废旧天然胶胶粉应用研究

以80目的废天然胶胶粉为研究对象,处理后将其分别以20%,30%的比例添加到天然混炼胶(NR)中,制备废胶粉/NR共混硫化胶;同时,通过邻苯二甲酸酐(PA)和高芳烃油对胶粉进行处理改性,制备了全胶粉弹性体。拉伸强度测试表明,对于共混胶弹性体,NR混炼胶空白样的拉伸强度为19.21 MPa,添加20%,30%比例的胶粉/NR共混硫化胶的拉伸强度可以分别达到18.03 MPa,17.23 MPa;改性后制备的全胶粉混炼胶硫化样品拉伸强度达到8.12 MPa,超过了再生胶的国标标准。同时应用扫描电子显微镜SEM分析、比较了各试样断裂面的微观结构,应用比表面仪BET和SEM表征了胶粉的表面形貌与结构,发现胶粉表面呈现"绒球"状,具有较好的表面性能。     

New Route for Devulcanization of Natural Rubber and the Properties of Devulcanized Rubber

Devulcanization of natural rubber (NR) compound was carried out by means of benzoyl peroxide as a devulcanizing agent by two different techniques namely (a) chemical process and (b) mechano-chemical process. Furthermore, the effects of time and concentration of devulcanizing agent on the devulcanization process were investigated. The extent of devulcanization of natural rubber was studied by estimation of percent devulcanization, volume fraction of rubber after swelling, Mooney viscosity and crosslinked density. The devulcanized natural rubber obtained from mechano-chemical process was blended with virgin natural rubber in different proportions. The mechanical properties and morphology of the revulcanized blends were examined and found to be interesting. Thus, waste rubber could be reused successfully by this technique.     

Effect of Hybrid Tackifiers on Adhesion Properties of Epoxidized Natural Rubber-Based Pressure-Sensitive Adhesives

Viscosity, peel and shear strength of epoxidized natural rubber (ENR)-based pressure-sensitive adhesive was studied by using hybrid tackifiers consisting of a mixture of coumarone-indene resin and petro resin. The coumarone-indene resin concentration was fixed at 40 parts per hundred parts of rubber (phr). The concentration of petro resin, however, was varied from 20 to 80 phr. Toluene and polyethylene terephthalate (PET) film were used as the solvent and coating substrate respectively throughout the experiment. Viscosity of adhesive was determined by a HAAKE Rotary Viscometer whereas peel and shear strength was measured by a Lloyd Adhesion Tester. Results show that viscosity and shear strength decreases with increasing petro resin concentration. However, peel strength exhibits a maximum value at 40 phr petro resin, an observation which is attributed to maximum wettability and compatibility of adhesive on the substrate. ENR 25-based adhesive exhibits higher viscosity and peel strength but lower shear strength compared to the ENR 50 adhesive system.     

Possible use of sludge ash as filler in natural rubber

Potential use of sludge ash as a filler in NR was studied. In this study, two grades of sludge ash namely SA-300 and SA-700 were prepared by sintering sludge waste obtained from concentrated natural rubber (NR) latex production at 300 and 700 °C, respectively. Properties of NR filled with various contents of SA-300 and SA-700 were then investigated and compared with those of NR filled with precipitated calcium carbonate (CaCO₃). The results reveal that, regardless of the filler type, both scorch time (t _s1) and optimum cure time (t _c90) decrease whereas hardness and modulus increase with increasing filler loading. At a given loading, both SA-300 and SA-700 give shorter scorch time and cure time with higher hardness and modulus than CaCO₃. Due to their higher specific surface area and greater cure activation efficiency, SA-300 and SA-700 provide better reinforcement, i.e., greater tensile strength; tear strength and abrasion resistance than CaCO₃. Taken as a whole, it could be said that the two grades of sludge ash could be utilized as rubber fillers with economic advantage.     

