Enhancement of the mechanical and tribological properties of carboxylated acrylonitrile butadiene rubber filled with cryptocrystalline graphite by different preparation methods

As a cost-effective and environmentally friendly natural mineral, cryptocrystalline graphite (CG) is applied in rubber materials and its performance has been evaluated. In this work, the filler dispersion and mechanical and tribological properties of carboxylated acrylonitrile butadiene rubber (XNBR)/CG composites by different preparation methods were studied. XNBR/CG composites prepared by latex blending (XNBR/CG-L) exhibited better mechanical and tribological performance, higher toughness, and lower heat build-up than those prepared by mechanical blending (XNBR/CG-M). These differences were ascribed to the filler dispersion degree, filler amount and dispersed size, and also filler–rubber interfacial interaction. Adding CG was conducive to improving the stability of the friction coefficient and reduced the wear rate via the formation of graphite lubricant and transfer films. The tribological performance of XNBR/CG-L was superior to that of XNBR/CG-M because of the improved tensile strength, tear resistance, and toughness as well as lower temperature rise. Scanning electron microscopy (SEM) and optical microscope observation showed a smoother worn surface, less and smaller wear debris of XNBR/CG-L, and a more uniform transfer film on the steel counterpart surface. The relevant results provided new insight into the performance and structural design of CG/rubber composites.     

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     

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。     

Friction and wear properties of NBR/PVC composites

Acrylonitrial butadiene rubber (NBR)/Polyvinyl chloride (PVC) composites with different PVC content were prepared. The effect of PVC content on the mechanical strength and tribological properties of the NBR/PVC composites was investigated. The morphologies of the worn traces and debris of NBR/PVC composites and worn traces of mating ball were observed using a scanning electron microscope (SEM). It was found that the friction and wear of NBR/PVC was lower than that of NBR without PVC. The NBR/PVC composite with 30% PVC content showed the best synthetic mechanical and tribological properties. The inferior elastic properties and the lesser deformation under the applied load of composites with PVC resulted in hysteric force and adhesion force decrease, which leading to a lower friction and wear of NBR/PVC composites. The frictional failure unit of NBR70/PVC30 composite being smaller should be an important reason of the wear of the composite being lowest. The lubricating effect of PVC played an important role in decreasing the friction coefficient and wear of NBR/PVC composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

芳纶纤维增强丁腈橡胶的摩擦性能

研究了芳纶纤维增强丁腈橡胶(NBR)复合材料的物理机械性能和摩擦性能,并用扫描电子显微镜分析了芳纶纤维增强NBR复合材料的磨损表面和磨屑形貌。结果表明,芳纶的加入提高了NBR的拉伸强度;随着芳纶用量的增大,复合材料的扯断伸长率降低;芳纶的加入降低了NBR的摩擦系数和磨损率;当芳纶用量为20份时,复合材料的综合性能最佳。加入芳纶对NBR摩擦磨损形式的改变是NBR摩擦性能提高的重要原因。     

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。     

Fracture properties of natural rubber filled with hybrid carbon black/nanoclay

Hybrid carbon black (CB) and nanoclay (NC) in a rubber matrix have provided superior mechanical performances over conventional composites. Yet the fracture and fatigue properties have not been fully explored. In this paper, the mechanical properties of the hybrid-filled natural rubber (NR) were investigated with regard to the tensile strength, fatigue crack growth (FCG) and cut resistance. The ruptured crack tip and the torn surface were studied by using optical microscopy and scanning electron microscopy (SEM), respectively. It was found that the fatigue resistance at large tearing energy and cut strength were enhanced with hybrid filler. Subsidiary cracks were observed at the ruptured tip in rubber with NC. Morphology analysis revealed that the hybrid filler led to a rougher torn surface than rubber with non-hybrid filler. It was proposed that the clay layers constructed a dual phase filler network with CB aggregates. The filler network could cause strength anisotropy in the matrix and introduce more energy dissipation mechanisms to the system, resulting in enhanced fatigue resistance.     

