The Effect of Filler Loading and Epoxidation on Paper-Sludge-Filled Natural Rubber Composites

The effect of filler loading and epoxidation on curing characteristics, dynamic properties, tensile properties, morphology, and rubber-filler interactions of paper-sludge-filled natural rubber compounds have been studied. Two different types of natural rubber, SMR L and ENR 50, having 0% and 50% of epoxidation and conventional vulcanization were used. Paper sludge was used as a filler and the loading range was from 0 to 40 phr. Compounding was carried out using a laboratory-sized two-roll mill. The scorch time for both rubber compounds decreased with filler loading. The cure time was found to decrease with increasing filler content for SMR L vulcanizates, whereas for ENR 50, the cure time seemed to be independent of the filler loading. Dynamic properties, i.e., maximum elastic torque, viscous torque, and tan delta, increase with filler loading in both grades of natural rubber. Results also indicate that both rubbers show increment in tensile modulus but inverse trend for elongation at break and tensile strength. However, for a fixed filler loading, ENR 50 compounds consistently exhibit higher maximum torque, modulus at 100% elongation, and modulus at 300% elongation, but lower elongation at break than SMR L compounds. In the case of tensile strength, ENR 50 possesses higher tensile strength than SMR L at 10 to 20 phr, but the difference is quite small at 30 and 40 phr. These findings might be associated with better rubber-filler interaction between the polar hydroxyl group of cellulose fiber and the epoxy group of ENR 50.     

Organoclay Filled Natural Rubber Nanocomposites: The Effects of Filler Loading

Organoclay filled natural rubber (NR) nanocomposites were prepared using a laboratory two-roll mill. The effect of organoclay loading up to 10 phr was studied. The vulcanized nanocomposites were subjected to mechanical, thermal, and swelling tests. The results indicated that the tensile strength and elongation at break reached optimum at 4 phr of organoclay loading, and the incorporation of organoclay increased the tensile modulus and hardness of NR nanocomposites. The thermal degradation was shifted to a higher temperature and the weight loss decreased with incorporation of organoclay. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) were employed to characterize the microstructure of NR nanocomposites. Results from TEM and XRD show the formation of intercalated and exfoliated individual silicate layers of organoclay filled NR nanocomposites particularly at low filler loading (< 4 phr).     

Interaction Between Fumed-Silica and Epoxidized Natural Rubber

Epoxidized natural rubber (ENR)/fumed silica vulcanizates were prepared by mechanical mixing method. Fumed silica content can affect mechanical properties of the composites, and ten parts per hundreds of rubber (phr) fumed silica lead to the best tensile strength. The interaction between ENR and fumed silica was characterized by Kraus equation, crosslink density (tested by NMR), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA) and scanning electron microscope (SEM). The results showed that the dispersion of silica in ENR was better than in natural rubber (NR), hydrogen bond was produced between ENR and fumed-silica in ENR/silica blends, and glass transition temperature of ENR/silica vulcanizate was higher than pure ENR vulcanizate. TGA and DMA confirmed that there was intense interaction between ENR and silica.     

Abrasion Property of Epoxidized Natural Rubber

The abrasion resistance of two grades of epoxidized natural rubber (ENR 25 and ENR 50) and one grade of styrene-butadiene rubber (SBR) were studied using an Akron abrasion tester. An accelerated sulfur vulcanization system with 2-mercaptobenzothiazole (MBT) as the accelerator is used throughout the study. Carbon black (N 330), precipitated silica, and calcium carbonate were chosen as the fillers. The range of sulfur and filler loadings was from 1 to 5 phr and 10 to 50 phr, respectively. Mixing was done on a two-roll mill. Results obtained show that for all the rubbers studied, the volume loss due to abrasion decreases with increasing sulfur loading and passes through a minimum at about 3 phr of sulfur. This observation is attributed to the changes of cross-link types from monosulfidic to polysulfidic crosslink as sulfur concentration is increased. However, further sulfur loading would cause a “tight” cure, thus increasing the abrasion loss. For sulfur loading less than 3 phr, ENR 25 indicates the highest abrasion loss, followed by SBR and ENR 50. For the filled stock, minimum loss is observed at about 35–40 phr of filler. Reinforcing filler such as carbon black exhibits better abrasion resistance than calcium carbonate, a nonreinforcing filler. The abrasion loss increases at higher filler loading due to the dilution effect of fillers. Ozone plays an important role in the abrasion property of unsaturated rubbers, as reflected by the higher abrasion loss in the presence of ozone.     