Effect of Poly(Vinyl Acetate) on Mechanical Properties and Characteristics of Poly(Lactic Acid)/Natural Rubber Blends

Natural rubber grafted with poly(vinyl acetate) copolymer (NR-g-PVAc) was synthesized by emulsion polymerization. Three graft copolymers were prepared with different PVAc contents: 1 % (G1), 5 % (G5) and 12 % (G12). Poly(lactic acid) (PLA) was melt blended with natural rubber (NR) and/or NR-g-PVAc in a twin screw extruder. The blends contained 10–20 wt% rubber. The notched Izod impact strength and tensile properties were determined from the compression molded specimens. The effect of NR mastication on the mechanical properties of the PLA/NR/NR-g-PVAc blend was evaluated. Characterization by DMTA and DSC showed an enhancement in miscibility of the PLA/NR-g-PVAc blend. The temperature of the maximum tan δ of the PLA decreased with increasing PVAc content in the graft copolymer, i.e., from 71 °C (pure PLA) to 63 °C (the blend containing 10 % G12). The increase in miscibility brought about a reduction in the rubber particle diameter. These changes were attributed to the enhancement of toughness and ductility of PLA after blending with NR-g-PVAc. Therefore, NR-g-PVAc could be used as a toughening agent of PLA and as a compatibilizer of the PLA/NR blend. NR mastication was an efficient method for increasing the toughness and ductility of the blends which depended on the blend composition and the number of mastications.     

A Novel Environmentally Compatible Bio-Based Product from Gelatin and Natural Rubber: Physical Properties

The objective of the present work was to study the preparation of a novel bio-based product from gelatin (GT) and natural rubber (NR) using potassium persulphate (KPS) as an initiator. The GT and NR composites (GT/NR composites) containing KPS were formed in an aqueous latex solution. The chemical structure of the GT/NR composite was characterized by ATR-FTIR, and XRD. The highest tensile strength was observed in a 9/1 GT/NR composite and the elongation at break of this composite was improved by the addition of both NR and glycerol. In addition, the swelling ratio increased as a function of increasing GT content in the composite. The thermal stability of the GT was improved after the formation of the chemical interaction between the NR and GT helped by the KPS. The best ratio of the GT/NR composite was 3/7 GT/NR. This environmentally friendly composite easily decomposed in natural soil within 30 days. The novel biopolymer showed high mechanical properties, water resistance and was produced in an environmentally compatible process. The NR was able to improve some of the physical and mechanical properties of GT biofilms produced from the composite. Possible future applications of this composite are for medical materials, and the packaging and life extension of food products.     

Study on the Effect of Dicumyl Peroxide on Structure and Properties of Poly(Lactic Acid)/Natural Rubber Blend

In attempt to enhance the compatibility of NR in PLA matrix, and furthermore to enhance mechanical properties of PLA, PLA/NR blends with strong interaction were prepared in Haake internal mixer, using dicumyl peroxide (DCP) as cross-linker. The effects of dicumyl peroxide on morphology, thermal properties, mechanical properties and rheological properties of PLA and PLA/NR blends were studied. The results indicated that dicumyl peroxide could increase the compatibility of poly(lactic acid) and natural rubber. With small amount of dicumyl peroxide, the effect on NR toughening PLA was enhanced and the tensile toughness of PLA/NR blends was improved. When the DCP content was up to 0.2 wt%, the PLA/NR blend reached the maximum elongation at break (26.21 %) which was 2.5 times of that of neat PLA (the elongation at break of neat PLA was 10.7 %). Meanwhile, with introducing 2 wt% DCP into PLA/NR blend, the maximum Charpy impact strength (7.36 kJ/m²) could be achieved which was 1.8 times of that of neat PLA (4.18 kJ/m²). Moreover, adding adequate amount of DCP could improve the processing properties of blends: the viscosity of PLA/NR blend decreased significantly and the lowest viscosity of the blends could be achieved when the DCP content was 0.5 wt%.     

Utilization of limestone dust waste as filler in natural rubber

The possibility of using limestone dust waste (LDW) as a filler in natural rubber (NR) was investigated. First, the basic properties of LDW were characterized; LDW was then incorporated into NR and the compound properties were determined. Comparison of the reinforcing effect of LDW and other commercial fillers such as light-precipitated calcium carbonate (PCC) and nanoprecipitated calcium carbonate (NPCC) was made. The results revealed that even though the addition of LDW has little effect on compound processability, it has a negative effect on most mechanical properties, e.g., tensile strength, tear strength, and abrasion resistance, of the vulcanizate. Among the three fillers, the degree of reinforcement could be placed in the following order: NPCC > PCC > LDW. Due to their relatively low specific surface area and thus low reinforcement ability, both LDW and PCC can be grouped as nonreinforcing fillers, whereas NPCC, the specific surface area of which is relatively high, could be grouped as a semi-reinforcing filler for rubber.     

