Effect of modified single‐wall carbon nanotubes on mechanical and morphological properties of thermoplastic elastomer nanocomposites based on (polyamide 6)/(acrylonitrile butadiene rubber)

Thermoplastic elastomer nanocomposites based on acrylonitrile butadiene rubber (NBR) and polyamide 6 (PA6), with acid functionalized single‐wall carbon nanotubes (SWNT), were prepared via a direct melt‐mixing process in an internal mixer. The influence of SWNT content (0, 0.5, 1, 1.5) on morphological properties of PA6/NBR with different ratios (80/20, 70/30, 60/40) were then investigated. Characterization of nanocomposites was conducted by using transmission electron microscopy, scanning electron microscopy, differential scanning calorimetry, and mechanical properties. Scanning electron microscopy micrographs proved the droplet‐matrix blend morphology in which the size of NBR droplets decreased as the SWNT loading increased, suggesting dispersion of SWNT in the PA6 phase. It was further proved by transmission electron microscopy images, showing homogenous dispersion of SWNT in the PA6 phase. Differential scanning calorimetry results showed a slightly reduced percentage of crystallinity in samples containing SWNT. The mechanical properties of nanocomposites indicated an enhancement in tensile strength, modulus, and hardness on increasing SWNT content. J. VINYL ADDIT. TECHNOL., 22:336–341, 2016. © 2014 Society of Plastics Engineers     

聚合物改性碳纳米管及其对PVC增韧的研究

通过原子转移自由基聚合法合成了PMMA-Br、PBA-Br和PMMA-b-PBA-Br3种聚合物,采用叠氮法分别用它们修饰单壁碳纳米管(SWNT)。通过红外光谱、拉曼光谱、热失重法和透射电子显微镜综合分析了其修饰效果;并用经聚合物修饰的SWNT制备了PVC/SWNT纳米复合材料。结果表明,在100gPVC中加入0.1g经聚合物修饰的SWNT后,纳米复合材料的力学性能明显提高,其中PVC/PMMA-b-PBA-SWNT纳米复合材料的冲击强度是纯PVC的4倍;PVC/PMMA-SWNT纳米复合材料的冲击强度是纯PVC的3.2倍,断裂伸长率提高了2.5倍,拉伸强度提高了16%,弯曲强度提高了18%;PVC/PBA-SWNT纳米复合材料的拉伸强度和断裂伸长率分别是纯PVC的1.13倍和2.26倍;通过扫描电子显微镜分析了聚合物的增韧机理。     

丁腈橡胶/聚氯乙烯共混物的阻尼性能

考察了丁腈橡胶/聚氯乙烯共混物中硫化体系、炭黑种类、增塑剂用量及组分比对材料阻尼性能的影响.结果表明,丁腈橡胶/聚氯乙烯共混物的交联密度增大,其损耗因子峰向高温方向移动,峰值升高,损耗因子不小于0.5的温度区域变窄;相比高耐磨炭黑而言,用半增强炭黑作填料可使丁腈橡胶/聚氯乙烯共混物呈现更好的阻尼性能;随着增塑剂邻苯二甲酸二辛酯用量的增加,共混物的损耗因子峰值升高,但该峰向低温方向移动;丁腈橡胶/聚氯乙烯共混物(质量比为70/30)的损耗因子不小于0.5的阻尼温域相对较宽,适用于常温,且力学性能较好.     

Study on the damping of EVM based blends

The mechanical and damping properties of blends of ethylene‐vinyl acetate rubber(VA content >40 wt %) (EVM)/nitrile butadiene rubber (NBR) and EVM/ethylene‐propylene‐diene copolymer (EPDM), both with 1.4 phr BIPB (bis (tert‐butyl peroxy isopropyl) benzene) as curing agent, were investigated by DMA. The effect of polyvinyl chloride (PVC), chlorinated polyvinyl chloride (CPVC), and dicumyl peroxide (DCP) on the damping and mechanical properties of both rubber blends were studied. The results showed that in EVM/EPDM/PVC blends, EPDM was immiscible with EVM and could not expand the damping range of EVM at low temperature. PVC was miscible with EVM and dramatically improved the damping property of EVM at high temperature while keeping good mechanical performance. In EVM/NBR/PVC blends, PVC was partially miscible with EVM/NBR blends and remarkably widened the effective damping temperature range from 41.1°C for EVM/NBR to 62.4°C, while CPVC mixed EVM/NBR blends had an expanded effective damping temperature range of 63.5°C with only one damping peak. Curing agents BIPB and DCP had a similar influence on EVM/EPDM blends. DCP, however, dramatically raised the height of tan δ peak of EVM/NBR = 80/20 and expanded its effective damping temperature range to 64.9°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

