Dynamic mechanical properties of styrene‐butadiene composites reinforced by defatted soy flour and carbon black co‐filler

Carboxylated styrene‐butadiene (SB) composites reinforced by a mixture of defatted soy flour (DSF) and carbon black (CB) were investigated in terms of their dynamic mechanical properties. DSF is an abundant renewable commodity and has a lower cost than CB. DSF contains soy protein, carbohydrate, and whey. Aqueous dispersions of DSF and CB were first mixed and then blended with SB latex to form rubber composites using freeze‐drying and compression molding methods. At 140°C, a single filler composite reinforced by 30% DSF exhibited roughly a 230‐fold increase in the shear elastic modulus compared to the unfilled SB rubber, indicating a significant reinforcement effect by DSF. Mixtures of DSF and CB at three different ratios were investigated as co‐fillers. Temperature sweep experiments indicate the shear elastic moduli of the co‐filler composites are between that of DSF and CB composites. Strain sweep experiments were used to study the fatigue and recovery behaviors of these composites. Compared with the DSF composites, the recovery behaviors of the 30% co‐filler composites after the eight consecutive deformation cycles of dynamic strain were improved and similar to that of 30% CB composite. Strain sweep experiments also indicated that the co‐filler composites have a greater elastic modulus than the CB reinforced composites within the strain range measured. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Flow properties of natural rubber composites filled with defatted soy flour

The linear and nonlinear viscoelastic properties of natural rubber composites reinforced with defatted soy flour (DSF) were studied. DSF is an abundant, renewable commodity, and its rigid nature makes it suitable as a reinforcement phase in rubber composites. At small strain, the elastic modulus of a 30% filled composite was about 20 times higher than the unfilled rubber. Greater reinforcement was observed for carbon black filled composites than for DSF filled composites at filler concentrations of 10 and 20%. At high strain, values of the relaxation modulus dropped more rapidly for highly filled DSF composites. At high shear rates in a capillary viscometer, a small reinforcement effect remained for all composites, and lower die swell was observed for DSF composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Characterization of defatted soy flour and elastomer composites

Defatted soy flour (DSF) is an abundant renewable commodity and is more economically favorable then soy protein isolate or soy protein concentrate. DSF contains soy protein, soy carbohydrate, and soy whey. The aqueous dispersion of DSF was blended with styrene‐butadiene latex to form elastomer composites. The inclusion of soy carbohydrate increased the tensile stress in the small strain region, but reduced the elongation at break. The shear elastic modulus of the composites showed an increase in the small strain region, consistent with its stress‐strain behavior. The inclusion of soy carbohydrate and soy whey also improved the recovery behavior in the nonlinear region. At small strain, the shear elastic modulus of 30% filled composites at 140°C was about 500 times higher than that of the unfilled elastomer, indicating a significant reinforcement effect generated by DSF. Compared with soy protein isolate (SPI), the stress softening effect and recovery behavior under dynamic strain indicate the addition of soy carbohydrate and soy whey may have increased the filler‐rubber interaction. In general, the DSF composites gave better mechanical properties compared with the protein composites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 353–361, 2005     

Microwave absorbing rubber composites containing carbon black and aluminum powder

Natural rubber (NR), epoxidized natural rubber (ENR), and chlorosulfonated polyethylene (CSM) composites filled with conductive carbon black and aluminum powder have been prepared by using a two‐roll mill. An electromagnetic interference shielding effectiveness of those rubber composites was carried out in the frequency range of 8–12GHz (X‐band microwave). The increase of filler loading enhanced shielding effectiveness of the rubber composites. Conductive carbon black was more effective in shielding than aluminum powder. Binary filler‐filled rubber composites showed higher shielding effectiveness than that of single filler‐filled rubber composites. It has been observed that the shielding effectiveness of these rubber composites could be ranked in the following order: ENR ≥ CSM > NR, whereas the mechanical properties of the rubber composites were in the order of CSM > ENR > NR. The correlation between shielding effectiveness and electrical conductivity as well as mechanical properties of the rubber composites are also discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Reinforcement effect of biomass carbon and protein in elastic biocomposites

Biomass carbon (BC) and soy protein (SP) were used to reinforce natural rubber (NR) biocomposites. The particle size of BC was reduced and characterized with elemental analysis, X‐ray diffraction, infrared spectroscopy, and particle size analysis. The rubber composite reinforced with the BC/SP and the composite reinforced with the BC of higher carbon content show useful tensile properties at an optimum filler fraction. The model analysis of the stress–strain behaviors provides insight into filler network characteristics. For the highly filled composites, the BC have less constraint on the polymer chains as shown by the temperature and frequency dependent modulus as well as the model analysis of stress softening effect. The presence of NR protein improves the filler–polymer adhesion for the composites reinforced with BC/SP. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