The Potential of Chicken Eggshell Waste as a Bio-filler Filled Epoxidized Natural Rubber (ENR) Composite and its Properties

Eggshell calcium carbonate (ECC) and eggshell calcium carbonate treated with high temperature (ECC-600) were prepared from chicken eggshell waste. ECC was obtained by crushing eggshell waste, eliminating membranes and followed by sieving. In the case of ECC-600, ECC powder was additionally heated at 600 °C for 2 h. Both were used to promote as fillers compared to that of commercial light-precipitated calcium carbonate (commercial CaCO₃) with various loading levels (i.e., 0, 25, 50 and 75 phr) in epoxidized natural rubber containing 25 mol% of epoxide group (ENR-25). Among the three types of fillers (i.e., ECC, ECC-600 and commercial CaCO₃), ECC filled materials showed superior vulcanization characteristics by the increasing of maximum torque (M_H) and cure rate index (CRI) with the reducing of cure time (t_c90) and scorch time (t_s2). The highest tensile properties as well as the lowest tension set value were also observed. Morphological property revealed that ECC was greater interfacial adhesion than those of others. In addition, dynamic mechanical properties of vulcanizates containing ECC, storage modulus (E′) was the highest and glass transition temperature (T _g ) shifted toward high temperature. Increasing of loading levels of any fillers affected the increase of M_H and CRI with reducing of t_c90 and t_s2. However, tensile properties decreased with increasing filler content but it did not affect T _g shifting except for a series of vulcanizates containing ECC.     

Possibility of using waste tire rubber and fly ash with Portland cement as construction materials

The growing amount of waste rubber produced from used tires has resulted in an environmental problem. Recycling waste tires has been widely studied for the last 20 years in applications such as asphalt pavement, waterproofing systems and membrane liners. The aim of this study is to evaluate the feasibility of utilizing fly ash and rubber waste with Portland cement as a composite material for masonry applications. Class C fly ash and waste automobile tires in three different sizes were used with Portland cement. Compressive and flexural strength, dry unit weight and water absorption tests were performed on the composite specimens containing waste tire rubber. The compressive strength decreased by increasing the rubber content while increased by increasing the fly ash content for all curing periods. This trend is slightly influenced by particle size. For flexural strength, the specimens with waste tire rubber showed higher values than the control mix probably due to the effect of rubber fibers. The dry unit weight of all specimens decreased with increasing rubber content, which can be explained by the low specific gravity of rubber particles. Water absorption decreased slightly with the increase in rubber particles size. These composite materials containing 10% Portland cement, 70% and 60% fly ash and 20% and 30% tire rubber particles have sufficient strength for masonry applications.     

Effect of Nucleating Agents on Physical Properties of Poly(lactic acid) and Its Blend with Natural Rubber

Poly(lactic acid) (PLA) presents high strength and modulus, but very low toughness as well as slow crystallization. Natural rubber (NR) was blended to enhance the toughness and nucleating agent was added to improve the crystallization. Cyclodextrin (CD), considered as a green compound, as well as calcium carbonate (CaCO₃) and talc were used as nucleating agents. Effects of these nucleating agents on crystallization, mechanical properties and morphology of neat PLA and PLA/NR blend were investigated. It was found that the addition of talc and CD decreased cold crystallization temperature (T_cc) of the PLA. Same result was obtained in PLA/NR blend containing talc. All nucleating agents increased the degree of crystallinity (Χ_C) of PLA, whereas only talc and CaCO₃ increased Χ_C of PLA in PLA/NR blends. The enhanced toughness of PLA by the addition of nucleating agent was attributed to its increased crystallinity, as well as decreased spherulite size. For PLA/NR blends, the increase in toughness was mainly contributed by the presence of the rubber.     

