Modification of epoxidised natural rubber film surface by polymerisation of methyl methacrylate

Epoxidised natural rubber (ENR) latex, having 25% of epoxide content, was prepared by in situ epoxidation reaction using performic acid. The ENR latex film surface was modified by immersing into methyl methacrylate (MMA) emulsion and then alkaline aqueous solution of ferrous ion/fructose for redox-initiated polymerisation. Increasing polymerisation time caused an increase in percent conversion of MMA swelled in ENR sheet. The presence of poly(methyl methacrylate) on the ENR surface was examined by attenuated total reflection-Fourier transform infrared spectroscopy. The nano-scale indentation experiment performed on the cross-section of the modified ENR sheet indicated that MMA polymerisation occurred mainly near the rubber’s surface. The surface morphology observed under scanning electron microscopy and atomic force microscopy revealed a pronounced roughness which, consequently, decreased the friction coefficient of ENR surface.     

Effects of methyl methacrylate grafting and in situ silica particle formation on the morphology and mechanical properties of natural rubber composite films

The effects of methyl methacrylate (MMA) grafting and in situ formation of silica particles on the morphology and mechanical properties of natural rubber latex (NRL) were investigated. MMA grafting on NRL was carried out using cumyl hydroxy peroxide/tetraethylene pentamine (CHPO/TEPA) as a redox initiator couple. The grafting efficiency of the grafted NR was determined by solvent extractions and the grafted NRL was then mixed with tetraethoxysilane (TEOS), a precursor of silica, coated by adherence to a glass surface to form a film and cured at 80°C. The resultant products were characterized by FT‐IR and transmission electron microscopy. The influence of varying the MMA monomer weight ratio on the surface morphology of the composites was investigated by scanning electron and atomic force microscopy. The PMMA (poly MMA) grafted NRL particles were obtained as a core/shell structure from which the NR particles were the core seed and PMMA was a shell layer. The silane was converted into silica particles by a sol–gel process which was induced during film drying at 80°C. The silica particles were fairly evenly distributed in the ungrafted NR matrix but were agglomerated in the grafted NR matrix. The root‐mean‐square roughness increased with an increasing weight ratio of MMA in the rubber. The in situ silica particles in the grafted NR matrix slightly increased both the modulus and the tear strength of the composite film. Copyright © 2008 John Wiley & Sons, Ltd.     

Rheological,mechanical and morphological properties of thermoplastic vulcanizates based on NR‐g‐PMMA/PMMA blends

Graft copolymer of natural rubber and poly(methyl methacrylate) (NR‐g‐PMMA) was prepared using semi‐batch emulsion polymerization technique via bipolar redox initiation system. It was found that the grafted PMMA increased with the increase of methyl methacrylate (MMA) concentration used in the graft copolymerization. The NR‐g‐PMMA was later used to prepare thermoplastic vulcanizates (TPVs) by blending with PMMA through dynamic vulcanization technique. Conventional vulcanization (CV) and efficient sulphur vulcanization (EV) systems were studied. It was found that the CV system provided polymer melt with lower shear stress and viscosity at a given shear rate. This causes ease of processability of the TPVs via extrusion and injection molding processes. Furthermore, the TPVs with the CV system showed higher ultimate tensile strength and elongation. The results correspond to the morphological properties of the TPVs. That is, finer dispersion of the small vulcanized rubber particles were observed in the PMMA matrix. Various blend ratios of the NR‐g‐PMMA/PMMA blends using various types of NR‐g‐PMMA (i.e. prepared using various percentage molar ratios of NR and MMA) were later studied via dynamic vulcanization by a conventional sulphur vulcanization system. It was found that increasing the level of PMMA caused increasing trend of the tensile strength and hardness properties but decreasing level of elongation properties. Increasing level of the grafted PMMA in NR molecules showed the same trend of mechanical properties as in the case of increasing concentration of PMMA used as a blend component. From morphological studies, two phase morphologies were observed with a continuous PMMA phase and dispersed elastomeric phase. It was also found that more finely dispersed elastomeric phase was obtained with increasing the grafted PMMA in the NR molecules. Copyright © 2005 John Wiley & Sons, Ltd.     

