Acrylic rubber‐fluorocarbon rubber miscible blends: Effect of curatives and fillers on cure,mechanical, aging,and swelling properties

The cure characteristics and mechanical properties of gum and filled acrylic rubber (ACM), fluorocarbon rubber (FKM), and their blends of varying compositions were studied both under unaged and aged conditions. The rheometric study showed that optimum cure properties were obtained using a mixed curing system of blocked diamine, hexamethylenediamine carbamate (Diak #1), and ammonium benzoate. From varying the curing agents, the optimum levels of Diak #1 and ammonium benzoate were found to be 1.5 and 2.5 phr, respectively. The addition of different fillers and their loading influenced the cure properties, with increased torque and reduced scorch safety. The gum and filled 50:50 (w/w) ACM‐FKM showed overall performance in strength properties. Postcuring improved the strength of all the systems, especially the systems with a higher proportion of FKM. None of the properties changed significantly during aging of the blends. FKM and the blends containing a higher proportion of FKM were affected least by aging. Swelling of the blends was reduced by the addition of fillers. Dynamic mechanical thermal analysis showed a single tan δ peak corresponding to a single phase transition for both cured and filled blends. The storage modulus of the blend increased from the gum blend to the filled blend, indicating the presence of polymer‐filler interaction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1442–1452, 2003     

A comparative study of aging characteristics and thermal stability of oil palm ash,silica, and carbon black filled natural rubber vulcanizates

Filler‐filled natural rubber (NR) vulcanizates were prepared by conventional laboratory‐sized two roll mills and cured using sulfuric system. The effect of thermal aging on physical properties and thermogravimetric analysis (TGA) of oil palm ash (OPA) and commercial fillers (i.e., silica vulkasil C and carbon black N330)‐filled NR vulcanizates at respective optimum loading and equal loading were studied. Before aging, the OPA‐filled vulcanizates showed comparable optimum strength as carbon black‐filled vulcanizates. The hardening of aged filler‐filled NR vulcanizates happened after aging, thereby tensile strength and elongation at break reduced while the modulus increased. Fifty phr carbon black‐filled vulcanizates showed better retention in tensile properties as compared to silica (10 phr) and OPA (1 phr). This was attributed to the addition of different filler loading and this finding was further explained when equal loading of filler‐filled vulcanizates was studied. Fourier transform infra‐red analysis showed chemical structure had changed and tensile fractured surface exhibited smooth appearance due to the deterioration in tensile properties after aging. TGA also denoted the thermal stability was depending on the amount of filler loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4474–4481, 2013     

Curing characteristics,morphology, thermal stability,mechanical properties,and irradiation resistance of methylethylsilicone/methylphenylsilicone rubber blends

Methylethylsilicone rubber (MESR)/methylphenylsilicone rubber (MPSR) blends were cured with 2,5‐dimethyl‐2,5‐di(tert‐butylperoxy)hexane. The curing characteristics, morphology, thermal behaviors, mechanical properties at different temperatures, radiation resistance, and thermal aging resistance of the MESR/MPSR blends were investigated. The results show that a high MPSR content could decrease the optimum curing time and improve the scorch safety. Dynamic mechanical analysis revealed that the glass‐transition temperature of the blends increased slightly with the addition of MPSR. Scanning electron microscopy showed that MESR and MPSR had good compatibility in the blends. Thermogravimetric analysis indicated that the thermal stability of the blends increased with increasing quantity of MPSR. The blends had excellent mechanical properties at low temperatures. However, these properties were significantly reduced when the temperature was increased. Moreover, changes in the mechanical properties decreased with increasing MPSR content at high temperatures, especially at temperatures higher than 100°C. In addition, the radiation resistance and thermal aging resistance of the blends increased with increasing MPSR content. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40529.     

Effects of fillers,maleated ethylene propylene diene diene rubber,and maleated ethylene octene copolymer on phase morphology and oil resistance in natural rubber/nitrile rubber blends

The phase morphology and oil resistance of 20/80 NR/NBR blends filled with different types of fillers and copolymers were investigated. In the case of filler effect, N220, N330, and N660 carbon blacks with different particle sizes were used. Additionally, the blends filled with nonblack‐reinforcing fillers, that is, precipitated and silane‐treated silica, were investigated. To study the compatibilization effect, maleated ethylene propylene diene rubber (EPDM‐g‐MA) and maleated ethylene octene copolymer (EOR‐g‐MA) were added to the blends. The results revealed that the addition of filler, either carbon black or silica, to the blend caused a drastic decrease in NR dispersed phase size. Carbon blacks with different particle sizes did not produce any significant difference in NR dispersed phase size under the optical microscope. Silica‐filled blends showed lower resistance to oil than did the carbon black–filled blends. In addition, it was determined that neither EOR‐g‐MA nor EPDM‐g‐MA could act as a compatibilizer for the blend system studied. The oil resistance of the blends with EPDM‐g‐MA is strongly affected by the overall polarity of the blend. In the case of EOR‐g‐MA, the oil resistance of the blends is significantly governed by both overall polarity of the blend and phase morphology. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1156–1162, 2003     

