Modification Of Rubber Research Articles

MODIFIKASI KOPOLIMER KARET ALAM SIKLIS GRAFTING ASAM OLEAT MENGGUNAKAN INISIATOR BENZOIL PEROKSIDA DAN BAHAN PENGISI BENTONIT-CETIL TRIMETIL AMONIUM BROMIDA

Research on the modification of Cyclic Natural Rubber (CNR) grafting Oleic Acid (OA) copolymer using initiator of Benzoyl Peroxide (BPO) and the filler of bentonite-Cetil Trimethyl Ammonium Bromide (CTAB) has been carried out, which aims to determine the method of modifying Cyclic Natural Rubber (CNR) and Oleic Acid (OA) so it can produce CNR-g-OA copolymer through grafting method with BPO initiator mixed together with bentonite-CTAB. This research was conducted in three stages. The first stage is the process of dissolving CNR using xylene. The second stage is the process of mixing CNR solution and OA with the composition (70:30) phr, followed by the addition of BPO initiator and bentonite-CTAB filler. The third stage is characterization using FTIR and Scanning Electron Microscopy (SEM). The results of the analysis using FT-IR showed an absorption at 1708,23 cm-1 which indicated the presence of C=O bonds from oleic acid which had been grafted on CNR, and increased intensity after addition of bentonite-CTAB at 1568,96 cm-1; 1446,13 cm-1; 1255,66 cm-1; and 866,94 cm-1. Characterization results using SEM showed that the mixing of Bentonite-CTAB in KAS-g-OA was evenly distributed and quite homogeneous.

Modification of Asphalt Rubber with Nanoclay towards Enhanced Storage Stability.

Asphalt rubber (AR), which is prepared by blending crumb rubber and bitumen, provides various advantages, including superior rutting resistance, lower road-tire noise and longer service life. However, contractors have expressed concerns regarding its poor storage stability, which in turn limits its wider application. This study aims to address the storage stability concern by incorporating nano-montmorillonite (nanoclay). Three types of nanoclay were dispersed into hot AR binder by high shear blending. The rheological properties of nanoclay-crumb rubber modifier (CRM)-modified bitumen were evaluated through Superpave performance grade (PG) tests and the storage stability was characterized by measuring the difference in softening points or complex moduli at the top and bottom portions of binders after lab-simulated storage. X-ray diffraction (XRD) evaluation was conducted to observe the variation of nanoclay layer gap distance for mechanism investigation. It was found that all selected nanoclays had insignificant effects on workability, rutting and fatigue properties. The layered nanoclay transformed to intercalated or exfoliated structures after interaction with bitumen fractions, providing superior storage stability. Among the three selected nanoclays, pure montmorillonite with Na+ inorganic group, which has an intermediate hydrophilic property and middle layer gap, showed the most obvious effect on enhancing the storage stability of AR.

Superhydrophobic micro-nano structures on silicone rubber by nanosecond laser processing

This paper demonstrates laser surface modification of silicone rubber using an economic and efficient nanosecond fibre laser. The resulting surface morphology shows that micro-nano structures leading to an increase in the surface slope were formed after processing. The effect of laser power on the surface wettability was investigated demonstrating that the contact angle of the silicone rubber surface increased with increasing laser fluence. The water contact angle on the treated surface reached ~160° with a rolling-off angle of ~3° when the laser fluence reached 10 J cm−2. After laser processing, both the roughness and root mean square slope of the silicone rubber surface increased with increasing fluence and reached maximum at a fluence of 10 J cm−2. An analysis of the pre- and post processing surfaces suggested there were no significant compositional changes, but there were some micro-structural changes to the polymer chain, namely, cleavage of the Si–O–Si bonds. It is thus proposed that the hierarchical micro-nano structures and hence the change in the root mean square slope of the silicone rubber surface induced by laser irradiation are the primary reasons for its superhydrophobicity. The preparation of superhydrophobic silicone rubber can have important applications in self-cleaning, anti-icing, and anti-pollution.