混炼方式对螺旋纳米碳纤维增强天然橡胶复合材料力学性能的影响

采用干法和湿法两种混炼工艺制备了螺旋纳米碳纤维(HCNFs)/炭黑(CB)/天然橡胶(NR)复合材料,通过扫描电镜、拉伸试验机和应变扫描仪分别对所制备复合材料的界面形貌、力学性能和Payne效应进行了测试分析,考察了混炼方式对复合材料宏观力学性能及Payne效应的影响。结果表明,与纯CB填料相比,在干湿两种混炼方式下,添加适量的HCNFs(1～6份)能提高HCNFs/CB/NR复合材料的300%定伸应力、扯断伸长率、拉伸强度和硬度。与干法混炼相比,湿法混炼能明显增强HCNFs/CB/NR复合材料的Payne效应,并提升在HCNFs高添加量(2～6份)条件下的拉伸强度和扯断伸长率,这主要源于湿法混炼能够有效改善HCNFs在橡胶基质中的分散性。     

Synergistic reinforcement of nanoclay and carbon black in natural rubber

The synergistic reinforcement of nanoclay (NC) and carbon black (CB) in natural rubber (NR) has not been much studied. Therefore, the reinforcement mechanism was probed using synchrotron wide‐angle X‐ray diffraction and transmission electron microscopy (TEM) observation and analyzed in terms of tube model theory. A synergistic effect in reinforcement between NC and CB was proved by the marked enhancement in tensile strength from 11.4 MPa for neat NR to 28.2 MPa for NR nanocomposite with 5 wt% NC and 20 wt% CB. From a study of crystallization under deformation it was found that crystallization plays a less important role in the reinforcement of NR/NC/CB. Analysis using tube model theory provided more evidence for the synergistic effect. NR containing a combination of NC and CB exhibited an increase of topological tube‐like constraints in comparison with NR/CB. That is to say, in NR/NC/CB nanocomposites, a CB–NC local filler network, as indicated by TEM images, induced a more entangled structure in which mobility of rubber chains was hindered for lateral fluctuations by the presence of neighboring chains. The synergistic reinforcement of NC and CB in NR/NC/CB nanocomposites can be reasonably understood as due to the formation CB–NC local filler networks. Copyright © 2010 Society of Chemical Industry     

Effective thermal conductivity of three‐phase styrene butadiene composites

Transient plane source technique was used for the simultaneous measurement of thermal conductivity and thermal diffisivity of three‐phase styrene butadiene rubber composites. Two series of styrene butadiene rubber composites were studied, having natural rubber as a variable filler in both the composites along with 10 phr of silica and clay, respectively. The measurements were done at room temperature and normal pressure. The experimental results show that there is a small variation in the thermal conductivity of both the composites with the filler (NR) fraction. It is interesting to note that the thermal conductivity shows a sharp decrease at 10 phr filler loading and then increases. The comparative study of these composites shows that the conductivity as well as the diffusivity of the silica reinforced composites is larger than that of the clay composites. The thermal conductivity of the filler NR has been evaluated using the Agari model. It has also been found that the composite with 40 phr of NR has the maximum thermal conductivity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1799–1803, 2000     

Comparative study on the natural rubber nanocomposites reinforced with carbon black nanoparticles and graphite oxide nanosheets

To achieve dramatic improvements in the performance of natural rubber (NR), the graphite oxide nanosheets (GON)‐reinforced NR nanocomposites have been prepared through solution mixing on the basis of pretreatment of graphite. The mechanical and thermal properties of GON/NR nanocomposites were characterized in contrast to the carbon black (CB)/NR nanocomposite. The mechanical properties of the GON‐reinforced NR showed a considerable increase compared to the neat NR and traditional CB/NR nanocomposite. The initial modulus of pure NR was increased for up to 53.6% when 7 wt% GON is incorporated. The modulus and strength of NR with GON appear to be superior to those of CB with the same filler content. The dispersion state of the nanofillers into NR was investigated by scanning electron microscopy and X‐ray diffraction, and the results indicated that nanofillers have been dispersed homogeneously in the NR matrix. Fourier transform infrared spectra showed possible interfacial interactions between fillers and NR matrix. Differential scanning calorimetry and thermogravimetric analysis showed that the T _g and thermal decomposition temperature of NR slightly increased with the addition of the fillers, especially for that of GON/NR nanocomposites. According to this study, application of the physical and mechanical properties of GON to NR can result in rubber products which have improved mechanical, physical, and thermal properties, compared with existing NR products reinforced with CB. POLYM. COMPOS., 38:1427–1437, 2017. © 2015 Society of Plastics Engineers     