Biopolymers as effective fillers in natural rubber: Composites versus biocomposites

Biocomposites of natural rubber (NR) blends were prepared with a variety of fillers obtained from renewable resources by a mastication technique. They were characterized for their mechanical properties and morphologies and compared with composites of the conventional filler carbon black (c‐black). The biopolymers exhibited an interesting trend and imparted strength to NR that was quite comparable to c‐black. Up to 30 phr of the fillers could be successfully incorporated; this led to enhancements in the mechanical strength. The properties were found to vary with the type and ratio of filler, namely, starch, cellulose, and chitin. The optimum mechanical strength of the biocomposites was observed at 10 phr. The results were interpreted on the basis of the morphology by scanning electron microscopy, which revealed strong filler–polymer interactions. The moisture‐uptake characteristics of the composites were studied. It was found that addition of biofillers did not lead to a significant increase in the moisture absorption. Furthermore, as the adhesion between the polymer matrix and fillers increased, the water uptake decreased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Swelling and mechanical properties of (acrylonitrile‐butadiene rubber)/(hydrogenated acrylonitrile‐butadiene rubber) blends with precipitated silica filled in gasohol fuels

This work studied the effects of hydrogenated acrylonitrile‐butadiene rubber (HNBR) and precipitated silica (PSi) loadings in acrylonitrile‐butadiene rubber (NBR) filled with 60 parts per hundred of rubber (phr) of carbon black (CB) for oil‐resistant seal applications in contact with gasohol fuel. The cure characteristics, mechanical properties, and swelling behavior of HNBR/NBR blends reinforced with PSi before and after immersion in ethanol‐based oils (E10, E20, and E85) were then monitored. This work studied the effects of PSi loading in rubber compounds on the mechanical properties of the rubber blends. The results suggested that the scorch time of CB‐filled NBR/HNBR was not affected by HNBR loading, but the cure time, Mooney viscosity, and torque difference increased with HNBR content. The swelling of the blends in E85 oil were relatively low compared with those in E10 and E20 oils. The recommended NBR/HNBR blend ratio for oil‐resistant applications was 50/50. Tensile strength and elongation at break before and after immersion in gasohol oils increased with HNBR loading, and the opposite effect was found for tensile modulus and hardness. PSi filler had no effect on scorch time, but decreased the cure time of the blends. The swelling level of the blends slightly decreased with increasing PSi content. The recommended silica content for optimum reinforcement for black‐filled NBR/HNBR blend at 50/50 was 30 phr. The results in this work suggested that NBR/HNBR blends reinforced with 60 phr of CB and 30 phr of silica could be potentially used for rubber seals in contact with gasohol fuels. J. VINYL ADDIT. TECHNOL., 22:239–246, 2016. © 2014 Society of Plastics Engineers     

The effect of interface characteristics on the static and dynamic mechanical properties of three‐component polymer alloys

The effect of interfacial characteristics on the structure‐property relationships of ternary polymer alloys and blends comprising polypropylene (PP), ethylene‐vinyl alcohol copolymer (EVOH) and glass beads (GB) or fibers (GF) was investigated. The systems studied were based on a binary PP/EVOH immiscible blend, representing a blend of a semi‐crystalline apolar polymer with a semi‐crystalline highly polar copolymer. The ternary systems studied consisted of filler particles encapsulated by EVOH, with some of the minor EVOH component separately dispersed within the PP matrix. Modification of the interfacial properties was done using silane coupling agents for the EVOH/glass interface and compatibilization using a maleic anhydride grafted PP (MA‐g‐PP) for the PP/EVOH interface. Both glass fillers increased the dynamic modulus and decreased the damping of the neat polymers and of their binary blends, especially in the rubbery region. GF has a more profound effect on both the modulus and the damping. Glass surface treatments and compatibilization have only a marginal effect on the dynamic mechanical behavior of the ternary blends. Yet, compatibilization shifted the polymers' T_gS to higher temperatures. Both glass fillers increased the elastic modulus of the binary blends, where GF performed better than GB as a reinforcing agent. GF slightly increased the strength of the binary blends while, GB reduced it. Both fillers reduced the ductility of the binary blends. The blends' mechanical properties were related to the morphology and their components' crystallinity. The compatibilizer increases both stiffness and strength and reduces deformability.     