Impact of graphene oxide nanoparticles and carbon black on the gamma radiation sensitization of acrylonitrile–butadiene rubber seal materials

Seals prepared from acrylonitrile–butadiene rubber (NBR) are primarily used in nuclear services. Nevertheless, at relatively high ionizing radiation doses, NBR seal materials may undergo radiation-induced degradation processes, leading to adverse effects on the sealing ability life. Herein, to strengthen the functional characteristics of NBR seals against radiation, graphene oxide (GO) nanoparticles were prepared and characterized by transmission electron microscopy, X-ray diffraction (XRD), Fourier transform infrared (FTIR), and ultraviolet/visible spectroscopies. Various NBR/GO composites fabricated with different ratios of GO nanoparticles and in the presence or absence of carbon black (CB) were investigated via cross-linking density, scanning electron microscopy, XRD, FTIR, and mechanical and thermal stability analyses. The synergistic effect of the simultaneous presence of GO and CB on the NBR seal sensitization to gamma radiation up to a dose of 1 MGy was studied. The physicomechanical properties were enhanced by adding GO nanosheets up to 3 phr and by incorporating 35 phr of a CB with GO until 5 phr. Further, the application of γ-irradiation resulted in an overall enhancement in the mechanical, physical, and thermal stability of the prepared composites up to 0.5 and 1 MGy with GO nanosheets in the absence or presence of CB particles, respectively. The mechanical measurements indicated significant increments by loading with GO nanosheets in the absence and presence of CB as well as by irradiation. The tensile strength elevated up to about 121%, 336%, and 366% by adding 3 phr GO, 3 GO:35 CB phr, and 5 GO:35 CB phr, respectively.     

The Properties of Acrylonitrile-Butadiene Rubber (NBR) Composite with Halloysite Nanotubes (HNTs) and Silica or Carbon Black

The properties of acrylonitrile-butadiene rubber (NBR) composites were studied at five different compositions of NBR/HNTs/Silica or NBR/HNTs/CB (i.e., 100/5/0, 100/4/1, 100/3/2, 100/2/3, 100/0/5 parts per hundred rubber (phr)). The tensile strength and modulus (M100) of both composites decreased, whereas elongation at break increased and maximum torque with increasing the silica or carbon black content. However, both composites show opposite trends for cure time and scorch time, where NBR/HNTs/Silica composite exhibited an increasing trend, while NBR/HNTs/CB composite shows the decreasing trend. The rubber-filler interaction studies showed that carbon black is a more reinforcing filler than silica.     

Influence of graphite particle size and shape on the properties of NBR

Four graphite powder fillers with different form and size were mixed with acrylonitrile butadiene rubber (NBR, acrylonitrile content at 26%) at 20, 40 and 60 phr of the filler loadings, and the obtained compounds were characterized by SEM, tensile test, friction and wear test. Through the SEM observation, it was found that the expanded graphite could not be broken down to small particles uniformly when blended with rubber on the twin‐roller. In the tensile test, the graphite with the smallest size possessed the best reinforcement ability as expected. The tribological properties of the rubber were improved when adding more graphite. The largest graphite particles imparted the lowest friction coefficient of the composites among four fillers, but the submicrometer graphite provided the best wear property to NBR. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4007–4015, 2006     

Composites based on CB/CF/Ag filled EPDM/NBR rubber blends with high conductivity

For many applications of conductive rubbers, it is desirable to endow the conductive rubber with high conductivity at low conductive filler loading. In this work, composites based on ethylene‐propylene‐diene monomer (EPDM) rubber and nitrile‐butadiene rubber (NBR) were prepared using carbon blacks, carbon fibers, and silver powders as fillers. As the weight fraction of silver powder increased, the hardness of composites increased gradually while the tensile strength and elongation at break decreased. SEM revealed that the EPDM/NBR blends exhibited a relatively co‐continuous morphology. The differential scanning calorimetry (DSC) curves reported the EPDM/NBR rubber blends were incompatibility. The thermogravimetry (TG) studies showed that adding a small amount of silver powder could improve the thermal stability of composites. These conductive composites exhibited good electrical property. At room temperature, when the total volume fraction of fillers was 15.20%, the volume resistivity of EPDM/NBR blend was only 0.0058 Ω cm. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41357.     

Friction properties of graphene reinforced nitrile rubber composites after thermal oxidation aging: Experiment and molecular dynamics simulation