Preparation and Characterization of Ethylene Vinyl Acetate (EVA)/Natural Rubber (SMR L)/Organoclay Nanocomposites: Effect of Blending Sequences and Organoclay Loading

Ethylene vinyl acetate (EVA)/natural rubber (SMR L)/organoclay thermoplastic elastomer nanocomposites were melt compounded in an internal mixer, Haake Rheometer, at 120°C and 50 rpm rotor speed. In this paper, we demonstrate the effect of different blending sequences and organoclay loading from 2 to 10 phr (parts per hundred resins) on the tensile properties, morphology, thermal degradation, flammability, and water absorption behavior of EVA/SMR L/organoclay nanocomposites. EVA/SMR L/organoclay TPE nanocomposites were prepared by three different blending sequences, and each exhibited different tensile properties. Results indicated that the presence of organoclay increases the tensile properties, resistance toward thermal degradation, resistance to water permeation, and flame retardancy for all the nanocomposites prepared via different blending sequences. However, the optimum results for all the properties studied were achieved when EVA was blended with organoclay first and SMR L was incorporated later into the blend. The optimum organoclay loading was achieved at 2 phr. Results from scanning electron microscopy (SEM) and X-ray diffraction (XRD) studies showed that at 2 phr organoclay loading, nanostructures of individual silicate layers were achieved, whereas at 8 phr organoclay loading, agglomeration was observed. Flammability of the nanocomposites decreased when the organoclay loading increased.     

The Effect of Epoxidized Natural Rubber (ENR-50) or Polyethylene Acrylic Acid (PEA) as Compatibilizer on Properties of Ethylene Vinyl Acetate (EVA)/Natural Rubber (SMR L) Blends

The effect of epoxidized natural rubber (ENR) or polyethylene acrylic acid (PEA) as a compatibilizer on properties of ethylene vinyl acetate (EVA)/natural rubber (SMR L) blends was studied. 5 wt.% of compatibilizer was employed in EVA/SMR L blend and the effect of compatibilizer on tensile properties, thermal properties, swelling resistance, and morphological properties were investigated. Blends were prepared by using a laboratory scale of internal mixer at 120°C with 50 rpm of rotor speed. Tensile properties, thermal properties, thermo-oxidative aging resistance, and oil swell resistance were determined according to related ASTM standards. The compatibility of EVA/SMR L blends with 5 wt.% of compatibilizer addition or without compatibilizing agent was compared. The EVA/SMR L blend with compatibilizer shows substantially improvement in tensile properties compared to the EVA/SMR L blend without compatibilizer. Compatibilization had reduced interfacial tension and domain size of ethylene vinyl acetate (EVA)/natural rubber (SMR L) blends.     

Curing Characteristics,Fatigue and Hysteresis Behaviour of Feldspar Filled Natural Rubber Vulcanizates

Curing characteristics, fatigue, and hysteresis behaviour of feldspar filled SMR L vulcanizates and feldspar filled ENR 50 vulcanizates were studied. Two different types of natural rubber, SMR L and ENR 50 having 0 and 50 mol% of epoxide groups were used. The feldspar filled natural rubber vulcanizates were compared at similar filler loading which were used at 0, 10, 20, and 30 phr of filler loading. The curing characteristics such as scorch time (t ₂) and cure time (t ₉₀) slightly increased with increasing feldspar loading for both rubber vulcanizates. Besides t ₂ and t ₉₀, maximum torque (M _HR) significantly increased for both rubbers with increasing feldspar loading. The fatigue test showed that fatigue life decreased with increasing extension ratio, strain energy and filler loading. As the filler loading increased, the poor wetting of the feldspar by the rubber matrix gave rise to poor interfacial adhesion between filler and rubber matrix. Results also indicate that the vulcanizates with the highest feldspar loading exhibited the highest hysteresis. The feldspar filled SMR L vulcanizates showed higher fatigue life and lower hysteresis compare to feldspar filled ENR 50 vulcanizates.     