氢化丁腈橡胶／超细全硫化粉末丁腈橡胶共混物的结构与性能研究

采用熔融共混工艺制备了氢化丁腈橡胶（HNBR）／超细全硫化粉末丁腈橡胶（UFPNBR）共混物,研究了共混物相态结构、动态力学性能、力学性能及老化性能,并与HNBR／NBR共混物作了对比。透射电镜观察表明：在HNBR／UFPNBR体系中,HNBR容易形成连续相,UFPNBR为分散相;在HNBR／NBR体系中容易形成双连续相结构。DMA动态力学性能分析表明：2种共混物都只有一个tanδ峰,且相容性较好。HNBR／UFPNBR共混物在玻璃化转变区的tanδ峰值逐渐降低,而HNBR／NBR体系的tanδ峰值先减小后增大。加入适量的UFPNBR能降低HNBR／UFPNBR共混物的压缩永久变形;与常规共混胶相比,HNBR／UFPNBR具有低脆性温度和良好的耐老化性能,但力学性能略低。     

Study of the Mechanical,Thermal Properties and Morphology of Polypropylene Nanocomposites in the Presence of Compatibilizer

In this work, the mechanical, rheological, and thermal properties and morphology of a polypropylene matrix reinforced with single-walled nanotubes (SWNTs) were investigated. Polypropylene-grafted-maleic acid was used as a compatibilizer to promote SWNTs dispersion. Compared to uncompatibilized nanocomposites, the tensile modulus of the material increased considerably when nanotubes and compatibilizer were employed. The rheological characterization results revealed that addition of SWNTs increased the storage modulus and complex viscosity at low frequencies. SEM revealed that the SWNTs were uniformly distributed when low concentrations of SWNTs were employed. The results of DSC indicated that the addition of SWNTs increased the crystallinity of nanocomposites.     

Single‐walled nanotube bucky paper and nanocomposite

A new processing method for the fabrication of single‐walled nanotube (SWNT)‐reinforced nanocomposites was developed to achieve uniform dispersion and high composition of the nanotubes in the nanocomposites. In this method, SWNTs were preformed as bucky paper by multi‐step dispersion and micro‐filtration of a suspension of nanotubes. The nanocomposites were then fabricated by infiltration of diluted epoxy resin through the bucky paper and hot pressing. The wetting of the nanocomposites was examined using scanning electron microscopy and atomic force microscopy. The results showed that the epoxy resin completely penetrated the bucky paper through the nanoporous structures. The results of dynamic mechanical analysis of the nanocomposites showed that the storage moduli of the nanocomposites increased by 200–250%. The tan δ curves indicated that the nanotubes had a strong influence on the damping properties of the nanocomposites. This processing technique is an effective method for fabricating nanocomposites with uniform dispersion and high composition of SWNTs. Copyright © 2006 Society of Chemical Industry     

聚异戊二烯/单壁碳纳米管复合材料的合成和性能研究

采用稀土催化剂利用原位聚合的方法,把聚异戊二烯接枝到单壁碳纳米管表面,制备了聚异戊二烯(PIp)/单壁碳纳米管(SWNT)复合材料。扫描电镜(SEM)被用来表征聚异戊二烯-接枝-SWNTs样品,显示相当均匀的聚合物出现在单个的或几束碳纳米管上。碳纳米管同聚异戊二烯的良好相容性提高了复合材料的玻璃化温度。大比表面积的碳纳米管和聚异戊二烯基质材料的较强的相互作用是聚异戊二烯纳米/碳纳米管复合材料具有独特性质原因。     