In vitro cytotoxicity evaluation of natural rubber latex film surface coated with PMMA nanoparticles

In order to increase surface roughness of the sulphur-prevulcanized natural rubber (SPNR) film and, hence, decrease the direct contact between the rubber and skin, the poly(methyl methacrylate) (PMMA) latex particles were deposited onto the SPNR film grafted with polyacrylamide (SPNR-g–PAAm). The surface coverage of PMMA particles on the SPNR-g–PAAm increased with increasing latex immersion time, particle size and concentration. Prior to the in vitro cytotoxicity evaluation on L-929 fibroblasts, the SPNR and SPNR-g–PAAm coated with PMMA particles were extracted by using the culture medium. Results showed that the cytotoxicity effect could be significantly reduced by coating PMMA particles onto the rubber film. At the extract concentrations of ≤12.5% for 24 h at 37 °C, no toxicity potential was detected. The study will be helpful for development of gloves designed for the hypersensitive person.     

Swift heavy ion induced modification in dielectric and microhardness properties of polymer composites

Polymer composites with different concentrations of organometallics (ferric oxalate) dispersed PMMA were prepared. PMMA was synthesized by solution polymerization technique. These films were irradiated with 120 MeV Ni¹⁰⁺ ions in the fluence range 10¹¹-5 × 10¹² ions/cm². The radiation induced modifications in dielectric properties, microhardness, structural changes and surface morphology of polymer composite films have been investigated at different concentrations of filler and ion-fluences. It was observed that electrical conductivity and hardness of the films increase with the concentration of the filler and also with the fluence. The dielectric constant (?) obeys the Universal law given by ?αfⁿ⁻¹. The dielectric constant/loss is observed to change significantly due to irradiation. This suggests that ion beam irradiation promotes the metal to polymer bonding and convert polymeric structure into hydrogen depleted carbon network. This makes the composites more conductive and harder. Surface morphology of the films has been studied using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The average surface roughness is observed to increase after irradiation as revealed by AFM studies. The SEM images show the blisters type of phenomenon on the surface due to ion beam irradiation.     

Bulk phase separation study by atomic force microscope friction imaging of natural rubber/poly(methyl methacrylate) film

The first observation of bulk phase separation in immiscible natural rubber (NR)/poly(methyl methacrylate) (PMMA) film using atomic force microscopy (AFM) is reported. Three different forms of AFM measurements: topographic, friction force imaging, and nanoindentation have been effectively used to investigate combined morphological and compositional mapping of the NR/PMMA system. The fracture temperature during sample microtoming and material physical properties could be responsible for the observed topographic contrast. The stronger contrast of friction imaging, relative to topographic imaging, is ascribed to local variations in mechanical properties of the phase-separated domains. Friction force imaging associated with nanoindentation response, performed under AFM force mode, highlights the AFM's ability for probing local friction, adhesion, and elastic properties, and for compositional mapping of heterogeneous polymer film. The resulting friction force imaging along with the response of the nanoindentation are in good agreement, indicating that PMMA exists mainly near the modified NR surface.     

Photograft Copolymerization of Methyl Methacrylate and Natural Rubber Using Quinoline-Bromine C.T. Complex as Photoinitiator in Benzene Solution

Photografting of poly(methyl methacrylate), PMMA chains on natural rubber (NR) chain backbones was studied in benzene solution using quinoline-bromine (Q-Br₂) charge transfer complex as photoinitiator and MMA as monomer at 35°C in visible light. Analysis of overall products for determination of grafting efficiencies was done following a method of selective extraction of only the free rubber fraction by benzene-petroleum ether mixtures followed by separation of the NR-PMMA graft copolymer from free PMMA in the residue (taken in benzene solution) by fractional precipitation with methanol. High grafting efficiencies in the range of 75–95% were easily and generally obtained. Effects of variation of concentrations of initiator, rubber, and monomer on grafting efficiencies were examined and reported. Prior photodegradation of the rubber resulted in substantial lowering in grafting efficiencies. Overall mechanism of graft copolymerization has been discussed.     

Grafting of methyl methacrylate onto natural rubber in supercritical carbon dioxide

The grafting of the methyl methacrylate (MMA) monomer onto natural rubber (NR) was carried out by supercritical carbon dioxide (scCO₂) swelling polymerization with benzoyl peroxide (BPO) as an initiator. Fourier transform–infrared spectroscopy (FT–IR) was used to confirm the formation of graft copolymers with the characteristic bands of symmetric C?O and C? O? C stretching vibrations at 1728 cm^?1 and 1147 cm^?1, respectively. The effects of the rubber‐to‐monomer ratio, amount of initiator, reaction time, and pressure on the monomer grafting level (GL) and grafting efficiency (GE) were investigated, and the optimum conditions for the preparation of NR‐g‐MMA were found to be 70:30 of the rubber‐to‐monomer ratio, 1.2% of the initiator content, and the reaction pressure of 23 MPa for 6 h. The thermal behavior of the NR and the different NR/MMA molar ratio grafted copolymer samples was studied by differential scanning calorimetry (DSC). The observed glass transition temperature (T_g) was consistent with the GL. The tensile strength, modulus of elasticity, elongation at break, hardness, and oil resistance of graft copolymers were determined and compared with the values of NR and that of polymerization products prepared in traditional toluene solution. The results showed that the tensile strength, modulus of elasticity, hardness and oil resistance were greatly improved after modification in scCO₂. Copyright © 2007 John Wiley & Sons, Ltd.     