炭黑/煤矸石/碳纳米管复合填料体系对天然橡胶性能的影响研究*

利用硝酸氧化法对碳纳米管(CNTs)进行纯化,并用环氧天然橡胶(ENR)进行改性处理。结合胶质量分数测定结果表明, ENR用量15%(质量)时效果最佳。采用胶乳凝聚法制备CNTs/天然橡胶(NR)母料。煤矸石粉(CG)经高温煅烧和表面改性处理。 将CNTs/天然橡胶(NR)母料、CG和炭黑(CB)通过机械混炼法与天然橡胶及配合剂混合,制备CB/CG/CNTs/NR复合材料,并对复合材料进行硫化特性及物理机械性能。结果表明： CNTs延迟硫化效应明显;相比炭黑,CG对硫化具有促进作用。硫化特性和甲苯溶胀法测定结果表明,在填料份数相同的条件下,单独由CB填充的NR有最大的交联密度,CNTs对交联密度影响不明显。物理机械性能测试结果表明,当CG：CB：CNTs=17.5:16.5:1(Phr)时,NR硫化胶的300%定伸应力和扯断伸长率明显高于单独由CB填充NR,而拉伸强度与之接近,复合填料样填充NR具有较好的综合性能。扫描电镜测试结果表明,复合填料在NR基体中分布均匀。     

Aggregate structure and effect of phthalic anhydride‐modified soy protein on the mechanical properties of styrene‐butadiene copolymer

The aggregate structure of phthalic anhydride (PA) modified soy protein isolate (SPI) was investigated by estimating its fractal dimension from the equilibrated dynamic strain sweep experiments. The estimated fractal dimensions of the filler aggregates were less than 2, indicating that these particle aggregates have a distorted or broken two‐dimensional sheet‐like structure. The results also indicated that the aggregate structure has a greater effect on the composite reinforcement than the overall aggregate size. Tensile strength, elongation, Young's modulus, and toughness of hydrolyzed/modified soy composites are comparable with those of carbon black reinforced composites at 10–15% filler fraction. The moduli of PA‐modified SPI composites were less sensitive to the pH of the composite preparation compared to the unmodified SPI. The composites prepared at acidic pH, with lower filler fraction, or filled with hydrolyzed/modified SPI are more elastic and less fatigue. The composites of PA‐modified SPI had better recovery properties when prepared at acidic instead of alkali pH. PA‐modified hydrolyzed SPI composites prepared at acidic pH showed a similar recovery property to that of carbon black reinforced composites, but with greater shear elastic moduli. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and properties of styrene‐butadiene rubber nanocomposites blended with carbon black‐graphene hybrid filler

Graphene has become an attractive reinforcing filler for rubber materials, but its dispersion in rubber is still a big challenge. In this work, a novel carbon black‐reduced graphene (CB‐RG) hybrid filler was fabricated and blended with styrene‐butadiene rubber (SBR) via simple two‐roll mill mixing. The prepared CB‐RG hybrids had a microstructure with small CB agglomerates adsorbed onto graphene surfaces. CB acted as a barrier preventing the RG sheets from restacking even after drying. Homogeneous dispersion of graphene sheets in SBR matrix was observed by the mechanical mixing method based on the application of the CB‐RG hybrid fillers. Dynamic mechanical analysis showed that Tg of the SBR/CB‐RG blend was higher than that of the SBR/CB blend indicating strong interfacial interactions between RG and SBR due to the high surface area of graphene and the π‐π interaction between SBR and graphene. The tensile properties of SBR/CB‐RG composites improved significantly and the volume resistivity decreased compared with the SBR/CB blends. The thermal stability of SBR composites filled with CB and CB‐RG showed slight difference. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41309.     

