Effects of substitution for carbon black with graphene oxide or graphene on the morphology and performance of natural rubber/carbon black composites

In this study, nanosheets including graphene oxide (GO) and reduced graphene oxide (rGO), were incorporated into natural rubber (NR), to study the effects of substituting GO or rGO for carbon black (CB) on the structure and performance of NR/CB composites. The morphological observations revealed the dispersion of CB was improved by partially substituting nanosheets for CB. The improvements in static and dynamic mechanical properties were achieved at small substitution content of GO or rGO nanosheets. With substitution of rGO nanosheets, significant improvement in flex cracking resistance was achieved. NR/CB/rGO (NRG) composites has a much lower heat build‐up value compared with NR/CB/GO (NG) composites at a high load of nanosheets. However, both GO and rGO tended to aggregate at a high concentration, which led to the poor efficiency on enhancing the dynamic properties, or even deteriorate the performance of rubber composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41832.     

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     

Simultaneous reduction and surface functionalization of graphene oxide and the application for rubber composites

The simultaneous reduction and functionalization of graphene oxide (GO) was realized through a chemical grafting reaction with a functionalization agent N,N-bis(3-aminopropyl)methylamine (APMEL). The reduced and functionalized reduced GO (rGO-APMEL) sheets can be well dispersed in water without any added surfactant and the formed stable rGO aqueous dispersion can be kept for a long time, which can be used for the preparation of rubber–graphene (GE) composites by latex mixing. The electrostatic interaction between rGO–APMEL (positively charged) and natural rubber latex particles (negatively charged) leads to the formation of NR/rGO–APMEL composites with strong interaction. Compared with blank NR, the tensile strength and modulus for NR/rGO–APMEL increase with the rGO–APMEL loading. Especially, when the filler content is 5 phr, the tensile strength of NR/rGO–APMEL-5 increases by 32.7%, as a control the tensile strength of NR/GO-5 and NR/rGO-5 decrease by 20.1 and 15.6%, respectively. The entanglement-bound rubber tube model was used to analyze the reinforcing effect of GE on NR/rGO–APMEL nanocomposites at a molecular level. This study may provide us a novel approach to prepare well dispersed and exfoliated rGO–polymer nanocomposites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47375.     

用作载重子午线轮胎胎面胶的炭黑填充粉末NR结构与性能研究

以天然胶乳和炭黑N234为原料,采用凝聚共沉法制备炭黑填充型粉末NR[P(NR/CB)],研究炭黑用量和不同配方对胶料硫化特性、物理性能、交联密度、微观结构、Payne效应及动态力学性能的影响,并与采用传统机械混炼法制备的炭黑/NR(CB/NR)进行对比.结果表明,与CB/NR硫化胶相比,P(NR/CB)硫化胶具有较高的拉伸强度、撕裂强度、回弹值和抗湿滑性能以及较低的滚动阻力,耐屈挠性能和耐磨性能大致相当,而动态压缩生热和压缩永久变形则降低了近50%.     

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。     

Effect of reynolds number on the dispersion of carbon black in natural rubber latex and filler–rubber interfacial interaction in high‐speed jet flow field

A novel strategy of high‐speed impinging jet processing technique was developed to prepare rubber composites by directly mixing natural rubber latex (NRL) with carbon black (CB). The results showed that CB could be more evenly dispersed into natural rubber by jet compounding technique, compared with the traditional dry process. The dispersion of carbon black was improved at higher Reynolds number because of more intensive shear force. Furthermore, a high performance of natural rubber latex/CB composite was gained by jet compounding technique. When compared to the traditional dry process, the mechanical properties and abrasion resistance of the composite prepared by the jet compounding technique were greatly improved because of the improved filler–rubber interaction at higher Reynolds number. POLYM. COMPOS., 34:1071–1075, 2013. © 2013 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。     

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.     

一段混炼时间对石墨烯/天然橡胶/溶聚丁苯橡胶复合材料性能的影响

采用一段密炼和二段开炼的两段混炼工艺制备氧化石墨烯(GO)/天然橡胶(NR)/溶聚丁苯橡胶(SSBR)和还原氧化石墨烯(rGO)/NR/SBR复合材料,研究一段混炼时间对GO/NR/SSBR和rGO/NR/SSBR复合材料性能的影响。结果表明:随着一段混炼时间的延长,GO/NR/SSBR和rGO/NR/SSBR复合材料的Fmax和FL增大,t90缩短;邵尔A型硬度、300%定伸应力、拉伸强度和撕裂强度呈先增大后减小的趋势,导电性能和导热性能呈先提高后降低的趋势,气密性能呈先提高后平稳再降低的趋势。     

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.     