Thermal,Rheological, Mechanical and Morphological Behavior of High Density Polyethylene and Carboxymethyl Cellulose Blend

In this study water soluble sodium carboxymethyl cellulose (CMC) was blended with high density polyethylene (HDPE) by peroxide-initiated melt compounding technique. The compatibility of the blended polymers were carried out by silane crosslinking agent. A series of blends were prepared by varying the CMC contents up to a maximum of 50 phr. The physical properties of non-crosslinked and crosslinked blends were investigated in detail. FTIR analysis of crosslinked blend confirmed the presence of Si–O–Si and Si–O–C absorption peaks at 1050 and 1159 cm^?1. Thermal stability of crosslinked blends improved as compared to its non-crosslinked congener. Rheological study of crosslinked blends illustrated high complex viscosity and dynamic shear storage modulus. The tensile strength of virgin polyethylene was 8.1 MPa whereas the maximum tensile strength of 19.6 MPa was observed in crosslinked blend. Similarly lower deformation was observed in crosslinked blends under static load. Scanning electron microscopy of crosslinked formulations also showed strong adhesion between the polymers interface. The compatibility of HDPE and CMC is attributed to both free radical and condensation reactions.     

Rheological and Thermal Properties of the PLA Modified by Electron Beam Irradiation in the Presence of Functional Monomer

Polylactic acid (PLA) has been modified by electron beam radiation in the presence of glycidyl methacrylate (GMA) to enhance the melt strength of PLA. The modified PLA was prepared by varying both the amount of GMA and the irradiation dose and was characterized by observing the thermal properties, the melt viscoelastic properties and the gel fraction. For comparison, virgin PLA was also irradiated. All irradiated virgin PLA had a lower complex viscosity and a storage modulus compared to virgin PLA due to irradiation-induced chain scission. However, these properties were remarkably improved due to formation of long chain branching and retarding chain scission if GMA was introduced in this system. The increase in melt viscoelastic property was much dependent on the irradiation dose. At optimum doses of radiation, it showed maximum complex viscosity and storage modulus. The PLA irradiated with 20 kGy in the presence of 3 phr GMA showed a complex viscosity of about 10 times higher and a storage modulus of 100 times higher than those of virgin PLA at 0.1 rad/s. Gel fraction measurement revealed that chain scission and branching was more dominant than crosslinking. The biodegradability of irradiated PLA was slightly decreased by the presence of GMA.     

The Use of Interfacial Blend to Increase the Adhesion Properties of Natural Rubber/Polyvinylalcohol Multilayer Using Electron Beam Irradiation

Multilayers of natural rubber (NR) and polyvinylalcohol (PVA) were processed by casting natural rubber latex (NRL) then PVA with varying layer thickness. Adhesion between NR and PVA was found to be very poor, as determined with the peel method. The films of interfacial blend were composed of NRL and PVA having different ratios as a layer between NR/PVA layer, possessing good adhesion and exhibited one mechanical phase in tensile-elongation at break tests. The result of adhesion was confirmed by thermogravimetric analysis and scanning electron microscopy study. Also, adhesion was too strong for delamination at the interface when the unit of three layers NR/blend/PVA was irradiated at 25 kGy. To probe the effect of the adhesion difference on mechanical behavior and deformation of NR/blend/PVA layers at dry and wet conditions, the peel strength was examined as a function of layer thickness and aging time. The results indicated that the interfacial blend, irradiation process and film thickness were the key parameters affecting adhesion of NR/PVA layer.     

Utilization of Porous Carbons Derived from Coconut Shell and Wood in Natural Rubber

The porous carbons derived from cellulose are renewable and environmentally friendly. Coconut shell and wood derived porous carbons were characterized with elemental analysis, ash content, X-ray diffraction, infrared absorbance, particle size, surface area, and pore volume. The results were compared with carbon black. Uniaxial deformation of natural rubber (NR) composites indicate the composites reinforced with the porous carbon from coconut shell have higher tensile moduli at the same elongation ratio than the composites reinforced with wood carbon. 40 % coconut shell composite showed a fivefold increase in tensile modulus compared to NR. Polymer–filler interactions were studied with frequency dependent shear modulus, swelling experiments and dynamic strain sweep experiments. Both linear and non-linear viscoelastic properties indicate the polymer–filler interactions are similar between coconut shell carbon and wood carbon reinforced composites. The swelling experiments, however, showed that the polymer–filler interaction is greater in the composites reinforced with coconut shell instead of wood carbon.     