Preparation of poly(methyl methacrylate) microcapsules by in situ polymerization on the surface of calcium carbonate particles

Poly(methyl methacrylate) (PMMA) microcapsules were prepared by the in situ polymerization of methyl methacrylate (MMA) and N,N′-methylenebisacrylamide on the surface of calcium carbonate (CaCO₃) particles, followed by the dissolution of the CaCO₃ core in ethylenediaminetetraacetic acid solution. The microcapsules were characterized using fluorescence microscopy, atomic force microscopy, scanning electron microscopy, and Fourier transform infrared spectroscopy. The average sizes of the CaCO₃ particles and PMMA capsules were 3.8 ± 0.6 and 4.0 ± 0.6 μm, respectively. A copolymer consisting of MMA and rhodamine B-bearing MMA was also used to prepare microcapsules for fluorescent microscopy observations. Fluorescein isothiocyanate-labeled bovine serum albumin was enclosed in the PMMA microcapsules and its release properties were studied.     

Characterization of thin polymer‐like films formed by plasma polymerization of methylmethacrylate: A neutron reflectivity study

The microstructure of the plasma‐polymerized methylmethacrylate (ppMMA) films is characterized using neutron reflectivity (NR) as a function of the plasma reaction time or film thickness. Variation in the crosslink density normal to the substrate surface is examined by swelling the film with a solvent, d‐nitrobenzene (dNB). In the presence of dNB, uniform swelling is observed throughout the bulk as well as at the air surface, and silicon oxide interfaces. The results indicate that the MMA film prepared by plasma polymerization (ppMMA) has a uniform crosslink density from air surface to substrate surface. Additionally, the scattering length density of the plasma‐polymerized MMA film (SLD ≈ 0.750 × 10⁻⁶ Å⁻²) is much lower than that of a conventional PMMA film (SLD = 1.177 × 10⁻⁶ Å⁻²). The increase in film thickness following dNB sorption is 7.5% and at least 36% for the ppMMA and PMMA films, respectively. This suggests that the films formed by plasma polymerization are different from conventional polymers in chemical structure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2522–2530, 2004     

Surface characterization of polybutadiene and natural rubbers oxidized by silver(II)

Silver (II) ion is a powerful oxidizing mediator that was used for surface modification of vulcanized polybutadiene rubber (BR) and natural rubber (NR) through mediated electrochemical oxidation (MEO). Scanning electron microscopy (SEM) pictures showed that surface morphology of the oxidized rubbers was changed so that some cracks and holes appeared on the surface in macroscopic scale. This is possibly due to chain scission caused by alkane group formation which is in turn in accordance with the attenuated total reflection Fourier transform infrared (ATR-FTIR) spectra. The amounts of hydroxyl and carbonyl type surface functional groups were also increased in both oxidized rubbers. The results obtained by atomic force microscopy (AFM) showed that the surface roughness for both rubbers was changed significantly from nano- to micro-scale. Energy dispersive X-ray analysis (EDXA) expresses that surface concentration of atomic oxygen for both BR and NR was increased significantly. Also surface polarity of the treated rubbers was enhanced based on contact angle measurements leading to a higher hydrophilicity. Finally it was found that silver(II) has a somewhat greater oxidation impact on the surface of natural rubber than polybutadiene rubber.     