We established friction models for pure NBR, GNS/NBR, and GO/NBR composites through molecular dynamics (MD) simulation. Our study focused on the impact of GNS and GO on the friction properties of nitrile rubber (NBR) composite materials after undergoing thermal oxygen aging. Based on the simulation results, it can be observed that the GNS/NBR and GO/NBR composites' coefficient of friction (COF) decreases by 20.8% and 24.8%, respectively, at 348 K. Additionally, the abrasion rate is reduced by 17.4% and 25.7%, respectively, for the same composites. Adding GNS and GO can effectively improve the friction performance of the NBR composite system, and compared with GNS, GO shows a better enhancement effect. Pure NBR and GO/NBR composite materials were prepared by mechanical blending method, and the friction properties of GO-enhanced NBR composite materials were studied. The experimental results show that the GO/NBR composite material can maintain a low friction and wear coefficient after thermal and oxygen aging. It shows that adding GO can effectively improve the friction properties of NBR composite systems and slow down the weakening effect of aging on the friction properties of NBR composite materials. This is because the GO surface contains wealthy functional groups such as epoxy groups, which enhances the binding strength between the GO and NBR interface so that the GO/NBR composite material exhibits better friction properties and thermal oxygen aging resistance. In addition, the wear surface was characterized by scanning electron microscopy (SEM), revealing the damage mechanism of friction and wear of NBR composite materials.     

Effect of pulverized coal/carbon black hybrid fillers on mechanical properties and thermal stability of styrene butadiene rubber composites

Pulverized coal (coal) possesses a layered structure similar to graphite and is a potential reinforcing filler. In this paper, ball milling is used to reduce the particle diameter of coal. The coal is modified with KH-560 to obtain K-COAL and prepared K-COAL/styrene-butadiene rubber (SBR) composites. In addition, carbon black (CB) is modified to obtain CB-Si69, K-COAL and CB-Si69 are added to SBR in different ratios to prepare COAL/CB/SBR composites. The results show that the addition of K-COAL can improve the vulcanization performance, thermal stability, and mechanical properties of SBR composites, but the reinforcing effect is weak. In the COAL/CB/SBR composites, the vulcanization and mechanical properties of the composites gradually increase with the increase of CB, while those of the thermal stability decrease. The tensile strength of the 10 phr COAL/30 phr CB/SBR composite is 24.1 MPa, which is elevated by 1105% and 205% compared with the pure SBR and 40 phr K-COAL/SBR composites, respectively. The composites maintain high elasticity while the tensile strengths are greatly improved, and the mechanical properties are significantly enhanced. In conclusion, this paper provides a reference for the clean utilization of coal and shows new possibilities for finding new fillers to replace CB.     

酸性活性修饰剂对白泥/丁腈橡胶复合材料力学性能的影响

利用丙烯酸和对乙烯苯磺酸作为白泥的修饰剂,对白泥进行湿法修饰,而后利用石蜡对白泥进行二次包覆制备了有机修饰活性白泥,并将其作为橡胶填料填充到丁腈橡胶(NBR)中制备了修饰白泥/NBR(400:100)母胶,而后将母胶填充到NBR中制备了不同白泥含量的白泥/NBR复合材料。考察了不同修饰量制备的母胶对复合材料硫化性能的影响、母胶及用量对NBR复合材料的性能影响。实验结果表明:当加入修饰剂的用量逐步增加(以干白泥质量计算)时,母胶填充的白泥/NBR复合材料的力学性能呈现先增大后减小的趋势。酸性活性剂用量为白泥2%的母胶且母胶份数为100phr时其白泥/NBR复合材料的力学性能达到最佳值。但是两种活性修饰剂修饰的白泥母胶在改性NBR性能上存在差异:丙烯酸修饰白泥母胶制备的白泥/NBR复合材料的力学性能为拉伸强度8.3MPa、扯断伸长率386%、300%定伸应力3.7MPa、硬度79;乙烯苯磺酸修饰白泥母胶的力学性能为拉伸强度9.8MPa、扯断伸长率652%、300%定伸应力4.2MPa、硬度78。研究表明:利用丙烯酸、对乙烯苯磺酸作为白泥的修饰剂并制备橡胶母胶可大幅度提高橡胶材料的力学性能,可作为白泥综合利用的一种有效方法。     

温度对酚醛树脂/丁腈橡胶复合材料摩擦学性能的影响

采用机械共混法将酚醛树脂（PF）与丁腈橡胶（NBR）进行混合而制得PF/NBR复合材料,研究了PF用量对NBR的拉伸性能、撕裂性能及硬度的影响,使用多功能材料表面性能综合测试仪、三维表面形貌仪和扫描电子显微镜对力学性能最优的PF/NBR复合材料试样A 2（添加5份PF）在不同温度下的摩擦性能进行了探究,并与未添加PF的试样A 0进行了对比,此外还对PF/NBR复合材料的磨损机理进行了初步分析。结果表明,当温度超过75 ℃时,试样A 0的摩擦系数曲线整体呈持续上升的趋势,同时其表面有较多孔洞,分子间结合力下降,耐磨性变差,而试样A 2的摩擦系数则基本保持稳定,磨损行为表明其磨损机理由磨粒磨损逐渐转变为黏着磨损;相对于试样A 0而言,试样A 2在高温下仍能保持较好的摩擦性能。     