Effect of modification conditions of coal gangue on properties of natural rubber composites

The purpose of this work is to study the reinforcement effect of modified coal gangue (CG) on natural rubber (NR); carbon black (CB) was taken as reference filler. The addition of CG and CB to NR with the total filler loading fixed at 35 phr. The orthogonal experiment was employed to reveal the modification conditions on reinforcing properties. The results show that modification conditions such as weight ratio of coupling agent (CA), calcining temperature (CT), and calcining time (CM) affect the strengthening properties of CG, and CA is the most important factor influencing the tensile strength of NR, the order of influence can be expressed as CA > CT > CM. The optimum modification conditions are CT 800°C, CM 1 hr, and CA 2%. 300% modulus of NR composites filled with modified CG (17.5 phr)/CB (17.5phr) hybrid filler is similar to NR filled with CB alone at same filler loading, while elongation at break increases significantly for existent of CG. The effect of heat treatment and modification conditions of CG were tested by particle size distribution, scanning electron microscopy, Fourier transform infrared spectra, and X‐ray diffraction. The results show that the specific surface area of CG increased and hydroxyl group in crystal structure of CG removed under heat treatment. Dynamic mechanical analysis results show that the storage modulus and tan δ of CG filled NR composites are higher while T_g is less than that of CB, indicating the existence of a strong and stiff interface between filler and NR matrix. POLYM. COMPOS., 35:1911–1917, 2014. © 2014 Society of Plastics Engineers     

Effect of carbon black/nanoclay hybrid filler on the dynamic properties of natural rubber vulcanizates

In this study, natural rubber (NR) nanocomposites based on carbon black (CB) and two poly(ethylene glycol) (PEG)‐modified clay hybrid filler were fabricated. The morphology and mechanical properties were studied. The dynamic properties of NR vulcanizates were investigated over a range of strain amplitude at two temperatures. It was found that NR with hybrid filler exhibits superior mechanical properties over that with CB as single phase filler. The hybrid filler causes a significant alteration in the dynamic properties of rubber. The Payne effect becomes more pronounced in rubber with modified clay. A decrease in loss factor (tanδ) was observed for rubber with hybrid filler also. The results revealed that the inclusion of nanoclay (NC) could induce a stronger and more developed filler network. Because of the anisotropy of the nanolayers, NC would depress the reconstruction of filler network, or lower the reformation rates when broken down under deformation, giving rise to lower tanδ value at broad temperature range as well as strain amplitude. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Interfacial Interactions of Silica and Natural Rubber Enhanced by Hydroxyl Telechelic Natural Rubber as Interfacial Modifier

The incompatibility between hydrophilic silica and hydrophobic rubber is an important problem on using silica in nonpolar rubber. In this study, hydroxyl telechelic natural rubber (HTNR) that contains hydroxyl‐terminated groups was introduced into silica‐reinforced natural rubber (NR) in order to improve the bonding strength between rubber and silica. The properties of silica‐reinforced NR compounds and vulcanizates as a function of varying silica contents were evaluated at a fixed HTNR concentration at 8% wt/wt of silica content. The results show that the improvement of silica dispersion and decreasing of filler–filler interactions (Payne effect) were obtained in the NR compounds and vulcanizates with HTNR addition. The enhancements in tensile properties, crosslink density, abrasion resistance, heat build‐up, and thermal properties of the silica‐reinforced NR vulcanizates with added HTNR confirmed that HTNR performed good as interfacial modifier of silica. In the study, the optimum properties of silica‐reinforced NR vulcanizate were achieved at 30 phr silica with 2.4 phr HTNR. However, HTNR still showed poorer efficiency than the synergy between commercial silane coupling agent, bis [3‐(triethoxysilyl) propyl] tetrasulphide (TESPT) and diphenylguanidine (DPG) when used in silica‐reinforced NR vulcanizate. J. VINYL ADDIT. TECHNOL., 26:291–303, 2020. © 2019 Society of Plastics Engineers     

Curing characteristics and mechanical properties of rattan‐powder‐filled natural rubber composites as a function of filler loading and silane coupling agent

Curing characteristics, tensile properties, morphological studies of tensile fractured surfaces using scanning electron microscopy (SEM), and the extent of rubber filler interactions of rattan‐powder‐filled natural rubber (NR) composites were investigated as a function of filler loading and silane coupling agent (CA). NR composites were prepared by the incorporation of rattan powder at filler loading range of 0–30 phr into a NR matrix with a laboratory size two roll mill. The results indicate that in the presence of silane CA, scorch time (t_s2), and cure time (t₉₀) of rattan‐powder‐filled NR composites were shorten, while, maximum torque (M_H) increased compared with NR composites without silane CA. Tensile strength and tensile modulus of composites were enhanced whereas elongation at break reduced in the presence of silane CA mainly due to increase in rubber‐filler interaction. It is proven by SEM studies that the bonding between the filler and rubber matrix has improved. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Studies on the preparation and mechanical properties of esthetic polymeric dental restoratives using silane treated silica microfiller via freeze‐drying

