碳纳米管表面处理及其在铜基复合材料中的应用

碳纳米管因特殊结构带来的优异性能而被海内外学者广泛关注,以碳纳米管为增强相制备铜基复合材料是使铜基导体同时具有高强度和高导电性能的有效途径。然而,由于碳纳米管表面能高、表面反应活性低,碳纳米管/铜复合材料制备的过程中存在增强体分散性差和界面结合强度弱两大问题,从而阻碍了复合材料高性能的实现。在碳纳米管/铜复合材料的制备过程中,采用适当的方法对碳纳米管进行表面处理能改变碳纳米管的表面结构和反应活性,在改善碳纳米管的分散性的同时增强碳纳米管与铜基体的界面结合,从而提高碳纳米管的增强效率,保证复合材料良好的综合性能。然而,表面处理过程可能会破坏碳纳米管的结构完整性,影响碳纳米管的本征性能,进而影响其增强效果,或可能在基体中引入其他杂质,影响复合材料的导电和导热性能。因此,在进行表面处理时应综合考虑其对碳纳米管结构性能及复合材料增强作用的影响。近年来,研究者们通过优化碳纳米管表面处理工艺突破了碳纳米管/铜复合材料在制备过程的难点,在保证铜基体优异的导电、导热性能的同时,大幅提高了碳纳米管/铜复合材料的力学性能。碳纳米管表面处理工艺类型大致可分为机械球磨、化学表面改性、表面镀层和联合表面处理四类。传统的机械球磨表面处理对碳纳米管的结构破坏较大;化学表面改性又分为共价表面改性和非共价表面改性,非共价表面改性在保持碳纳米管完整的管状结构和优异性能的同时,提高了碳纳米管在溶液中的分散性,但用于复合材料制备时会给基体引入有机杂质,影响复合材料性能;共价表面改性和表面镀层是铜基复合材料制备过程中最为常用和有效的表面处理方法,其能够在提高碳纳米管在基体中的分散性能的同时改善碳纳米管表面的反应活性,从而形成碳纳米管和铜基体之间强度较高的反应结合界面,实现碳纳米管/铜复合材料高强高导的综合性能。此外,可通过综合利用各种表面处理方法,结合各表面处理工艺的优势,获得更为优异的改性效果。本文从碳纳米管表面处理工艺的基本类型以及碳纳米管表面处理对铜基复合材料结构和性能的影响两方面阐述了碳纳米管表面处理在铜基复合材料中的应用和研究进展,并对其未来的研究方向进行了展望。     

Effects of interface characteristics on mechanical properties of carbon nanotube reinforced polymer composites

Abstract

Carbon nanotubes (CNTs) possess exceptional mechanical properties and are therefore suitable candidates for use as reinforcements in composite materials. To take full advantage of their exceptional properties, load sharing mechanisms needs to be understood in the composite materials. Load transfer in composites is achieved through the fibre/matrix interface. In the present paper, finite element method is used to investigate the effects of interface behaviour on carbon nanotube based composite mechanical properties. The effective nanocomposite mechanical properties are evaluated using a three-dimensional nanoscale representative volume element (RVE). In this RVE approach, a single nanotube and the surrounding polymer matrix are modelled. Two cases of perfect bonding and an elastic interface are considered. In addition, the rule of mixtures relations is used to validate the results of numerical models. The results indicate that mechanical properties of nanocomposite materials are significantly influenced by the interface strength.     

Mechanical characterization of copper coated carbon nanotubes reinforced aluminum matrix composites

In this investigation, carbon nanotube (CNT) reinforced aluminum composites were prepared by the molecular-level mixing process using copper coated CNTs. The mixing of CNTs was accomplished by ultrasonic mixing and ball milling. Electroless Cu-coated CNTs were used to enhance the interfacial bonding between CNTs and aluminum. Scanning electron microscope analysis revealed the homogenous dispersion of Cu-coated CNTs in the composite samples compared with the uncoated CNTs. The samples were pressureless sintered under vacuum followed by hot rolling to promote the uniform microstructure and dispersion of CNTs. In 1.0 wt.% uncoated and Cu-coated CNT/Al composites, compared to pure Al, the microhardness increased by 44% and 103%, respectively. As compared to the pure Al, for 1.0 wt.% uncoated CNT/Al composite, increase in yield strength and ultimate tensile strength was estimated about 58% and 62%, respectively. However, in case of 1.0 wt.% Cu-coated CNT/Al composite, yield strength and ultimate tensile strength were increased significantly about 121% and 107%, respectively.     

Quantitative evaluation of initial galvanic corrosion behavior of CNTs reinforced Mg–Al alloy

The macroscopic corrosion phenomenon of the CNTs reinforced Mg composites remarkably occurred in the moist environment, due to a large potential of the galvanic cells formed between α-Mg matrix and CNTs. Therefore, it is necessary to reduce the potential difference at their interfaces in order to obstruct the galvanic corrosion phenomenon. In this study, AZ61B alloy composites reinforced with CNTs (CNT/AZ61B) were fabricated by powder metallurgy method, and their potential differences between CNTs and the α-Mg matrix were reduced by concentration of Al atoms around CNTs via heat treatment. The potential distribution around CNTs was measured by using scanning Kelvin probe force microscopy (SKPFM). Heat treatment of CNT/AZ61B composites at 823 K for 10 h caused the obvious concentration of Al atoms around CNTs, and resulted in the remarkable decrease of the potential difference at the interface between the α-Mg matrix and CNTs. Additionally, the salt water immersion test results indicated that the corrosion rate of CNTs/AZ61B composite materials after heat treatment was obviously reduced to less than about 30% of the non-treated composite material. Thus, the changes of α-Mg matrix potential by concentrating Al atoms around CNTs was effective to improve initial galvanic corrosion resistance of CNTs reinforced Mg composites.     

