–2638, 2003     

轮胎胶囊修补初探

探索了因气泡、杂胶，裂口，滥泡等造成的报废胶囊的修补方法，确定修补胶料配方为：生胶100；硬脂酸2；石蜡1；树脂8；炭黑55；促进剂1；其它11。硫化工艺条件为；蒸汽压力1.2MPa；风压0.3-0.4MPa。并讨论了胶浆制备，胶囊选择和打磨，胶料填充，胶囊检查修整等具体步骤。     

Study of metal poisoning in natural rubber–based tire‐tread compound

In the present study the effect of metal poisoning was studied in a natural rubber (NR)–based tire‐tread compound. The experimental compound contained 1000 ppm copper metal as an additional ingredient. A detailed study was carried out and the results of the experimental compound were compared against a control compound having no metal ion. The effect of metal poisoning was not significant in the case of the green experimental compound, even after prolonged storage of 150 days. However, the cured experimental compound deteriorated substantially after ageing in aerobic‐, anaerobic‐, oil‐, and outdoor‐ageing conditions. The ozone resistance property of the experimental compound also proved to be inferior. The degradation kinetic of metal poisoning was found to be a first‐order reaction and the service life (as expressed by the half‐life period) was drastically reduced for the poisoned compound. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1492–1499, 2005     

Effect of replacement of castor oil and polychloroprene by chlorinated paraffin in butyl compounds of tyre‐curing bladder

Ways are explored to increase the life and to reduce the cost of tyre‐curing bladders by improving their mechanical and ageing properties. Nine formulations have been designed which involve the partial replacement of polychloroprene (PC) and castor oil (CO), both individually and simultaneously, by chlorinated paraffin (CP) in the butyl bladder compound. The compounds have been tested for various cure properties such as initial torque, minimum torque, scorch time, optimum cure time, cure rate, maximum torque and reversion time. The vulcanized samples have been tested for mechanical properties such as tensile stress at 300 % elongation, tensile strength at break, ultimate elongation, rubber deterioration by dynamic fatigue test and Shore‐A hardness before and after ageing. The results show that tensile strength at break and ultimate elongation decrease, while tensile stress at 300 % elongation increase except in one case (when PC was partially replaced by CP). Simultaneous and individual replacement of CO by CP results in a decrease in hardness of up to 3 phr (base recipe CO 5 phr), whereas further replacement of CO by CP results in an increase in hardness. Tensile stress at 300 % elongation and Shore‐A hardness increase up to a limit while tensile strength at break and ultimate elongation decrease with ageing. © 2000 Society of Chemical Industry     

改进配方提高胶囊使用寿命

研究以202树脂等量替代2402树脂在胶囊配方中的应用效果。202树脂的软化点和羟甲基质量分数波动均较小；加入202树脂的胶料ML增大，t10延长，硫化速度加快，硫化胶的拉伸强度、扯断伸长率及撕裂强度增大，邵尔A型硬度和300％定伸应力减小；采用202树脂生产的胶囊平均使用寿命为218次，提高50％以上。     

Continuous devulcanization of waste tires by using a Co‐rotating twin screw extruder: Effects of screw configuration,temperature profile,and devulcanization agent concentration

Recently, for reasons both economical and environmental, recycling of waste tires based on (styrene butadiene rubber)/(natural rubber) (SBR/NR) has been widely considered. Response surface methodology (RSM) has been used to predict SBR/NR devulcanization behavior in a co‐rotating twin screw extruder. In this study, variable parameters were barrel temperature, screw configuration, and content of devulcanization agent. A Box‐Behnken design for the three variables, at three levels, was chosen. The sol fraction of devulcanized rubber, Δtorque (difference between maximum and minimum curing torque), and mechanical properties of revulcanizate samples were considered as the responses. The results indicated that an increase of devulcanization agent content at a certain temperature caused the sol fraction to increase. Samples including a higher sol fraction showed a lower cross‐link density. Sol fraction for high shear rate screw configuration was lower than that for other screw configurations. Tensile strength of revulcanized rubber showed a decrease with a rise of devulcanization temperature. Moreover, a relationship connecting the residence time in the extruder with stagger angle and length of different kneading blocks were obtained. J. VINYL ADDIT. TECHNOL., 19:65–72, 2013. © 2013 Society of Plastics Engineers     

Recycling of polypropylene‐based eco‐composites

BACKGROUND: Renewable resources and recyclable thermoplastic polymers provide an attractive eco‐friendly quality as well as environmental sustainability to the resulting natural fibre‐reinforced composites. The properties of polypropylene (PP)‐based composites reinforced with rice hulls or kenaf fibres were investigated with respect to their recyclability. Rice hulls from rice processing plants and natural lignocellulosic kenaf fibres from the bast of the plant Hibiscus cannabinus represent renewable sources that could be utilized for composites. Maleic anhydride‐grafted PP was used as a coupling agent to improve the interfacial adhesion between fillers and matrix. Composites containing 30 wt% reinforcement were manufactured by melt mixing and their mechanical and thermal properties were determined. The composites were then pelletized and reprocessed by melt mixing. Finally, structure/properties relationships were investigated as a function of the number of reprocessing cycles. RESULTS: It is found that the recycling processes do not induce very significant changes in flexural strength and thermal stability of the composites. In particular PP‐based composites reinforced with kenaf fibres are less sensitive to reprocessing cycles with respect to PP‐based composites reinforced with rice hulls. CONCLUSION: The response of PP‐based composites reinforced with rice hulls or kenaf fibres is promising since their properties remain almost unchanged after recycling processes. Moreover, the recycled composites are suitable for applications as construction materials for indoor applications. In fact, the flexural strength and modulus of these materials are comparable to those of conventional formaldehyde wood medium‐density fibreboards. Copyright © 2008 Society of Chemical Industry     