Improved cure characteristics and mechanical properties of an epoxidized natural rubber filled with cerium oxide nanoparticles: Influence of epoxide levels and filler loading

In this study, cerium oxide nanoparticles (nanoceria, CeNP) were used as a nanofiller in epoxidized natural rubber with varying epoxide levels, including 25% epoxidation (ENR-25) and 50% epoxidation (ENR-50). Co-precipitation methods were employed to synthesize a pure phase of CeNP with an average particle size of 11.4 ± 2.0 nm. CeNP was characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy. The effect of CeNP loading with 0–3 parts per hundreds of rubber (phr) on the properties of rubber nanocomposites was explored. ENR-25 nanocomposites with 1 phr of CeNP exhibited higher tensile strength and elongation at break compared to ENR-50 nanocomposites. These findings correspond to a lower Payne effect, improved scorch safety, and better processability. The strongest and most effective CeO₂–ENR interactions via silane linkages are expected to outperform sulfur crosslinking in ENR-25 having 1 phr of CeNP. Microstructural evaluation of an ENR-25 sample containing 1 phr of CeNP indicated well-distributed nanofillers in the ENR-25 matrix, indicating that CeNP and ENR-25 appeared to be well-matched. Hardness of all ENR nanocomposites increased with CeNP loading. The cracking resistance, creep properties, and thermal stability of rubber nanocomposites were unaffected by addition of CeNP in the ENR-25 and ENR-50 samples.     

Dependence of Adhesion Properties of Cross-linked Epoxidized Natural Rubber (ENR 25)-Based Pressure-Sensitive Adhesives on Benzoyl Peroxide Loading in the Presence of Gum Rosin and Petroresin Tackifiers

The effect of benzoyl peroxide loading on the adhesion properties of cross-linked epoxidized natural rubber (ENR 25)-based adhesives was studied using gum rosin and petroresin as tackifiers. Toluene and polyethylene terephthalate (PET) were used as solvent and coating substrate, respectively. The adhesion properties were determined by a Lloyd adhesion tester operating at 30 cm min^?1. Results indicate that the loop tack and peel strength of gum rosin and petroresin pass through a maximum value at 2 parts per hundred parts of rubber (phr) and 3 phr benzoyl peroxide concentration, respectively, an observation which is attributed to the optimum cross-linking of ENR 25 where optimum, cohesive and adhesive strength is obtained. The shear strength, however, increases steadily with increasing benzoyl peroxide loading due to the steady increase in the cohesive strength. At the optimum benzoyl peroxide concentration, the petroresin-based adhesive consistently exhibits higher adhesion properties compared to that of gum rosin-based adhesives. The adhesion properties of both adhesive systems increase with increasing coating thickness.     

Blends of Epoxidized Natural Rubber with Chloroprene Rubber

Blends of ENR (epoxidized natural rubber) with CR (chloroprene rubber) were prepared throughout the composition, and important properties of the vulcanizates, both unaged and aged (air and oil) rubber, were determined. Dynamic measurement showed a single tan δ peak for the blends, and the peak temperature monotonically decreased with increasing CR content, resulting also in an increase of resilience at room temperature. Flex crack resistance of CR above room temperature, and oil resistance of ENR were increased in the blends.     

Dependence of Peel Adhesion on Molecular Weight of Epoxidized Natural Rubber

The effect of molecular weight of two grades of epoxidized natural rubber (ENR)—i.e., ENR 25 and ENR 50—on the peel strength of an adhesive is studied using coumarone-indene resin, gum rosin, and petro resin as tackifiers. Toluene and polyethylene terephthalate (PET) film acted as the solvent and substrate, respectively. A SHEEN hand coater was used to coat the adhesive on the substrate to give coating thicknesses of 30, 60, 90, and 120 µm. The peel strength of adhesive was determined using a Lloyd Adhesion Tester operating at 30 cm/min. Results show that peel strength has a maximum value at a molecular weight of 6.8 × 10⁴ and 3.9 × 10⁴ for ENR 25 and ENR 50, respectively, an observation which is attributed to the combined effects of wettability and mechanical strength of the rubber at the respective optimum molecular weight of ENR. Peel strength increases with coating thickness for all the tackifiers investigated, with a gum rosin-based adhesive exhibiting the highest peel strength.     

Influence of interfacial compatibilizer,silane modification,and filler hybrid on the performance of NR/NBR blends

The effects of epoxidized natural rubber (ENR) as a compatibilizer, silane in situ modification, and filler hybrid on the properties of natural rubber/acrylonitrile–butadiene rubber blends were systematically studied. Phase change with the incorporation of ENR was quantitatively characterized via atomic force microscope quantitative nanomechanics technique. The results show that ENR could greatly reduce the dispersed domain size and increase the interfacial thickness; however, this compatibilizing effect reached the limit when ENR content was 5 parts per hundred rubber (phr). If the content is further increased, the redundant ENR start to gather at the interface and thus form a third phase. The macroscopic dynamic performance measurement was well in accordance with the microscale observation; the blend with 5 phr of ENR presented the lowest heat generation. The results also revealed that silane modification could significantly improve the overall properties, which benefited from better filler dispersal as evidenced by transmission electron microscopy. Finally, the effect of filler hybrid [silica and carbon black (CB)] was studied. It turned out that the blend containing 20 phr silica and 32 phr CB synchronously possessed high wet grip property, low rolling resistance, and high wear resistance, which makes it very promising for the high-performance tire application. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47421.     