Kinetics of the thermal degradation and thermal stability of conductive silicone rubber filled with conductive carbon black

The kinetics of the thermal degradation and thermal stability of conductive silicone rubber filled with conductive carbon black was investigated by thermogravimetric analysis in a flowing nitrogen atmosphere at a heating rate of 5°C/min. The rate parameters were evaluated by the method of Freeman–Carroll. The results show that the thermal degradation of conductive silicone rubber begins at about 350°C and ends at about 600°C. The thermal degradation is multistage, in which zero‐order reactions are principal. The kinetics of the thermal degradation of conductive silicone rubber has relevance to its loading of conductive carbon black. The activation energies are temperature‐sensitive and their sensitivity to temperature becomes weak as temperature increases. In addition, the conductive silicone rubber filled with conductive carbon black has better thermal stability than that of silicone rubber without any fillers. Also, conductive silicone rubber filled with conductive carbon black has better thermal stability than that of silicone rubber filled with the same amount of silica. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1548–1554, 2003     

Carbon black filled powdered natural rubber: Preparation,particle size distribution,mechanical properties,and structures

Carbon black (HAF) filled powdered natural rubber (P(NR/HAF)) was prepared and the particle size distribution, mechanical properties, and micromorphology of P(NR/HAF) were studied. A carbon black–rubber latex coagulation method was developed for preparing carbon black filled free‐flowing, noncontact staining NR powders with particle diameter less than 0.9 mm. A powdering mechanism model was put forward to describe the powdering process, which shows that the key technical points consist in the surfactant with good emulsification properties and the polymer coating resin with good film forming properties. SEM analysis shows that carbon black and rubber matrix have formed a macroscopic homogenization in the P(NR/HAF) particles without contact staining, and carbon black particles are well dispersed in rubber matrix with diameter of about 50–150 nm. P(NR/HAF) vulcanizate showed better mechanical properties than bale natural rubber/carbon black blends (NR/HAF) and simple NR latex/carbon black blends (NRL/HAF), which depends primarily upon the absence of free carbon black, the fine dispersion of filler on the rubber matrix, and the better interaction between carbon black and rubber matrix due to the proper preparation condition of noncontact staining carbon black filled powdered NR. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1763–1774, 2006     

Dielectric and mechanical properties of natural nanofibers‐reinforced ethylene propylene diene rubber: Carrot foliage and corn gluten

A study has been carried out to investigate the dielectric and mechanical properties of composites based on reinforcing carrot foliage (CF) and corn gluten meal (CGM) as by‐products of food processing units into ethylene propylene diene rubber matrix. Transmission electron microscope micrographs indicate that both types of fillers are in the nanoscale. The permittivity ε′ and dielectric loss ε″ were measured in the frequency domain and at room temperature ～ 25°C. The increase in ε′ and ε″ by increasing filler content is due to its reinforcing nature which was found to be more pronounced in case of CF than CGM. The mechanical properties are found to increase in the same manner. The values obtained for ε′ and ε″recommend such composites to be used in the electrical insulation purposes. The analysis of composite morphology indicated that at low concentration both types of fillers are fine distributed in the EPDM matrix, whereas at higher filler loading aggregation of filler is clearly appeared. The composites under investigation are found to be highly thermal aging resistant as both electrical and mechanical properties are slightly affected by such aging. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Effects of radiation pretreatments on the rubber adsorption power and reinforcing properties of fillers in rubber compounds

Radiation damage to fillers such as carbon black, graphite and silica induced by high doses of γ‐radiation or neutrons dramatically increases their ability to adsorb rubber irreversibly. In fact, the ‘bound rubber’, ie the amount of non‐extractable rubber which remains irreversibly linked to the filler matrix, increases dramatically in radiation‐treated fillers. The increased adsorption power of radiation‐damaged fillers has been attributed to the formation of a higher concentration of surface defects in the form of trapped free radicals, fullerene‐like structures and other kinds of defects. The mechanical properties of rubber compounds filled with radiation‐treated carbon blacks show a significant increase in their reinforcing effects, in line with the increased ability to form ‘bound rubber’. © 2001 Society of Chemical Industry     

Synergistic effect of plasma‐modified halloysite nanotubes and carbon black in natural rubber—butadiene rubber blend