Chemical modification of nitrile rubber in the latex stage by functionalizing phosphorylated cardanol prepolymer: A bio-based plasticizer and a renewable resource

The present investigation deals with the functionalization of acrylonitrile butadiene rubber (NBR) by chemically grafting phosphorylated cardanol prepolymer (PCP) onto its backbone chain. The grafting of PCP onto NBR was accomplished in the latex stage successfully using benzoyl peroxide as the free radical initiator. The functionalized NBR (PCP- g-NBR) is characterized by ultraviolet–visible spectroscopy, Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, and gel permeation chromatography. PCP- g-NBR exhibited an increase in molecular weight (4.4%) with an increase in the polydispersity. The grafting parameters have been optimized using “Taguchi L9table” and the optimum conditions were found to be “3 phr of initiator concentration, 15 phr of the PCP concentration, reaction temperature of 70°C and reaction time of 6 h.” The percentage grafting and grafting efficiency were calculated to be 7.28 and 80.37%, respectively, under optimum processing conditions. The PCP- g-NBR exhibited a reduction in Wallace plasticity number as well as the Mooney viscosity and an enhanced plasticity retention index (PRI) as compared to neat NBR. The rheological measurements exhibited a higher flow behavior index for PCP- g-NBR than the NBR itself. Differential scanning calorimetry and dynamic mechanical analysis results exhibited a decrease in glass transition temperature on functionalization of NBR confirming enhanced plasticization. Thermogravimetric analysis results displayed an increase in thermal stability of the functionalized NBR than that of virgin NBR. The physico-mechanical properties of the PCP- g-NBR vulcanizates were at par with or even better than the neat NBR vulcanizates. 3-(4,5-Dimethylthiazol-2yl)-2,5-diphenyltetrazolium bromide assay and hemolysis studies indicated NBR and PCP- g-NBR are nontoxic and biocompatible.

Grafting of glycerol methacrylate onto silicone rubber using γ-rays: derivatization to 2-oxoethyl methacrylate and immobilization of lysozyme

Abstract

Effect of urea deproteinization on catalytic hydrogenation of natural rubber latex

Natural rubber is unsaturated biopolymer which has low resistance to heat, oxygen, and ozone. Chemical modification of natural rubber by catalytic hydrogenation can improve its oxidative property. In this study, the catalytic hydrogenation of natural rubber was investigated in latex phase after reduction of protein content with urea. Hydrogenation of deproteinized natural rubber latex was performed by using diimide which generated insitu from hydrazine hydrate/hydrogen peroxide and catalyst (boric acid, cupric sulfate and cupric acetate) at 70°C for 5 h. The hydrogenation system was stabilized with sodium dodecyl sulphate. The hydrogenation of deproteinized natural rubber (HDPNR) was confirmed by FTIR analysis. The result indicated that cupric sulphate was extremely active catalyst which was showed by the elimination of C=C transmittance bands at 1660 cm-1 on HDPNR spectra and highest degree of hydrogenation. Furthermore, urea deproteinization increased possibility of side reactions during catalytic hydrogenation as seen on the reduction of gel content compared to undeproteinized natural rubber.

Physicochemical properties of liquid natural rubber bearing fluoro groups for hydrophobic surfaces

The modification of liquid natural rubber (LNR) has attracted interests among chemists as it brings improvements to several of its properties and widens its application to various fields. LNR can be modified into fluorinated LNR (F-LNR) which is of interest to industries due to its remarkable properties, including low surface energies, high thermal stabilities, together with its significant hydrophobic characters. In this work, a new route to prepare fluorinated rubber was presented. Hydroxylated LNR (OH-LNR) was initially synthesized in good yield via oxidation in the presence of tungsten complex catalyst and acetic acid with hydrogen peroxide as an oxidant. The optimum hydroxyl content of 57.0% was obtained within 6 h reaction time at 90 °C. In the second step, the esterification of OH-LNR using pentadecafluorooctanoyl chloride (PDFOC) under mild conditions was conducted, leading to LNR bearing fluoro groups in the side chain of LNR (F-LNR). ATR-FTIR spectroscopy was used to elucidate the structure and determine any changes in the functional groups that may have been induced during the reaction. 1H NMR spectroscopy was employed to reveal that a high fluorine content of 48.6% was obtained using 3:1 molar ratio of OH-LNR:PDFOC for 8 h at 50 °C. The microstructure of F-LNR was further analyzed using 19F NMR and 13C NMR spectroscopies, and the results confirmed the presence of fluorine in LNR. Thermogravimetric analyses also indicated that the modification improved thermal stability of the LNR. Contact angle measurements were also conducted to verify the hydrophobicity of the fluorinated rubber and the results obtained showed that F-LNR exhibited higher hydrophobicity than LNR.