Preparation and Electron Beam Irradiation of PVC/ENR/CNTs Nanocomposites

Poly (vinyl chloride), PVC/epoxidized natural rubber blend, ENR/carbon nanotubes, CNTs nanocomposites were prepared using melt intercalation and solution blending methods. In both preparation methods PVC: ENR: CNTs ratios were fixed at 50:50:2, while the 50/50 PVC/ENR blend without the addition of CNTs was used as control. The PVC/ENR/CNTs nanocomposites were exposed to electron beam (EB) irradiation at doses ranging from 0–200 kGy. The effects of two different preparation methods on the tensile properties, gel fraction and morphology of the PVC/ENR/CNTs nanocomposites were studied. Prior to EB irradiation, the addition of 2 phr of CNTs caused a drop in the tensile strength (Ts) of the 50/50 PVC/ENR blend, implying poor distribution of CNTs in the PVC/ENR blend matrix. However upon EB irradiation, the nanocomposites prepared by the melt blending method exhibited higher values of Ts as compared to the neat PVC/ENR blend due to occurrence of radiation-induced cross-linking in the PVC/ENR blend matrix. Transmission electron microscopy (TEM) images proved that a better dispersion of CNTs in PVC/ENR blend matrix can be achieved by melt intercalation compared to solution blending and the dispersion of CNTs was improved by irradiation. Scanning electron microscopy (SEM) results showed a distinct failure surface with formation of rough structure for the irradiated nanocomposites, which explains the higher values of tensile properties compared to the non-irradiated nanocomposites.     

环氧化天然橡胶复合材料性能研究

采用新方法制备环氧化天然橡胶(ENR)/白炭黑和天然橡胶(NR)/ENR/白炭黑复合材料,并对其性能进行研究。结果表明:ENR/白炭黑复合材料的热稳定性优于ENR;在NR/ENR并用胶中加入白炭黑和硅烷偶联剂KH-550,NR/ENR/白炭黑复合材料0℃时的损耗因子(tanδ)增大,65℃时的tanδ值减小,复合材料的抗湿滑性能提高,滚动阻力减小。     

Thiol Addition to Epoxidized Natural Rubber: Effect on the Tensile and Thermal Properties

Epoxidized natural rubber (ENR) samples of various epoxidation degrees were synthesized from natural rubber (NR) latex, and 25 mole% epoxide of ENR was used to prepare ENR room temperature-curable films for coating applications. The films were prepared from rubber solutions. Trimethylolpropane tris(2-mercaptoacetate) (TMP-SH) was used as a curing agent. The effect of the thiol additive on the tensile and thermal properties of epoxidized natural rubber (ENR) was investigated. For the sake of comparison, NR and TMP-SH-containing formulations were also prepared.

It was observed that the addition of TMP-SH improved the tensile, thermal and swelling properties of ENR, indicating the formation of crosslinks. On the other hand, the addition of TMP-SH didn't improve the properties of NR, indicating the absence of reaction with TMP-SH. On the basis of data on the properties of the ENR films of this work it is demonstrated that these are appropriate for coating applications.     

Adhesion Property of Benzoyl-Peroxide-Cured Epoxidized Natural Rubber/Acrylonitrile-Butadiene Rubber Blend Adhesives to Polyethylene Terephthalate Film

The loop tack, peel strength and shear strength of cross-linked epoxidized natural rubber (ENR-50)/acrylonitrile-butadiene rubber (NBR) blend adhesives were studied in the presence of coumarone-indene resin. Benzoyl peroxide was used as the cross-linking agent with dosage ranging from 1 to 5 parts per hundred rubber by weight (phr). Toluene was used as the solvent throughout the investigation. A SHEEN hand coater was used to coat the adhesive on a polyethylene terephthalate substrate at 60 and 120 μm coating thickness. The adhesive was cured at 80°C for 30 min prior to testing on a Lloyd adhesion tester operating at various testing rates from 10 to 60 cm min^?1. Results show that loop tack and peel strength of the ENR-50/NBR adhesives pass through a maximum value at 4 phr of benzoyl peroxide dosage. This observation is attributed to the increase in cohesive strength which culminates at 4 phr benzoyl peroxide loading. However, shear strength increases steadily with dosage of benzoyl peroxide due to the continuous increase in the cohesive strength as crosslinking of the rubber blend proceeds. In all cases, the adhesion properties increase with increasing coating thickness and testing rates.     