Effect of single-walled carbon nanotubes on thermal and electrical properties of silicon nitride processed using spark plasma sintering

Si₃N₄ nanocomposites reinforced with 1-, 2-, and 6-vol% single-walled carbon nanotubes (SWNTs) were processed using spark plasma sintering (SPS) in order to control the thermal and electrical properties of the ceramic. Only 2-vol% SWNTs additions were used to decrease the room temperature thermal conductivity by 62% over the monolith and 6-vol% SWNTs was used to transform the insulating ceramic into a metallic electrical conductor (92 S m⁻¹). We found that densification of the nanocomposites was inhibited with increasing SWNT concentration however, the phase transformation from α- to β-Si₃N₄ was not. After SPS, we found evidence of SWNT survival in addition to sintering induced defects detected by monitoring SWNT peak intensity ratios using Raman spectroscopy. Our results show that SWNTs can be used to effectively increase electrical conductivity and lower thermal conductivity of Si₃N₄ due to electrical transport enhancement and thermal scattering of phonons by SWNTs using SPS.     

Covalent addition of diethyltoluenediamines onto carbon nanotubes for composite application

Diethyltoluenediamines (DETDA) was grafted to single‐walled carbon nanotubes (SWNTs) through diazonium‐based addition for improving dispersion and interfacial bonding in SWNT/epoxy nanocomposites. Characterization results of Fourier Transformed Infrared spectroscopy and Raman spectroscopy validated covalent bonding between DETDA and carbon nanotubes. The degree of functionalization was about 4% based on thermo‐gravimetric analysis. Interfacial bonding strength was computed in the presence of chemical bonding and the computation results indicated that the interfacial shear strength in the presence of functionalized carbon nanotubes was significantly enhanced. The experimental test revealed that the tensile strength of nanocomposites was enhanced about 23% and Young's modulus about 25%, with 0.5 wt% loading of functionalized‐nanotubes. These considerable improvements further verified the load‐transfer enhancement in the functionalized‐SWNTs/epoxy nanocomposites. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

丁腈橡胶/聚氯乙烯共混胶

探讨了丁腈橡胶(NBR)中的结合丙烯腈质量分数、NBR／聚氯乙烯(PVC)(质量比,下同)、增塑剂邻苯二甲酸二辛酯(DOP)用量、PVC聚合度对NBR／PVC共混胶性能的影响,研究了NBR／低聚合度PVC共混胶的力学性能及加工流动性能。结果表明,随着NBR中结合丙烯腈质量分数的增加,NBR／PVC共混胶的耐油性能明显增强,力学性能也相应有所改善;NBR／PVC为80／20～60／40时．NBR／PVC共混胶的综合性能较好;DOP用量对NBR／PVC共混胶性能的影响不大;聚合度为700的PVC更适合于生产NBR／PVC共混胶,其力学性能、加工流动性能、耐老化性能与德国Bayer公司生产的牌号为Perbunan NT／VC3470B的NBR／PVC共混胶相当。     

机械共混法制备丁腈橡胶/聚氯乙烯/有机蒙脱土纳米复合材料的结构及性能

用机械共混法将4种牌号的有机蒙脱土(OMMT)与丁腈橡胶(NBR)/聚氯乙烯(PVC)共混,制备了纳米复合材料,并对其微观结构、硫化特性、力学性能以及耐油性进行了考察.结果表明,该复合材料具有插层型结构;4种牌号的OMMT均能提高共混胶的硫化速率,且能提高纳米复合材料的力学性能,其中牌号为FMR 11的OMMT增强效果最好,当其用量为6份时,纳米复合材料的拉伸强度比纯胶提高了49.96%,撕裂强度提高了36.9%,扯断伸长率也有所提高;随着OMMT用量的增加,纳米复合材料的耐油性逐渐提高.     