High-performance natural rubber nanocomposites with marine biomass (tunicate cellulose)

Due to the importance in economic and environmental benefits, marine biomass has gained increasing attention in recent years. In this work, marine biomass-based materials were prepared and characterized. Highly reinforcing cellulose nanocrystals (CNCs) with length of 1–2 μm and aspect ratio of ~75 were extracted from tunicates (t-CNCs), and CNCs with length of 100–300 nm and aspect ratio of ~15 from cotton (c-CNCs) were presented for comparison. In order to enhance interfacial interactions between CNCs and rubber, modification of natural rubber (NR) was conducted via epoxidation reaction to obtain epoxidized NR (ENR). Fully bio-based rubber nanocomposites were produced by latex mixing. Compared with NR nanocomposites, hydrogen bonding formed between ENR and CNCs, which led to homogeneous dispersion of CNCs and enhanced interfacial adhesion between them. Moreover, t-CNCs with longer length and larger aspect ratio facilitate filler entanglements, which led to higher reinforcing efficiency. Consequently, both hydrogen bonding and filler entanglements contributed to the improved mechanical properties of ENR/t-CNCs nanocomposites.

Modification of liquid silicone rubber by octavinyl-polyhedral oligosilsesquioxanes and silicon sol

To develop an efficient and bio-compatible way to improve the thermal and mechanical properties of addition type liquid silicone rubber (LSR), a series of modified LSR samples were prepared by introducing octavinyl-polyhedral oligosilsesquioxanes (VPOSS) and high purity silicon sol singly or in combination before vulcanization. Significant correlation was found between the loading rate of VPOSS and thermal properties. However, mechanical properties were negatively correlated with VPOSS content within the range experimented, which may be ascribed to material defect caused by uneven distribution and aggregation. Furthermore, test results approved that the introducing of silicon sol indeed affected the stabilities of the polymer by restraining the material defect caused by the aggregation of POSS molecules and improving cross link density. For example, adding 10%-20% of silicon sol into VPOSS(1.0%) modified LSR will increase tear resistance by 43.9%-85.7%, elongation at break by 31.7%-57.3%, residue at 800 °C in N2 atmosphere by 32.0%-37.9%, residue at 650 °C in air atmosphere by 70.9%-91.6%, respectively. This work proves that, to incorporate VPOSS into LSR by hydrosilylation, and to use silicon sol as dispersant and reinforce filler can become an efficient way to improve the mechanical property, thermal stability and bio-compatibility of LSR in the future.

Chemical Modification of Butyl Rubber with Maleic Anhydride via Nitroxide Chemistry and Its Application in Polymer Blends.

Butyl rubber (isobutylene–isoprene–rubber, IIR) was functionalized in solution with a nitroxide moiety taking advantage of the unsaturations present in the isoprene units of IIR, and was further grafted with maleic anhydride (MA) or styrene–MA (SMA) to produce IIR-g-MA and IIR-g-SMA. In one of the functionalization techniques used, the molecular structure of the IIR was preserved as the chain-breaking reactions are prevented from occurring. The resulting graft copolymers were tested as compatiblizers/impact modifiers blended with Nylon-6, and one of them was preliminarily tested as a coupling agent in the preparation of nanocomposites of IIR and an organo-clay. Blends of PA-6/IIR-g-MA exhibited a significant increase in impact resistance at increasing loads of the modified IIR, as well as a good rubber particle dispersion in the polyamide matrix. On the other hand, the performance of IIR-g-SMA as an impact modifier of PA, or as a coupling agent in the preparation of rubber-organoclay nanocomposites, is marginal.