聚苯胺改性蒙脱土/天然橡胶纳米复合材料的制备与性能

采用原位聚合法制备了聚苯胺质量分数为20% 的聚苯胺改性蒙脱土,并以此作为增强剂利用机械混炼法制备了聚苯胺改性蒙脱土( PANI － MMT) /天然橡胶( NR) 纳米复合材料。使用X 射线衍射仪、傅里叶变换红外光谱仪及扫描电镜等对PANI － MMT 和PANI － MMT/NR 复合材料的结构进行了表征,并考察了PANI － MMT/NR 复合材料的力学性能。结果表明,PANI － MMT/NR 复合材料形成了插层型纳米结构; 与普通的有机蒙脱土/NR 复合材料相比,PANI － MMT/NR 复合材料的力学性能明显提高,PANI － MMT 添加质量为20 份时其力学性能达到最好,并超过了添加40 份炭黑N 660 的NR 的力学性能。     

The reinforcing mechanism study of carbon nanotube in the NR matrix

The reinforcement mechanism of CNT in rubber matrix is an important and interesting subject. In this paper, carboxyled multi-walled carbon nanotubes (CNT) were used to prepare natural rubber (NR) nanocomposites (CNT/NR). CNT/NR composites were formed by mechanical blending method and the properties such as tensile strength, tensile modulus, tear strength, elongation at break and hardness were studied. The results of Mechanical property show that the physical property of NR filled with 9 phr CNT (CNT/NR-9) is similar to that with 30 phr carbon black (CB) (CB/NR-30). In addition, the dispersion and interaction between CNT and NR were also studied by scanning electron microscope, transmission electron microscope, dynamic mechanical testing system and bound-rubber analysis. According to the results, CNT is considered to exhibit random orientations and form “string bag” structure in rubber matrix and the reinforcement mechanism of CNT is different to that of CB.     

Rare earth compounds modified carbon black filled powdered natural rubber: Preparation,morphology and properties

Ten types of rare earth (RE) compounds modified carbon black (HAF‐RE) were prepared using chemical‐deposit method, then HAF‐RE were mixed with natural rubber latex to prepare HAF‐RE filled powdered natural rubber [P(NR/HAF‐RE)] by a carbon black/rubber latex coagulation method. It is found that most of the P(NR/HAF‐RE) vulcanizates showed better mechanical properties, especially higher tensile modulus, and tensile strength, compared with none‐rare earth modified carbon black filled powdered natural rubber [P(NR/HAF)]. Dysprosium (Dy) modified carbon black (HAF‐Dy) filled powdered natural rubber [P(NR/HAF‐Dy)] was chosen for intensive investigation because of its better comprehensive mechanical properties. It is found that the adding of Dy compounds could help to get smaller particles with narrower particle size distribution, and results from the SEM analysis show that carbon black has been dispersed in rubber matrix uniformly with diameter of 50–150 nm. The TEM analysis showed that Dy compounds could obviously reduce the aggregation of primary particles of carbon black, and promote the dispersion of carbon black in P(NR/HAF‐Dy) particles. © 2008 Wiley Periodicals, Inc. JAppl Polym Sci 2008     

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     

Dispersion,Mechanical and Thermal Properties of Epoxy Resin Composites Filled with the Nanometer Carbon Black

The nanometer carbon black (CB) was employed to prepare epoxy resin/carbon black (EP/CB) composites by blending-casting method. The different modified methods of silicone coupling agent were used to improve the dispersion of CB in epoxy resin. The mechanical and thermal properties of EP/CB composites were investigated. Experimental results showed that the mechanical properties increased at first, but decreased with excessive addition of CB. When the mass fraction of CB was 2%, the mechanical properties were maximum. The use of modified CB significantly enhanced the mechanical properties of the composites. For given CB loading, the CB modified by pretreatment method displayed better dispersion in the epoxy resin than that of the direct mixing method. SEM observation revealed that the tensile fracture surface of the composite filled with 2 wt% modified CB held more microcracks than that of 5 wt% modified CB, and the formed microcracks could consume more energy of rupture, finally to have better tensile strength. DSC analysis showed that the glass transition temperature (Tg) of the composites increased with the increasing mass fraction of CB.     