Effect of Magnesium Oxide Loading on Adhesion Properties of ENR 25/NBR Blend Adhesives in the Presence of Petro Resin and Gum Rosin Tackifiers

The adhesion properties of magnesium oxide filled epoxidized natural rubber (ENR 25)/acrylonitrile-butadiene rubber (NBR) blend adhesives were studied using petro resin and gum rosin as tackifiers. Toluene was used as the solvent throughout the experiment. Five different loadings, i.e. 10, 20, 30, 40 and 50 phr magnesium oxide was used in the adhesive formulation. The SHEEN hand coater was used to coat the adhesive on polyethylene terephthalate at 30 and 120 µm coating thickness. The tack, peel strength and shear strength were determined by a Lloyd adhesion tester operating at 30 cm min^?1. Results shows that all the adhesion properties of the ENR 25/NBR adhesives show a maximum value at 10 phr filler loading. Loop tack and peel strength pass through a maximum, an observation which is associated to the optimum wettability of adhesive on the substrate. For the shear test, maximum shear strength occurs due to the optimum cohesive strength of the adhesive. Results also show that all petro resin based adhesives have higher adhesion properties than gum rosin based adhesive. In all cases, the adhesion properties of adhesives also increase with increasing coating thickness.     

Fabrication of Admicelled Natural Rubber by Polycaprolactone for Toughening Poly(lactic acid)

Natural rubber (NR) with polycaprolactone (PCL) core–shell (NR-ad-PCL), synthesized by admicellar polymerization, was acted as an impact modifier for poly(lactic acid) (PLA). PLA and NR-ad-PCL were melt-blended using a co-rotating twin screw extruder. The morphology of PLA/NR-ad-PCL blends showed good adhesion as smooth boundary around rubber particles and PLA matrix. Only 5 wt% of rubber phase, NR-ad-PCL was more effective than NR to enhance toughness and mechanical properties of PLA. The contents of the NR-ad-PCL were varied from 5, 10, 15 and 20 wt%. From thermal results, the incorporation of the NR-ad-PCL decreased the glass transition temperature and slightly increased degree of crystallinity of PLA. Mechanical properties of the PLA/NR-ad-PCL blends were investigated by dynamic mechanical analyser, pendulum impact tester and universal testing machine for tension and flexural properties. The increasing NR-ad-PCL contents led to decreasing Young’s and storage moduli but increasing loss modulus. Impact strength and elongation at break of the PLA/NR-ad-PCL blends increased with increasing NR-ad-PCL content up to 15 wt% where the maximum impact strength was about three times higher than that of pure PLA and the elongation at break increased to 79%.     

Promoting the use of crumb rubber concrete in developing countries

The use of accumulated waste materials in third world countries is still in its early phases. It will take courage for contractors and others in the construction industry to recycle selected types of waste materials in the concrete mixes. This paper addresses the recycling of rubber tires accumulated every year in Jordan to be used in concrete mixes. The main objectives of this research were to provide more scientific evidence to support the use of legislation or incentive-based schemes to promote the reuse of accumulated waste tires. This research focused on using crumb tires as a replacement for a percentage of the local fine aggregates used in the concrete mixes in Jordan. Different concrete specimens were prepared and tested in terms of uniaxial compression and splitting tension. The main variable in the mixture was the volumetric percentage of crumb tires used in the mix. The test results showed that even though the compressive strength is reduced when using the crumb tires, it can meet the strength requirements of light weight concrete. In addition, test results and observations indicated that the addition of crumb rubber to the mix has a limited effect toward reducing the workability of the mixtures. The mechanical test results demonstrated that the tested specimens of the crumb rubber concrete remained relatively intact after failure compared to the conventional concrete specimens. It is also concluded that modified concrete would contribute to the disposal of the non-decaying scrap tires, since the amount being accumulated in third world countries is creating a challenge for proper disposal. Thus, obliging authorities to invest in facilitating the use of waste tires in concrete, a fundamental material to the booming construction industry in theses countries, serves two purposes.     