Microencapsulation of imidazole curing agents by spray‐drying method

An epoxy resin–imidazole system was used to form the adhesives for the anisotropic conducting film (ACF), and a latent curing system was necessary for the ACF. In this study, imidazoles were microencapsulated for the latent curing system. Polycaprolactone (PCL) was used as the wall material, and the spray‐drying method was used to form the microcapsule. The imidazoles used in this study were imidazole, 2‐methylimidazole, and 2‐phenylimidazole. The effect of the ratio of PCL to imidazoles, and the effect of PCL molecular weight were investigated during the microcapsule formation. The amount of imidazoles in the microcapsule was measured using thermogravimetric analyzer and elemental analysis. The permeability of the microcapsules was measured in ethanol, and the shelf life of the microcapsules was studied for the epoxy resin. The curing behavior of these microcapsules to epoxy resin was examined using differential scanning calorimeter. In the curing reaction, the microcapsule of imidazoles exhibited delayed kinetic behaviors compared to pure imidazoles. And the curing times were estimated at 150 and 180°C using an indentation method. These microcapsules of imidazoles exhibited a long shelf life, and the curing did not occur in some of the microcapsule–epoxy resin systems at 20°C for 15 days. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal curing of glass‐epoxy prepregs by luminescence spectroscopy

In this study, we investigated the application of the luminescence spectroscopy technique in steady‐state conditions to study glass fiber‐epoxy F161 prepregs. We conducted this study by comparing the results obtained from the intrinsic fluorescence with Fourier transform near infrared spectroscopy. The extrinsic fluorescence of 9‐anthroic acid (9‐AA) was also used. Fourier transform infrared spectroscopy was also used to characterize the epoxide resin. The prepregs containing 9‐AA and those that did not were heat‐treated at 177°C (F161) for 1100 min at a 2°C/min heating rate. The results obtained by both methods indicated that the crosslinking reaction could be monitored by analysis of the spectral changes of the emission bands of the prepreg and 9‐AA. The intrinsic emission at 320 nm was attributed to the fluorophore group containing the epoxy ring and was used to calculate the conversion degree. The photophysical behavior of the 9‐AA probe indicated a reduction of free volume of the polymeric matrix with curing process. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Water‐repellent finishing of cotton fabrics by ultraviolet curing

Cotton fabrics were water‐repellent‐finished by radical ultraviolet curing of silicone and urethane acrylates with different formulations. The fabrics were impregnated with undiluted resins and with toluene solutions or water emulsions. Moreover, cationic ultraviolet‐curable systems were also investigated, such as an epoxy‐functional polysiloxane and mixtures of an epoxy resin with hydroxyl‐containing silicone additives. The gel content and polymerization yield were considered for the ultraviolet‐curing process evaluation. Water‐resistance properties were determined in terms of the contact angle, wettability, moisture adsorption, and water vapor permeability measurements, whereas the morphology and surface composition of treated fabrics were examined with scanning electron microscopy and energy‐dispersive X‐ray analysis. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Microwave‐induced devulcanization for poly(ethylene–propylene–diene) recycling

The production of high quantities of end‐of‐life rubbers is an environmental problem of growing importance. Because of their crosslinked nature, such rubbers cannot be easily reprocessed, and actually, they are mainly wasted or reused after a simple mechanical grinding. In this study, a microwave (MW)‐induced thermal treatment at temperatures above 300°C was proposed to obtain partial devulcanization of a poly(ethylene–propylene–diene) (EPDM) rubber filled with carbon black. The use of MWs showed to be a very fast and simple technique, which allowed the production of a treated rubber with a relatively low degree of crosslinking, a slight revulcanization ability, and suitability for reuse in conjunction with virgin rubber. Preliminary mechanical characterization, performed on the revulcanized samples, indicated that the virgin and treated rubber were able to establish a good interface adhesion, which led to performances better than those of similar materials where the recycled part was made of ground untreated EPDM. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The curing of UF resins studied by low‐resolution 1H‐NMR

A series of UF resins and one MUF resin were studied by low‐resolution ¹H‐NMR. The mobility of the resin during curing could be followed by measuring the spin‐spin relaxation time (T₂) with curing time. The relative curing behavior was similar to that found by traditional gel time measurements. In addition, extra features in the T₂ plots with curing time showed at what point the bulk of the condensation reactions took place. The speed of cure was also related to the chemical groups in the liquid resin, and it was found that the linear methylol groups were mainly responsible for the curing speed of the resins. By studying the curing with different hardener levels and glue concentrations it was found that a UF resin is more sensitive to the glue mix concentration than an MUF resin. A cured resin was also studied after curing to investigate postcuring effects. Water seemed to play the biggest role in the postcure, with substantial amounts present immediately after cure, which decreased with curing time and aging. For the low mol ratio resins studied here further curing reactions did not seem to play a major role in the post curing phenomenon. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 754–765, 2000