Polymeric dental restorative composites were prepared using silica filler where the surface was treated with γ‐methacryloxypropyltrimethoxysilane and decanted solvents by the freeze‐drying method. This treatment improved the miscibility of the filler with 2,2′‐bis‐[4‐(methacryloxy‐2‐hydrbxypropoxy)‐phenyl]‐propane/triethyl‐eneglycoldimethacrylate resin matrix and enhanced the esthetic properties of the composite. Diametral tensile strength (DTS) and flexural strength (FS) of the dental composite were measured, and the effect of drying methods in the surface treatment of filler on the mechanical properties of the composite was also investigated. Dental restorative composites prepared by the freeze‐drying method showed substantially higher DTS and FS values than those prepared by the conventional heat‐drying method. This resulted in increasing the loading percentage of filler in the resin matrix, and thereby, DTS values were increased dramatically. Dispersion of silica filler in the resin matrix and surface characteristics were examined by scanning electron microscopy. Various esthetic grades of dental composites were successfully prepared using iron oxide pigments, and its Hunter L. a. b. values of vita color‐shade were also investigated.     

Cure characteristics,mechanical, thermal,and coloring properties of natural rubber/dye‐loaded shell powder composites

To explore the application of shell powder (SP) in rubber, a dye‐loaded SP (DSP) bio‐filler based on SP and Congo red was incorporated into natural rubber (NR). The adsorption experiments demonstrated that the maximum monolayer adsorption capacity of Congo red onto SP was 69.3 mg/g. The effect of aluminate coupling agent and DSP was investigated by evaluating the cure characteristics, mechanical, thermal, and coloring properties of NR/DSP composites. It was suggested that the optimum amount of aluminate coupling agent was 2 wt %, and the best tensile strength (24.80 MPa) of vulcanizates was achieved at the DSP content of 20 phr, while other mechanical properties such as tear strength kept increasing with the addition of DSP. Furthermore, the improved thermal stability and uniform color distribution of the NR composites was obtained. The results indicate that DSP is promising to become a low‐cost filler and pigment for rubber materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45750.     

Carbon nanotubes/carbon black synergistic reinforced natural rubber composites

Abstract

Carbon black (CB) and carbon nanotubes (CNTs) filled natural rubber (NR) composites were prepared. In order to overcome the dispersion of CNTs in rubber matrix, the surface modification of CNTs with bis-(γ-triethoxysilylpropyl)-tetrasulphide (Si-69) was undertaken, and a two-step mixing process, i.e. the use of twin roll mill followed by mixing in a Haake Banbury mixer (TR-THM) was used. The structure and mechanical properties were investigated. The results show that the Si-69 treated CNTs (S-CNTs) were dispersed in the rubber matrix uniformly. Compared with CB/NR composites without CNTs, the S-CNTs/CB/NR composites have better mechanical properties. When the ratio of S-CNTs/CB/NR was 5 : 20 : 100, the tear strength was improved by ～60%, and the mechanical properties reached a maximum. Dynamical mechanical analysis (DMA) reveals that with increasing content of CNT, the elastic modulus of composites at room temperature increases, and the maximum loss tangent and the corresponding glass transition temperature of composites decrease.     

Effect of coal gangue/carbon black/multiwall carbon nanotubes hybrid fillers on the properties of natural rubber composites

The objective of this study was to investigate three kinds of filler with completely different morphology on mechanical properties of natural rubber (NR). Coal gangue (CG) are derived from natural deposits are composed principally by illite and quartz. CG, carbon black (CB), and multiwalled carbon nanotube (CNT) were used as hybrid fillers in NR. CNTs were dispersed into NR latex by ultrasonic irradiation and then the mixed latex were coagulated to obtain the CNTs/NR masterbatch, then mechanical mixing method was employed to prepare the CG/CB/CNTs/NR composites. The addition of CG, CB, and CNTs to NR was varied with the total filler loading fixed at 35 phr. The mechanical properties of NR composites were studied in terms of tensile and dynamic mechanical analysis (DMA). The results showed that the tensile strength and modulus 300% (M300) of all hybrid samples were higher than the composites only loaded CG; and the highest tensile strength of NR loaded with hybrid fillers achieved at sample of loading amount of CG 17.5, CB 15.5, and CNTs 2 phr, whose M300 and elongation at break was obviously higher than that of only CB loaded NR composites; The inclusion CG improves the tensile strength of NR without the sacrifice of its extensibility, while CB and CNTs brings together the enhancement in the ultimate strength and the reduction in the extensibility. DMA results revealed that the existence of CG can improve the dispersion of CB and CNTs in NR matrix. POLYM. COMPOS., 37:3083–3092, 2016. © 2015 Society of Plastics Engineers