Use of waste rubber as concrete additive.

For resource reutilization, scrap tyres have long been investigated as an additive to concrete to form 'Rubcrete' for various applications and have shown promising results. However, the addition of rubber particles leads to the degradation of physical properties, particularly, the compressive strength of the concrete. In this study, a theoretical model was proposed to shed light on the mechanisms of decrease in compressive strength due to the addition of rubber particles as well as improvement in compressive strength through modification of particle surfaces. The literature suggests that the compressive strength can be improved by soaking the rubber particles in alkaline solution first to increase the inter-phase bonding between the rubber particles and cement. Instead, we discovered that the loss in compressive strength was due to local imperfections in the hydration of cement, induced by the addition of heterogeneous and hydrophobic rubber particles. Microscopic studies showed that the rubber particles disturbed the water transfer to create channels, which were prone to cracking and led to a loss in the compressive strength. Unexpectedly, no cracking was found along the surfaces of the rubber particles, indicating that the bonding strength between the rubber particles and cement phases was not the critical factor in determining the compressive strength. Therefore, a theoretical model was proposed to describe the water transfer in the Rubcrete specimens to explain the experimental data. In the model, the local water available for hydration (Q) is: Q = -A(slv)/6piv, where Q, A(slv), and v are mass flow rate (kg s(-1)), Hamaker constant (J), and dynamic viscosity (m2 s(-1)), respectively. By maximizing the quantity Q and, in turn, the Hamaker constant A(slv), the compressive strength could be improved. The Hamaker constant A(slv) for water film on rubber particle surfaces was smaller than that for the hydrated cement particles; the water transfer rate was lower in the presence of rubber particles because the Hamaker constant A(slv) for water film on rubber particle surfaces was smaller than that on the hydrated cement particles. Thus, the compressive strength of Rubcrete could be improved by increasing the Hamaker constant of the system. This was achieved by increasing the refractive indices of the solids (n(s)). The refractive indices of materials increase with increases in functional groups, such as OH and SH on the surface. The model provided a possible mechanism for the efficacy of treating rubber particles with NaOH in improving the compressive strength. By using NaOH solution treatment, an oxygen-containing OH group was formed on the rubber surface to increase the Hamaker constant of the system, leading to higher compressive strength. Based on this mechanism, a novel method for modification of the rubber particles was also proposed. In this process, the rubber particles were partially oxidized with hot air/steam in a fluidized bed reactor to produce the hydrophilic groups on the surface of the particles. Preliminary results obtained so far are promising in accordance with the theory.     

Dispersion and Reinforcing Potential of Carboxymethylated Nanofibrillated Cellulose Powders Modified with 1-Hexanol in Extruded Poly(Lactic Acid) (PLA) Composites

Bionanocomposites of poly(lactic acid) (PLA) and chemically modified, nanofibrillated cellulose (NFC) powders were prepared by extrusion, followed by injection molding. The chemically modified NFC powders were prepared by carboxymethylation and mechanical disintegration of refined, bleached beech pulp (c-NFC), and subsequent esterification with 1-hexanol (c-NFC-hex). A solvent mix was then prepared by precipitating a suspension of c-NFC-hex and acetone-dissolved PLA in ice-cold isopropanol (c-NFC-hex_sm), extruded with PLA into pellets at different polymer/fiber ratios, and finally injection molded. Dynamic mechanical analysis and tensile tests were performed to study the reinforcing potential of dried and chemically modified NFC powders for PLA composite applications. The results showed a faint increase in modulus of elasticity of 10?% for composites with a loading of 7.5?% w/w of fibrils, irrespective of the type of chemically modified NFC powder. The increase in stiffness was accompanied by a slight decrease in tensile strength for all samples, as compared with neat PLA. The viscoelastic properties of the composites were essentially identical to neat PLA. The absence of a clear reinforcement of the polymer matrix was attributed to poor interactions with PLA and insufficient dispersion of the chemically modified NFC powders in the composite, as observed from scanning electron microscope images. Further explanation was found in the decrease of the thermal stability and crystallinity of the cellulose upon carboxymethylation.