The Effect of Silica on the Peel Adhesion of Epoxidized Natural Rubber-Based Adhesive Containing Coumarone-Indene Resin

The peel strength of silica filled on two grades of epoxidized natural rubber (ENR), i.e., ENR 25 and ENR 50 adhesive were investigated using coumarone-indene as the tackifying resin. Toluene was used as the solvent throughout the study. Result shows that peel strength increases with increase in silica loading due to the concentration effect of the filler. Peel strength, however, shows maximum value at 40 phr silica for both ENR 25 and ENR 50 an observation that is attributed to the maximum wettability and compatibility of adhesive on the substrate.     

Thermal properties and aging characteristics of chemically modified oil palm ash-filled natural rubber composites

The chemically modified oil palm ash (OPA) with the cetyltrimethylammonium bromide (CTAB) solution was prepared prior to compounding with the natural rubber and other curing ingredients. The aging resistance and thermal stability of CTAB-modified OPA-filled natural rubber composites were evaluated in the same manner as non-modified OPA samples. The retention tensile properties after thermal aging was measured and based on the result shown, the CTAB-modified OPA-filled natural rubber composites imparted insignificant effect to aging resistance as compared to the non-modified OPA-filled natural rubber composites at very low OPA loading; however, the effect became apparent beyond 3 phr OPA loading where the CTAB-modified OPA-filled natural rubber composites provided better aging resistance than the corresponding non-modified OPA-filled natural rubber composites. The thermogravimetric analysis indicated that the CTAB-modified OPA-filled natural rubber composites exhibited lower thermal stability which showed lower temperature at their respective weight loss and lesser char residue than that of non-modified OPA-filled natural rubber composites. This was attributed to the CTAB which started to decompose at the temperature of 210 °C. However, for the range from ambient temperature to 210 °C, the CTAB-modified OPA-filled natural rubber composites produce better thermal stability than those of non-modified OPA-filled natural rubber composites.     

Properties of Ferrite-Filled Natural Rubber Composites

Nickel zinc ferrite (Ni-ZnFe₂O₄)-filled natural rubber (NR) composite was prepared at various loading of ferrite. The tensile properties included in this study were tensile strength, tensile modulus and elongation at break. The tensile strength and elongation at break of the composites increased up to 40 parts per hundred rubber (phr) of ferrite and then decreased at higher loading whereas the tensile modulus was increased gradually with increasing of ferrite loading. Scanning electron microscopy (SEM) was used to determine the wettability of filler in rubber matrix. From the observation, the increase of filler loading reduced the wettability of the filler. Thermal stability of the composites was conducted by using a thermogravimetry analyser (TGA). The incorporation of ferrite in NR composites enhanced the thermal stability of NR composites. The swelling test results indicate that the swelling percentage of the composites decreased by increasing of ferrite loading. The initial permeability, μ_i and quality factor, Q of magnetic properties of NR composites achieved maximum value at 60 phr of ferrite loading for frequency range between 5000–40,000 kHz. The maximum impedance, Z _max of the NR composites was at the highest value at 80 phr ferrite loading for frequency range between 200–800 MHz.     

Improvement of Physicochemical Properties of Natural Rubber and Polyvinyl Alcohol Blends by Radiation Vulcanization

Variable compositions of natural rubber latex (NRL) and polyvinyl alcohol (PVA) have been blended. The contents of PVA in the blends were varied from 0.5 phr to 3.0 phr and the total solids contents of NRL was fixed to 50%. The blends were irradiated at different irradiation doses (0–20 kGy) in the presence of normal butylacrylate (n-BA). The permanent set; swelling ratio and elongation at break point of the blended films at all compositions decrease with the increase of radiation doses whereas increase is observed in cross-linking density, gel content, tensile strength and modulus. Sharp changes of all the properties were observed between 3–5 kGy radiation doses. On the other hand, at higher radiation doses, ≥ 5 kGy, the permanent set, swelling ratio, gel content did not show any appreciable change whereas cross-linking density, tensile strength, modulus and elongation at break point are changed. The maximum cross-linking density of blend is observed with 2.0 phr PVA at 12 kGy radiation. The highest value of modulus and tensile strength of the same blend are found at 10 kGy and 5 kGy respectively. Blends with 2.0 phr PVA for all compositions proved to be optimum for improving varies properties at 5–12 kGy radiation doses.