Relationship between dispersion metric and properties of PMMA/SWNT nanocomposites

Particle spatial dispersion is a crucial characteristic of polymer composite materials and this property is recognized as especially important in nanocomposite materials due to the general tendency of nanoparticles to aggregate under processing conditions. We introduce dispersion metrics along with a specified dispersion scale over which material homogeneity is measured and consider how the dispersion metrics correlate quantitatively with the variation of basic nanocomposite properties. We then address the general problem of quantifying nanoparticle spatial dispersion in model nanocomposites of single-walled carbon nanotubes (SWNTs) dispersed in poly(methyl methacrylate) (PMMA) at a fixed SWNT concentration of 0.5% using a ‘coagulation’ fabrication method. Two methods are utilized to measure dispersion, UV-vis spectroscopy and optical confocal microscopy. Quantitative spatial dispersion levels were obtained through image analysis to obtain a ‘relative dispersion index’ (RDI) representing the uniformity of the dispersion of SWNTs in the samples and through absorbance. We find that the storage modulus, electrical conductivity, and flammability property of the nanocomposites correlate well with the RDI. For the nanocomposites containing the same amount of SWNTs, the relationships between the quantified dispersion levels and physical properties show about four orders of magnitude variation in storage modulus, almost eight orders of magnitude variation in electric conductivity, and about 70% reduction in peak mass loss rate at the highest dispersion level used in this study. The observation of such a profound effect of SWNT dispersion indicates the need for objective dispersion metrics for correlating and understanding how the properties of nanocomposites are determined by the concentration, shape and size of the nanotubes.     

Synthesis of water-soluble single-walled carbon nanotubes by RAFT polymerization

Water-soluble single-walled carbon nanotubes (SWNTs) were synthesized by grafting poly(acrylamide) (PAM) from the surface of SWNT via reversible addition-fragmentation chain transfer (RAFT) polymerization. The RAFT agents were covalently attached to the SWNTs by functionalizing SWNTs with in situ generated diazonium compounds. The product was characterized by means of FT-IR, Raman, ¹H NMR, TGA and TEM. The results showed that PAM chains had successfully grafted from SWNT by RAFT polymerization. The amount of PAM grown from SWNT increased with the polymerization time. The acrylamide conversion increased linearly with the polymerization time, indicating the “living” characteristics of the RAFT polymerization. TEM was utilized to image PAM-g-SWNT, showing relatively uniform polymer coatings present on the surface of individual, debundled nanotubes.     

DMA analysis of the damping of ethylene–vinyl acetate/acrylonitrile butadiene rubber blends

The mechanical and damping properties of blends of ethylene–vinyl acetate rubber (VA content > 40% wt) (EVM)/acrylonitrile butadiene rubber (NBR), with 1.4 phr BIPB [bis (tert‐butyl peroxy isopropyl) benzene] as curing agent, were investigated by DMA and DSC. The effect of chlorinated polyvinyl chloride (CPVC), silica, carbon black, and phenolic resin (PF) as a substitute curing agent, on the damping and mechanical properties of EVM/NBR blends were studied. The results showed that 10 phr CPVC did not contribute to the damping of EVM700/NBR blends; Silica could dramatically improve the damping of EVM700/NBR blends because of the formation of bound rubber between EVM700/NBR and silica, which appeared as a shoulder tan δ peak between 20 and 70°C proved by DMA and DSC. This shoulder tan δ peak increased as the increase of the content of EVM in EVM/NBR blends. The tensile strength, modulus at 100% and tear strength of the blend with SiO₂ increased while the elongation at break and hardness decreased comparing with the blend with CB. PF, partly replacing BIPB as the curing agent, could significantly improve the damping of EVM700/NBR to have an effective damping temperature range of over 100°C and reasonable mechanical properties. Among EVM600, EVM700, and EVM800/NBR/silica blend system, EVM800/NBR/silica blend had the best damping properties. The EVM700/NBR = 80/10 blend had a better damping property than EVM700/NBR = 70/20. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

环氧树脂增强聚氯乙烯/丁腈橡胶共混胶的性能

用环氧树脂(EP)增强聚氯乙烯/丁腈橡胶(PVC/NBR)共混胶,研究了EP用量对共混胶力学性能的影响,考察了EP对炭黑增强PVC/NBR共混胶力学性能的影响,并用扫描电子显微镜分析了共混胶的微观形貌。结果表明,用EP增强PVC/NBR共混胶,胶料的力学性能提高,且老化后性能变化不明显。在EP用量为18份左右时共混胶的综合性能最佳。EP对炭黑增强PVC/NBR共混胶力学性能的改善有一定作用。EP在PVC/NBR共混胶中原位聚合生成了直径约为200 nm的纤维。     