Modification of Natural Rubber as a Resistant Material to Dimethyl Ether

Modification of Natural Rubber as a Resistant Material to Dimethyl Ether

Surface Modification of Natural Rubber by Sulfur hexafluoride (SF6) Plasma Treatment: A New Approach to Improve Mechanical and Hydrophobic Properties

Plasma treatments have faced growing interest as important strategy to modify the hydrophobic/hydrophilic characteristics of materials. However, challenges related to the plasma modification of polymers are the improvement of the chemical resistance without decreasing the mechanical resistance. In this letter, we present for the first time a plasma treatment, using Sulfur hexafluoride (SF6), analogous to vulcanization process, of natural rubber surface, which resulted in a chemical and tension resistance improvements. The natural rubber membranes were coated with glow discharge plasmas generated in sulfur hexafluoride (SF6) atmospheres at a total pressure of 160 mTorr and applying 70 W of radiofrequency. Plasma treatment increases the contact angles from 64° to 125° i.e. leading to a hydrophobic surface. The tension at rupture increased from 3.7 to 6.1 MPa compared to natural rubber without plasma treatment demonstrated by stress-strain investigation. These results provide a fast alternative approach to improve mechanical and chemical properties of rubber-based products.

PROPERTIES OF NR AND NR/ENR BASED RUBBER COMPOUNDS REINFORCED WITH CHOPPED AND SIZED CARBON FIBER

High elasticity, mechanical resistance and antivibration characteristic s of natural rubber (NR) are essential issue in the main area of vehicle tyres and high modulus demanding bearing applications. In this study, especially in bearing applications, where natural rubber modulus properties are limited, natural rubber has been reinforced with chopped and hydrocarbon sized carbon fiber to get improved tensile modulus. Besides, epoxidized natural rubber (ENR), which was produced by chemical modification of natural rubber, blended with NR and the compounds have been reinforced with epoxy sized carbon fiber. NR and NR/ENR based rubber compounds’ rheological, mechanical, and aging properties have been systematically investigated and evaluated.

Properties of Epoxidized Natural Rubber Tread Compound: The Hybrid Reinforcing Effect of Silica and Silane System

Modification of natural rubber via epoxidation process increases its compatibility with highly polar filler like silica. In this work, epoxidized natural rubber (ENR) reinforced with silica compound is evaluated for truck tire tread compound. The rheological, physical and dynamic properties as well as the bound rubber content of ENR-silica tread compound are discussed. The results show that ENR-silica compound has high chemically bound rubber indicating the good interaction and bonding between rubber and silica. In addition, the dynamic test shows the ENR-silica vulcanizate exhibit higher Tan delta at 0 °C and lower tan delta at 60 °C as compared to conventional natural rubber-carbon black vulcanizate, which gives indication of higher wet grip and lower rolling resistance of the ENR vulcanizate. The use of ENR reinforced with silica filler in tread compound is a unique combination that offers renewable material for greener tire application.

Biofunctionalization of silicone rubber with microgroove-patterned surface and carbon-ion implantation to enhance biocompatibility and reduce capsule formation.