Chemical degradation of an uncrosslinked pure fluororubber in an alkaline environment

The chemical degradation of an uncrosslinked pure fluoroelastomer (FKM; Viton A) in an alkaline environment (10% NaOH and 80 °C) was investigated. Scanning electron microscopy images showed that on a microscopic level, significant degradation substantially increased the surface roughness after prolonged exposure (e.g., 12 weeks). The molecular mechanisms of the chemical degradation processes at the surface were evaluated with X‐ray photoelectron spectroscopy and attenuated total reflectance/Fourier transform infrared spectroscopy. The results revealed that the early degradation proceeded primarily via dehydrofluorination reactions, creating double bonds in the rubber backbone. This further accelerated the degradation after longer exposure times. Furthermore, the resulting double bonds underwent nucleophilic attack by an aqueous NaOH solution to form several oxygenated species. All these species ultimately recombined to form crosslinks, as evidenced by the increase in the gel fraction and surface hardness (Shore A). The pronounced effect of chemical degradation through a reduction in the thermal stability of the pure FKM rubber upon exposure was also evident from thermogravimetric analysis and differential thermogravimetry. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6216–6229, 2004     

Effect of surface treatment with potassium permanganate on ultra-high molecular weight polyethylene fiber reinforced natural rubber composites

The effects of surface treatment using potassium permanganate on ultra-high molecular weight polyethylene (UHMWPE) fibers reinforced natural rubber (NR) composites were investigated. The results showed the surface roughness and the oxygen-containing groups on the surface of the modified fibers were effectively increased. The NR matrix composites were prepared with as-received and modified UHMWPE fibers added 0–6 wt%. The treated fibers increased the modulus and tensile stress at a given elongation. The tear strength increased with increasing fiber mass fraction, attained maximum values at 4 wt%. The hardness of composites exhibited continuous increase with increasing the fiber content. The dynamic mechanical tests showed that the storage modulus and the tangent of the loss angle were decreased in the modified UHMWPE fibers/NR composites. Several micro-fibrillations between the treated fiber and NR matrix were observed, which meant the interfacial adhesion strength was improved.     

Preparation and Characterization of Chitosan-Coated DBD Plasma-Treated Natural Rubber Latex Medical Surgical Gloves with Antibacterial Activities

The natural rubber latex (NRL) film taken from medical surgical gloves was surface-modified with a dielectric barrier discharge (DBD) plasma treatment under an air environment. The results showed that surface hydrophilicity of the NRL film increased after the plasma treatment due to the presence of oxygen-containing polar groups on the plasma-treated surface. An increase in plasma treatment time increased the surface roughness of the NRL film, and eventually decreased the mechanical properties. From the obtained results, the optimum plasma treatment time of 20?s was chosen. After immersion in a chitosan solution, the amount of chitosan deposited on the plasma-treated NRL film increased with increasing chitosan concentrations. The chitosan coating smoothed the surface of the plasma-treated NRL film and also improved the mechanical properties. The highest antibacterial activities of the chitosan-coated DBD plasma-treated NRL film against both Staphylococcus aureus and Escherichia coli were achieved when a 2?%(w/v) chitosan solution was used for the coating.     

Radiation grafting of methyl methacrylate on radiation crosslinked natural rubber film

Summary Grafting ofmethyl methacrylate (MMA) on radiation crosslinked natural rubber (NR) film has been investigated by mutual radiation grafting. The effect of experimental parameters like radiation dose, dose-rate, additives like acids and inorganic salts, solvents, monomer concentration, cross-linking density of the natural rubber film on the grafting extent has been studied.From the kinetic studies, a kinetic equation showing almost parabolic and linear dependence of grafting on concentration and dose rate, respectively, was deduced.Preliminary thermal stability studies of grafted films indicated that grafting of MMA does not enhance the thermal stability of NR.     

Chemical and nanomechanical analysis of rice husk modified by ATRP-grafted oligomer

Rice husk (RH), an abundant agricultural residue, was reacted with 2-bromoisobutyryl bromide, to convert it to a heterogeneous polyfunctional macroinitiator for Atom Transfer Radical Polymerization (ATRP). The number of active sites placed on the RH surface was small, but they were ATRP active. Non-polar methyl methacrylate (MMA) and polar acrylonitrile (AN) were polymerized from the RH, and a sequential monomer addition was used to prepare an amphiphilic PMMA-b-PAN copolymer on RH surface. FTIR qualitatively confirmed the grafting. Gravimetric and XPS analysis of the different RH surface compositions indicated thin layers of oligomeric PMMA, PAN, and PMMA-b-PAN. The modified surfaces were mapped by nanomechanical AFM to measure surface roughness, and adhesion and moduli using the Derjaguin-Muller-Toropov model. RH grafted with MMA possessed a roughness value of 7.92, and a hard and weakly adhering surface (13.1 GPa and 16.7 nN respectively) while RH grafted with AN yielded a roughness value of 29 with hardness and adhesion values of 4.0 GPa and 23.5 nN. The PMMA-b-PAN modification afforded a surface with a roughness value of 51.5 nm, with hardness and adhesion values of 3.0 GPa and 75.3 nN.     