Halloysite nanotubes (HNTs) were investigated concerning their suitability for rubber reinforcement. As they have geometrical similarity with carbon nanotubes, they were expected to impart a significant reinforcement effect on the rubber compounds but the dispersion of the nanofillers is difficult. In this work, HNTs were surface‐modified by plasma polymerization to change their surface polarity and chemistry and used in a natural rubber/butadiene rubber blend in the presence of carbon black. The aim of the treatment was to improve the rubber–filler interaction and the dispersion of the fillers. A thiophene modification of HNTs improved stress–strain properties more than a pyrrole treatment. The surface modification resulted in a higher bound rubber content and lower Payne effect indicating better filler–polymer interaction. Scanning electron microscopy measurements showed an increased compatibility of elastomers and fillers. As visualized by transmission electron microscopy, the thiophene‐modified HNTs formed a special type of clusters with carbon black particles, which was ultimately reflected in the final mechanical properties of the nanocomposites. The addition of HNTs increased loss angle. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Use of ground pistachio shell as alternative filler in natural rubber/styrene–butadiene rubber‐based rubber compounds

Bio‐based polymers and fillers draw a significant interest. Focus of this work is to use ground pistachio shell as alternative filler in a model natural rubber/styrene–butadiene rubber‐based conveyor belt compound. Compounds were prepared using a laboratory two‐roll mill by partial replacing of carbon black with pistachio shell. Cure characteristics, mechanical, thermal, morphological, and abrasion properties of pistachio shell containing vulcanizates have been studied. Increasing pistachio shell loading causes lower cure extent and lower tensile strength. However, abrasion resistance is significantly improved by incorporation of pistachio shell. Benefits of using pistachio shell as filler may include producing low price, environmentally friendly, and high abrasion resistant vulcanizates when some loses in tensile properties can be tolerated. POLYM. COMPOS., 35:245–252, 2014. © 2013 Society of Plastics Engineers     

Effect of fillers on morphological properties in NR/SBR blends for OTR tyres

Abstract

The blends of styrene butadiene rubber (SBR) and natural rubber (NR) are prepared using a two-roll mixing mill in the presence of different types of carbon blacks as reinforcing filler. The effects of fillers on cure characteristics and thermal, dynamic–mechanical, morphological properties of the blends are studied. The ISAF N231 type of carbon black shows a significant effect on tensile, tear and modulus properties by reacting at the interface between SBR/NR matrixes. The dynamic characteristics and storage modulus of SBR/NR with SAF N110 and SRF N774 types of carbon black show distinct characteristics in respect to all other blends in this system. The thermal stability of the rubber vulcanizates containing SAF N110 and SRF N774 types of carbon blacks is higher than other blend types. With the increasing percentage of SBR to NR, the thermal stability of the blend is increased. However, the heat buildup of the blends increases with the increase in SBR percentage.     

Electron beam modification of filled fluorocarbon rubber

The effect of electron beam irradiation on the properties of carbon black‐, silica‐, and clay‐filled fluorocarbon rubber has been studied over a range of radiation doses, loadings, and nature of the fillers. Compared to the unfilled irradiated rubber, the tensile strength and modulus improve with a decrease in the particle size of the carbon black filler. Similar improvement in these properties is observed with an increase in both the radiation dose and the amount of the filler upto a certain level. The dynamic mechanical analysis reveal an increased glass transition temperature (T_g), a reduced value of the mechanical loss factor at T_g. and an enhanced dynamic storage modulus for the filled samples. The results are explained with the help of sol‐gel analysis and volume fraction of rubber. It is observed that higher reinforcement in the case of the filled vulcanizate is obtained by electron beam modification, as compared to that using the conventional curing system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 2016–2025, 2000     

Effect of different types of filler and filler loadings on the properties of carboxylated acrylonitrile–butadiene rubber latex films

The effects of different types of fillers and filler loadings on the properties of carboxylated nitrile rubber (XNBR) latex were identified. Silica, mica, carbon black (CB; N330), and calcium carbonate (CaCO₃) were used as fillers with filler loadings of 10, 15, and 20 parts per hundred rubber. Furnace ashing and Fourier transform infrared analysis proved that interaction existed between the fillers and XNBR latex films. The morphology of the filled XNBR films was significantly different for different types of fillers. Mica and CaCO₃ fillers showed uneven distribution within the XNBR film, whereas other fillers, such as silica and CB, showed homogeneous distribution within the films. In the observation, silica and mica fillers also illustrated some degree of agglomeration. The mechanical properties (e.g., tensile and tear strengths) showed different trends with different types of fillers used. For silica and mica fillers, the mechanical properties increased with filler loadings up to a certain loading, and decreased with higher filler loadings. For CB filler, the mechanical properties increased gradually with increasing filler loadings. CaCO₃ fillers did not increase the mechanical properties. The crosslinking density of the XNBR films increased when they were incorporated with fillers because of the presence of elastomer–filler and filler–filler interactions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Guayule natural rubber composites: impact of fillers on their cure characteristics,dynamic and mechanical behavior