PurposeSilicone rubber implants have been widely used to repair soft tissue defects and deformities. However, poor biocompatibility can elicit capsule formation, usually resulting in prosthesis contracture and displacement in long-term usage. To overcome this problem, this study investigated the properties of silicone rubber materials with or without a microgroove-patterned surface and with or without carbon (C)-ion implantation.Materials and methodsAtomic force microscopy, X-ray photoelectron spectroscopy, and a water contact angle test were used to characterize surface morphology and physicochemical properties. Cytocompatibility was investigated by a cell adhesion experiment, immunofluorescence staining, a Cell Counting Kit-8 assay, and scanning electron microscopy in vitro. Histocompatibility was evaluated by studying the inflammatory response and fiber capsule formation that developed after subcutaneous implantation in rats for 7 days, 15 days, and 30 days in vivo.ResultsParallel microgrooves were found on the surfaces of patterned silicone rubber (P-SR) and patterned C-ion-implanted silicone rubber (PC-SR). Irregular larger peaks and deeper valleys were present on the surface of silicone rubber implanted with C ions (C-SR). The silicone rubber surfaces with microgroove patterns had stable physical and chemical properties and exhibited moderate hydrophobicity. PC-SR exhibited moderately increased dermal fibroblast cell adhesion and growth, and its surface microstructure promoted orderly cell growth. Histocompatibility experiments on animals showed that both the anti-inflammatory and antifibrosis properties of PC-SR were slightly better than those of the other materials, and there was also a lower capsular contracture rate and less collagen deposition around implants made from PC-SR.ConclusionAlthough the surface chemical properties, dermal fibroblast cell growth, and cell adhesion were not changed by microgroove pattern modification, a more orderly cell arrangement was obtained, leading to enhanced biocompatibility and reduced capsule formation. Thus, this approach to the modification of silicone rubber, in combination with C-ion implantation, should be considered for further investigation and application.

Developing the Surface Chemistry of Transparent Butyl Rubber for Impermeable Stretchable Electronics.

Transparent butyl rubber is a new elastomer that has the potential to revolutionize stretchable electronics due to its intrinsically low gas permeability. Encapsulating organic electronic materials and devices with transparent butyl rubber protects them from problematic degradation due to oxygen and moisture, preventing premature device failure and enabling the fabrication of stretchable organic electronic devices with practical lifetimes. Here, we report a methodology to alter the surface chemistry of transparent butyl rubber to advance this material from acting as a simple device encapsulant to functioning as a substrate primed for direct device fabrication on its surface. We demonstrate a combination of plasma and chemical treatment to deposit a hydrophilic silicate layer on the transparent butyl rubber surface to create a new layered composite that combines Si-OH surface chemistry with the favorable gas-barrier properties of bulk transparent butyl rubber. We demonstrate that these surface Si-OH groups react with organosilanes to form self-assembled monolayers necessary for the deposition of electronic materials, and furthermore demonstrate the fabrication of stretchable gold wires using nanotransfer printing of gold films onto transparent butyl rubber modified with a thiol-terminated self-assembled monolayer. The surface modification of transparent butyl rubber establishes this material as an important new elastomer for stretchable electronics and opens the way to robust, stretchable devices.

Electron and probe microscopy investigation of the surface of elastomers modified with antifriction fillers

The surface of frost-resistant elastomers (rubbers) based on nitrile-butadiene rubber and propylene- oxide rubber (pure and modified with fillers: ultrafine PTFE and carbon black) is investigated. Tribological tests show that the addition of carbon black produced the greatest effect: the friction coefficient decreases to 0.2 and remains virtually constant during cooling. Surface and subsurface defects are detected by SEM. These defects can affect the processes in the zone of friction and destruction of the sliding surface of rubber. It is demonstrated that the modification of propylene-oxide rubber results in surface smoothing; the effect is the most pronounced in the samples modified with carbon black. The potential to use scanning probe microscopy for local investigation of the surface of rubber is assessed. A conclusion is made about the adhesive properties of surfaces based on the obtained force–distance curves. The investigation of vibration parameters of a probe in contact with the surface provides an opportunity to estimate the surface elasticity. It is shown that the addition of carbon black results in an increase in hardness of the rubber samples and a drastic reduction in adhesion. At the same time, the introduction of ultrafine PTFE leads to a slight enhancement of the adhesion and hardness. It is concluded that carbon black is the best modifying additive for the studied elastomers.