Thermal and mechanical properties of single-walled carbon nanotubes-polypropylene composites prepared by melt processing

In this work well uniform dispersion of single-walled carbon nanotubes (SWNTs) in isotactic polypropylene (iPP) was achieved by shear mixing. The results obtained from the differential scanning calorimetry curves indicate that the addition of low SWNT amounts (less than 1 wt%) led to an increase in the rate of polymer crystallization with no substantial changes in the crystalline structure, as confirmed by X-ray diffraction. The tensile mechanical properties showed that Young’s modulus and tensile strength considerably increase in the presence of nanotubes, with a maximum for 0.75 wt%. The reinforcing effect of SWNTs was also confirmed by dynamic mechanical analysis where, by adding nanotubes, a noticeable increase in the storage modulus was detected. The beneficial effects of SWNT incorporation was underlined comparing the results obtained with those of carbon black used as a filler.     

Effect of NBR partitioning agent on the mechanical properties of PVC/NBR blends and investigation of phase morphology by atomic force microscopy

Poly(vinyl chloride) (PVC)/acrylonitrile–butadiene rubber (NBR) blends with different types of partitioning agent were obtained through melt blending. The samples were characterized according to the viscosities properties, torque rheometry and mechanical resistance as tensile testing, tear strength, and hardness. The morphology and phase imaging were studied using an atomic force microscopy operating in tapping mode (TMAFM). It was observed that the PVC/NBR blends with PVC as partitioning agent showed an increase in the tensile stress and Young’s modulus compared to the PVC/NBR blends with calcium carbonate as partitioning agent. The morphology of the blends examined by TMAFM evidenced the effect of the partitioning agent as obtained with other techniques.     

Synthesis of novel single-walled carbon nanotubes/poly (<Emphasis Type="Italic">p</Emphasis>-phenylene benzobisoxazole) nanocomposite

Poly (p-phenylene benzobisoxazole) (PBO) fibers are some of the strongest organic polymer fibers. However, the introduction of single-walled carbon nanotubes (SWNT) into the PBO backbone might lead to improvements in their alignment and physical properties. Therefore, SWNT was cut and functionalized by three oxidative cutting methods. After cutting, three different types of SWNT were obtained. Furthermore, copolymerization of SWNTs with PBO polymer was successfully carried out in a mixed solvent of polyphosphoric acid and methanesulfonic acid. The SWNTs were homogeneously distributed throughout the films of copolymerized products, as determined by Raman spectroscopy. The benzoxazole moieties could be formed between the carboxyl of SWNTs and o-aminophenol derivatives of PBO polymer. The length of SWNTs affected the dispersion and reaction activity. Short SWNTs could react with the PBO polymer more easily and form more covalent bonds.     

PVC／ABS共混体系的相容性与形态结构研究

采用种子乳液聚合技术在聚丁二烯（PB）乳胶粒子上接枝共聚苯乙烯（St）、α-甲基苯乙烯（α—MSt）和丙烯腈（AN）单体,合成了一系列不同AN结合量的ABS和α—MABS接枝共聚物。将其与聚氯乙烯（PVC）树脂熔融共混制得了PVC／AtkS共混物,利用扫描电镜（SEM）、透射电镜（TEM）和动态力学分析仪（DMA）对共混物的相容性和相结构进行了表征。结果发现,在PVC／ABS共混体系中,尽管改变接枝SAN共聚物的AN结合量,PVC和ABS接枝共聚物均为不相容体系;在ABS接枝共聚物中引入α-MSt后,当接枝SAN共聚物的AN结合量为18．7％～23．6％（质量分数）时,共混物在室温以上只存在1个tanδ峰,共混物成为相容体系,当AN结合量达到32．1％（质量分数）时,共混物成为部分相容体系。共混物的相区尺寸明显地依赖于接枝SAN共聚物中的AN结合量,与动态力学性能结果表现出良好的吻合。