炭黑在天然橡胶/溶聚丁苯橡胶硫化胶中的分散及其对性能的影响

考察了溶聚丁苯橡胶(SSBR)用量、炭黑的种类及用量对天然橡胶(NR)/SSBR硫化胶动态力学性能和力学性能的影响.结果表明,炭黑与SSBR的结合作用比与NR弱;随SSBR用量的增加,炭黑在NR/SSBR共混硫化胶中的分散性提高,Payne效应减弱,频率敏感性增强;随SSBR用量的增加,NR/SSBR共混硫化胶的拉伸强度和撕裂强度减小,扯断伸长率变化不大;而定伸应力则呈先减小后增大的趋势;随不同种类的炭黑在NR/SSBR硫化胶中分散性的提高,定伸应力呈上升趋势,损耗因子和压缩生热呈减小趋势.     

Viscoelastic properties of natural rubber composites reinforced by defatted soy flour and carbon black co‐filler

Filler mixtures of defatted soy flour (DSF) and carbon black (CB) were used to reinforce natural rubber (NR) composites and their viscoelastic properties were investigated. DSF is an abundant and renewable commodity and has a lower material cost than CB. Aqueous dispersions of DSF and CB were first mixed and then blended with NR latex to form rubber composites using freeze‐drying and compression molding methods. A 40% co‐filler reinforced composite with a 1 : 1 DSF : CB ratio exhibited a 90‐fold increase in the rubber plateau modulus compared with unfilled NR, showing a significant reinforcement effect by the co‐filler. The effect, however, is lower than that observed in the carboxylated styrene–butadiene rubber composites reported earlier, indicating a significant effect from the rubber matrix. The co‐filler composites have elastic moduli between those of DSF and CB reinforced composites. Stress softening and recovery experiments indicated that the co‐filler composites with a higher CB content tend to have a better recovery behavior; however, this can not be simply explained from the recovery behaviors of the single filler (DFS and CB) composites. CB composites prepared by freeze‐drying show a strain‐induced reorganization of fillers. Strain sweep experiment data fit with the Kraus model indicates the co‐filler composites with a higher CB content are more elastic, which is consistent with the recovery experiments. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

功能化还原氧化石墨烯/天然橡胶导热复合材料的性能研究

采用2-巯基苯并咪唑(防老剂MB,以下简称MB)对氧化石墨烯(GO)进行还原及功能化,同时与采用抗坏血酸(VC)对GO进行还原对比,分别制得MB还原氧化石墨烯(rGO-MB)和VC还原氧化石墨烯(rGO-VC),并采用胶乳共混法制备rGO-MB/NR和rGO-VC/NR复合材料,对其性能进行研究。结果表明:MB成功还原了GO,MB接枝到了GO上;与rGO-VC/NR复合材料相比,rGO-MB/NR复合材料具有较低的Payne效应和较高的结合胶含量,拉伸强度和导热性能均明显提高。     

KH-550对纤维素纳米晶替代炭黑补强天然橡胶的影响

本文采用酸水解工业微晶纤维素(MCC)制备纤维素纳米晶(NCC),将其与天然胶乳共凝沉,混炼时加入炭黑(CB),制备了天然橡胶(NR)/NCC/CB复合材料,研究了偶联剂KH-550对NR/NCC/CB(100/10/35)性能的影响,结果表明,KH-550用量为1-2phr时,NR/NCC/CB的硫化性能、混炼胶的加工性能、硫化胶的交联密度、抗屈挠龟裂性能、动态压缩疲劳生热、永久变形和耐磨耗性能明显改善。     

Piezoresistive behavior of graphene nanoplatelets/carbon black/silicone rubber nanocomposite

Silicon rubber (SR) filled with carbon black (CB) and carbon black (CB)/graphene nanoplatelets (GNPs) hybrid fillers are synthesized via a liquid mixing method. The effects of filler type on the electrical properties and piezoresistive properties (near the region of the percolation) of the conductive SR composites are studied. It is suggested that the conductivity of the composite filled with CB/GNPs hybrid fillers in the mass ratio of 2 : 4 is much higher than that in other ratio. Percolation threshold for CB/GNPs/SR is found to be 0.18 volume fractions lower than CB/SR. Moreover, force rang and linearity of GNPs/CB/SR is higher than CB alone filling system. And the repeatability of the GNPs/CB/SR composites is better than CB/SR. Not repetitive index () of them is 0.1 and 0.18, respectively. The results suggest that the GNPs/CB/SR composites provide a new route toward fabrication of flexible piezoresistive sensors with high performance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39778.