Radiation-induced grafting polymerization of MMA onto polybutadiene rubber latex

The grafting of methyl methacrylate (MMA) onto polybutadiene rubber latex by the direct radiation method was carried out. The effects of monomer concentration, absorbed dose and dose rate of gamma rays on the grafting yield were investigated. The graft copolymers were characterized by transmission electron microscopy (TEM), FTIR spectroscopy, and differential scanning calorimetry. TEM photographs revealed that the core–shell structures of latex particles are formed at low MMA content, and with the increasing of MMA content, the semi-IPN-like structure with core–shell could be developed due to the high gel fraction of polybutadiene (PBD) seed particles. In addition, infrared analysis confirmed that MMA could be grafted onto PBD molecular chains effectively under appropriate irradiation conditions. The interfacial adhesion between PBD rubber (core) and PMMA (shell) phases could be enhanced with the increase of MMA concentration.     

Chlorination and characterization of natural rubber and its adhesion to nitrile rubber

Chlorinated natural rubber (CNR) vulcanized sheets were prepared by immersing the NR sheets in sodium hypochlorite solution for various chlorination times ranging from 0 to 30 min. The degree of chlorination as indicated by X-ray Absorption Near-Edge Spectroscopy (XANES) implied that the chlorine content increases with the chlorination time from 0 to 10 min then levels off. Atomic Force Microscopy (AFM) showed an evolution of the surface roughness and stiffness. These two properties increased gradually with chlorination time. The bond strength between CNR and nitrile rubber (NBR) also increased gradually. The data showed cohesive failure beginning at 1 min and extending throughout the 30 min of the study. The maximum peel strength was found at 1 min of chlorination time and decreased afterwards. The decrease in peel strength was caused by the increase in surface stiffness of NR that acted as weak boundary layer. The surface stiffness governed the peel strength between NR and NBR.     

Impact modification of thermoplastics by methyl methacrylate and styrene-grafted natural rubber latexes

The preparation and characterization of polymer blends with structured natural rubber (NR)-based latex particles are presented. By a semicontinuous emulsion polymerization process, a natural rubber latex (prevulcanized or not) was coated with a shell of crosslinked polymethylmethacrylate (PMMA) or polystyrene (PS). Furthermore, core–shell latexes based on a natural rubber/crosslinked PS latex semi-interpenetrating network were synthesized in a batch process. These structured particles were incorporated as impact modifiers into a brittle polymer matrix using a Werner & Pfleiderer twin screw extruder. The mechanical properties of PS and PMMA blends with a series of the prepared latexes were investigated. In the case of PMMA blends, relatively simple core (NR)–shell (crosslinked PMMA) particles improved the mechanical properties of PMMA most effectively. An intermediate PS layer between the core and the shell or a natural rubber core with PS subinclusions allowed the E-modulus to be adjusted. The situation was different with the PS blends. Only core–shell particles based on NR-crosslinked PS latex semi-interpenetrating networks could effectively toughen PS. It appears that microdomains in the rubber phase allowed a modification of the crazing behavior. These inclusions were observed inside the NR particles by transmission electron microscopy. Transmission electron photomicrographs of PS and PMMA blends also revealed intact and well-dispersed particles. Scanning electron microscopy of fracture surfaces allowed us to distinguish PS blends reinforced with latex semi-interpenetrating network-based particles from blends with all other types of particles.     

Alkanolamide as an accelerator,filler-dispersant and a plasticizer in silica-filled natural rubber compounds

A feasibility study was carried out on the utilization of Alkanolamide (ALK) on silica reinforcement of natural rubber (NR) by using a semi-efficient cure system. The ALK was incorporated into the NR compound at 1.0, 3.0, 5.0, 7.0 and 9.0 phr. An investigation was carried out to examine the effect of ALK on the cure characteristics and properties of NR compounds. It was found that ALK gave shorter scorch and cure times for silica-filled NR compounds. ALK also exhibited higher torque differences, tensile modulus, tensile strength, hardness and crosslink density of up to 5.0 phr of ALK loading, and then decreased with further increases of ALK loading. The resilience increased with increased ALK loading. Scanning electron microscopy (SEM) micrographs proved that 5.0 phr of ALK in the silica-filled NR compound exhibited the greatest matrix tearing line and surface roughness due to higher reinforcement level of the silica, as well as better dispersion and cure enhancement.