Guayule natural rubber (GNR) is an alternative resource of Hevea natural rubber (HNR) with 99.9% cis content in its 1,4-polyisoprene chemical backbone. In this study, compounds were formulated independently with four different reinforcing fillers such as carbon black (HAF), precipitated silica (VN3), fume silica (FUM) and nanofly ash (NFA) for the advancement of GNR based products. The cure characteristic, dynamic-mechanical performance and mechanical properties of GNR composite were studied with the reinforcing effect of different fillers on GNR. The cure characteristic results demonstrated that HAF and FUM silica filled compounds had more processing safety than VN3 and NFA filled compounds. Viscoelastic parameters of the vulcanizates were studied by dynamic mechanical analysis to estimate the glass transition characteristics and dynamic behavior. The higher storage modulus of FUM silica vulcanizate was an indication of superior filler reinforcing nature and improved rolling resistance than other filled systems. Additionally, HRTEM analysis also proved the better filler dispersion ability of FUM silica in GNR matrix. The mechanical properties were studied with a variation of each filler loading of 8, 16, and 32 phr in GNR vulcanizates. The tensile strength of each filled system increased with an increase of filler content from 8 to 32 phr. In comparison, FUM silica GNR vulcanizates exhibited better mechanical properties, therefore, it was considered as a better structure-performance composite than those of HAF, VN3 and NFA filled composites.

     

石墨及其表面改性对硅橡胶导热性能的影响

用双辊混炼机将导热填料分散到聚甲基乙烯基硅氧烷中,再配以增强剂、硫化剂等,经模压硫化制得导热硅橡胶。研究了导热填料种类、石墨的表面改性和用量以及石墨与炭黑的复配对硅橡胶导热性和力学性能的影响。结果表明,在用量相同的情况下,导热填料的导热系数越高,其填充硅橡胶的导热性越好,且硅橡胶的导热系数随导热填料用量的增加而增大。石墨的表面改性改善了石墨与硅橡胶的界面相容性,使硅橡胶的力学性能和导热性都得到提高。不同粒径及颗粒形态的炭黑与石墨复合可改善硅橡胶的导热性和力学性能,导热硅橡胶的拉伸强度和扯断伸长率随复合填料中炭黑用量的增加而提高,当石墨与炭黑质量比为25/5时,硅橡胶的导热系数最高,综合性能较好。     

Mechanical and dynamic mechanical properties of rice husk ash–filled natural rubber compounds

A laboratory‐sized two‐roll mill was used to incorporate rice husk ash into natural rubber (NR). A conventional vulcanization system was used for curing and cure studies were carried out on a Monsanto rheometer. Physical testing of the NR vulcanizates involved determining tensile and tear resistances and hardness. Swelling behavior of NR compounds and scanning electron microscopy were used to investigate the interaction between rice husk ash and natural rubber. Also, dynamical mechanical thermal analysis was used to assess filler–rubber interactions in terms of storage modulus (E′) and loss tangent (tan δ). For comparison purposes, two commercial fillers, precipitated silica (Zeosil‐175) and carbon black (N774), were also used. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2331–2346, 2002     

Improvement in thermal conductivity and mechanical properties of ethylene‐propylene–diene monomer rubber by expanded graphite

Thermally conductive fillers are usually employed in the preparation of rubber composites to enhance thermal conductivity. In this work, ethylene‐propylene‐diene monomer rubber (EPDM)/expanded graphite (EG) and EPDM/graphite composites with up to 100 phr filler loading were prepared. Compared to EPDM/graphite compounds with the same filler loading, stronger filler network was demonstrated for EPDM/EG compounds. Thermal conductivity and mechanical properties of EPDM/graphite and EPDM/EG composites were compared and systematically investigated as a function of the filler loading. The thermal conductivity of both EPDM/graphite and EPDM/EG composites increased with increasing volume fraction of fillers, and could be well fitted by Geometric Mean Model. The thermal conductivity as high as 0.910 W · m⁻¹ · K⁻¹ was achieved for the EPDM/EG composite with 25.8 vol% EG, which was ∼4.5 times that of unfilled EPDM. Compared to EPDM/graphite composites, EPDM/EG composites exhibited much more significant improvement in thermal conductivity and mechanical properties, which could be well correlated with the better filler‐matrix interfacial compatibility and denser structure in EPDM/EG composites, as revealed in the SEM images of tensile fracture surfaces. POLYM. COMPOS., 38:870–876, 2017. © 2015 Society of Plastics Engineers