Modification of liquid silicone rubber by octavinyl‐polyhedral oligosilsesquioxanes

ABSTRACTTo develop an efficient, simple, and biocompatible method for improving the thermal and mechanical properties of an addition‐type liquid silicone rubber (LSR), octavinyl‐polyhedral oligosilsesquioxane (OPOSS) modified LSR samples were prepared through the addition of 0.5–4.0 wt % OPOSS as a modifier to a platinum‐based silicone curing system before vulcanization. The characterization and measurement of the OPOSS and LSR samples were carried out by Fourier transform infrared spectroscopy, X‐ray diffraction, NMR, gas chromatography/mass spectrometry (electron impact ionization), scanning electron microscopy, thermogravimetric analysis/differential scanning calorimetry, and universal testing. The experimental results show that the crosslinking of the OPOSS and LSR polymer had a significantly positive effect on the thermal and mechanical properties. Compared with the unmodified sample, its tensile strength was enhanced by 423–508%, its tear resistance was increased from 22 to 44%, the residue at 600 °C was increased by 36–75% in an N2 atmosphere and 8–65% in an air atmosphere, respectively. These results were obviously superior to those from other similar reported methods that used larger molecular or nonreactive polyhedral oligosilsesquioxane (POSS) derivatives as modifiers at similar POSS loadings. Furthermore, a significant correlation was found between the loading rate of OPOSS and the thermal properties. However, the mechanical properties seemed negatively correlated with the OPOSS content within the experimental range; this may have been due to a material defect caused by the uneven distribution and agglomeration. The results of this study proved that the incorporation of OPOSS into an LSR polymer matrix by a hydrosilylation reaction could be an efficient way to improve the mechanical properties, thermal stability, and biocompatibility of LSR in the future. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43906.

Surface modification of crumb rubber and its influence on the mechanical properties of rubber-cement concrete

In this paper, a surface modification method was proposed to introduce strong polarity groups to rubber surface to generate a strong chemical bond between the rubber and the cement matrix. Rubber was first oxidized with KMnO4 solution and then sulphonated with NaHSO3 solution. The Fourier transform-infrared (FT-IR) spectra and contact angle measurement showed that the oxidation and sulphonation process introduced a large number of hydrophilic hydroxyl and sulfonate to crumb rubber and decreased the contact angle between rubber surface and water, thus greatly improved the interfacial bonding strength between crumb rubber and cement paste. After the rubber surface modification, the adhesion strength of the rubber and cement paste was increased by 41.1%. It was also found in the mechanical tests that the rubber surface modification was quite useful to enhance the compressive strength and impact strength of rubber-cement concrete. The compressive strength of the concrete with 4% modified rubber powder was 48.7% higher than that with ordinary rubber powder. Based on the results, it is concluded that the surface modification of crumb rubber with KMnO4 and NaHSO3 solutions is an effective method to improve the mechanical properties of rubber-cement concrete.

RTV silicone rubber surface modification for cell biocompatibility by negative-ion implantation

A negative cluster ion implantation system was built on the injector of a GIC4117 tandem accelerator. Next, the system was used to study the surface modification of room temperature vulcanization silicone rubber (RTV SR) for cell biocompatibility. The water contact angle was observed to decrease from 117.6° to 99.3° as the C1− implantation dose was increased to 1×1016ions/cm2, and the effects of C1−, C2− and O1− implantation result in only small differences in the water contact angle at 3×1015ions/cm2. These findings indicate that the hydrophilicity of RTV SR improves as the dose is increased and that the radiation effect has a greater influence than the doping effect on the hydrophilicity. There are two factors influence hydrophilicity of RTV: (1) based on the XPS and ATR-FTIR results, it can be inferred that ion implantation breaks the hydrophobic functional groups (SiCH3, SiOSi, CH) of RTV SR and generates hydrophilic functional groups (COOH, OH, Si(O)x (x=3,4)). (2) SEM reveals that the implanted surface of RTV SR appears the micro roughness such as cracks and wrinkles. The hydrophilicity should be reduced due to the lotus effect (Zhou Rui et al., 2009). These two factors cancel each other out and make the C-implantation sample becomes more hydrophilic in general terms. Finally, cell culture demonstrates that negative ion-implantation is an effective method to improve the cell biocompatibility of RTV SR.