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     

Nitrile rubber/sliding graft copolymer damping material with significantly improved strength and damping performance

Nitrile rubber (NBR)/sliding graft copolymer (SGC) composites with significantly improved strength and damping property are successfully prepared. SGC is a novel kind of supramolecular material with sliding crosslink junctions. The micromorphology analyses of NBR/SGC composites indicate that the SGC phase with particle size less than 500 nm is fairly uniformly dispersed in the NBR matrix. As SGC content increases, the loss factors (tan δ) of NBR/SGC composites increase gradually. Specifically, the tan δ of NBR/SGC (100/40) is about 1.2 times higher than that of pristine NBR rubber. The tensile strength and elongation at break of NBR/SGC composites are unexpectedly improved after the addition of SGC. The significantly improved damping performance and tensile strength can be ascribed to the pulley effect of SGC and the strong interfacial hydrogen bonds between SGC and NBR. The high damping performance and good mechanical strength make the NBR/SGC composite a promising high-performance damping material. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47188.     

丁腈橡胶/乙丙橡胶并用胶性能的研究

研究丁腈橡胶(NBR)/三元乙丙橡胶(EPDM)并用比对力学性能、老化性能和耐油性能的影响以及增容剂对共混胶性能的影响.结果表明,在NBR/EPDM共混胶中随EPDM用量的增加,硫化胶的硬度、拉伸强度、撕裂强度和定伸应力呈现下降趋势、拉断伸长率及耐低温性能有所改善,降低了NBR的耐汽油性能,但提高了耐含乙醇汽油性能.随着增容剂CM用量的增加,硫化胶拉伸强度、撕裂强度、100％定伸应力及硬度都呈增大趋势,采用扫描电镜可以清晰的看到添加CM改性后NBR/EPDM共混胶相容性得到显著改善.     

Effects of fibre content and orientation on wear properties of basalt fibre/acrylonitrile–butadiene rubber composites

Basalt fibre (BF)/acrylonitrile–butadiene rubber (NBR) composites with various BF contents and orientations were prepared, and the curing, physical and mechanical properties and wear performance under block-on-ring abrasion conditions were evaluated. The results showed that the curing time was not obviously affected by the BFs. The addition of BFs increased the hardness but had negative influence on the tensile/tear strength of the NBR composites, especially when the BFs were oriented perpendicular to the tensile/tear direction with a high content, which should be due to the weak connection between the BFs and the rubber matrix. The coefficient of friction (COF) of the composites decreased significantly when BFs were added, whereas the content (3–30 phr) and the orientation of the fibres did not mainly affect the COF. Both parallel- and perpendicular-oriented BFs were effective at improving the wear resistance of the composites, and the former showed a better effect. With the BF content increase, the wear rate initially decreased and then remained basically stable. The COF and wear rate of the composites decreased by 27% and 35% when 12 phr BFs were added in a parallel direction. The excessive BFs, especially the perpendicularly-oriented BFs, led to fracture of the worn surface due to the abrasive grain wear caused by the crushed fibres.     

Influences of (3-aminopropyl)triethoxysilane on the tribological behaviors of basalt fiber/acrylonitrile-butadiene rubber composites under dry friction and water-lubricated conditions

The weak interaction between the basalt fiber (BF) and acrylonitrile-butadiene rubber (NBR) weakens the BFs' effects on improving the tribological performances of the NBR composites. To solve this problem, (3-aminopropyl)triethoxysilane (APTES) was introduced via mixing into the matrix or grafting on the BF surface, respectively. The characteristics, mechanical, and tribological properties of the composites were evaluated, and the effects of the APTES and its introduction methods on the tribological properties were the main focus. The APTES mixed in the rubber matrix decreased the friction coefficient (COF) of the NBR-based composites under both dry friction and water-lubricated conditions. Especially, the APTES hydrolysis under water-lubricated condition was conducive to the formation of the water film and thus dramatically decreased the COF. The COF of the BF0-A3 and the BF12-A3 were 51% and 30% lower than that of the BF0-A0 and the BF12-A0 under water lubrication, respectively. The APTES grafted on the BF surface increased the wear resistance of the BF/NBR composites attributed to the improvement of the interaction between the BFs and the NBR matrix. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48558.