Ag纳米晶颗粒/碳纳米管复合材料的制备与结构研究

利用热蒸发方法在多壁碳纳米管表面沉积Ag纳米颗粒,XRD结果显示,Ag纳米颗粒以晶体形态存在,同时透射电镜分析结果表明,Ag纳米晶颗粒引起碳纳米管横截面形变,从而形成Ag纳米晶颗粒/碳纳米管异质复合材料,这些纳米异质复合材料相互连接,形成网络化分布的结构.     

贵金属纳米颗粒的表面等离子共振研究

通过修正的Mie理论分别对单金属Ag、单金属Cu和Cu核Ag壳纳米颗粒/玻璃复合材料的吸收光谱进行了理论计算.计算结果表明,对单金属Ag纳米颗粒/玻璃复合材料,Ag的吸收峰位于425nm左右,不随颗粒尺寸变化而发生偏移;对单金属Cu纳米颗粒/玻璃复合材料,Cu的吸收峰也不随尺寸变化发生偏移但强度较弱;对Cu核Ag壳纳米...     

Microstructures and tensile behavior of carbon nanotube reinforced Cu matrix nanocomposites

Carbon nanotubes (CNTs) have been considered as an ideal reinforcement to improve the mechanical performance of monolithic materials. However, the CNT/metal nanocomposites have shown lower strength than expected. In this study, the CNT reinforced Cu matrix nanocomposites were fabricated by spark plasma sintering (SPS) of high energy ball-milled nano-sized Cu powders with multi-wall CNTs, and followed by cold rolling process. The microstructure of CNT/Cu nanocomposites consists of two regions including CNT/Cu composite region, where most CNTs are distributed, and CNT free Cu matrix region. The stress–strain curves of CNT/Cu nanocomposites show a two-step yielding behavior, which is caused from the microstructural characteristics consisting of two regions and the load transfer between these regions. The CNT/Cu nanocomposites show a tensile strength of 281 MPa, which is approximately 1.6 times higher than that of monolithic Cu. It is confirmed that the key issue to enhance the strength of CNT/metal nanocomposite is homogeneous distribution of CNTs.     

CNTs修饰及其增强Cu基复合材料的研究

碳纳米管(CNTs)经不同方法修饰后,通过湿式球磨法制备2%-CNTs/Cu(体积分数,下同)复合粉体,再通过H2退火-冷压烧结工艺制得2%-CNTs/Cu复合材料。结果表明:球磨短切后CNTs的长度变短,端口被打开,无定型碳增多,而混酸纯化后CNTs表面的杂质完全被除去,引入大量含氧活性基团;湿式球磨法可以将CNTs嵌入Cu基体中,并与其紧密结合形成片状复合结构,再经H2退火处理后得到超细晶复合粉体;短切和纯化都有利于CNTs在Cu基体的分散与结合,其中短切CNTs纯化后制得复合材料的抗拉强度和维氏硬度最高,分别为296MPa和139.8HV,较基体提高了123.6%和42.9%,归因于细晶强化和载荷传递。     

Fabrication and mechanical/conductive properties of multi-walled carbon nanotube (MWNT) reinforced carbon matrix composites

Multi-walled carbon nanotube (MWNT) reinforced carbon matrix (MWNT/C) composites have been explored using mesophase pitch as carbon matrix precursor in the present work. Results show that carbon nanotubes (CNTs)can enhance the mechanical properties of carbon matrix significantly. The maximal increment of the bending strength and stiffness of the composites, compared with the carbon matrix, are 147% and 400%, respectively. Whereas the highest in-plane thermal conductivity of the composites is 86 W m^− 1 K^− 1 which much lower than that of carbon matrix (253 W m^− 1 K^− 1).At the same time the electrical resistivity of the composites is much higher than that of matrix. It is implicated that CNTs seem to play the role of thermal/electrical barrier in the composites. FSEM micrograph of the fracture surface for the composites shows that the presence of CNTs restrains the crystallite growth of carbon matrix, which is one of factors that improve mechanical properties and decrease the conductive properties of the composites. The defects and curved shape of CNTs are also the affecting factors on the conductive properties of the composites.     

Wear and mechanical properties of carbon fiber reinforced copper alloy composites

The mechanical properties and wear behavior of lead-free metal matrix composite, and carbon fiber reinforced copper alloy composites were studied, and compared with a common leaded copper (Cu-6wt.%Zn-6wt.%Sn-3 wt.%Pb) alloy. The effects of carbon fibers and alloy element Sn on these properties were investigated. Carbon fiber/Cu–Sn–Zn composites showed higher hardness and bending strength than the leaded copper alloy when carbon fibers content is less than 12 vol.%. Tribological tests were conducted with disks made from these materials, and tested against a steel counterface. The carbon fiber/Cu–Sn–Zn composites showed higher wear resistance than the leaded copper alloy under a constant load of 50 N. Observations on surface morphology were utilized in understanding the wear properties of these materials. The results show that the wear mechanism of the leaded copper alloy is adhesive wear, while it is mainly adhesive wear accompanied by oxidative wear for the 12 vol.% carbon fiber/Cu–Sn–Zn composites. The 12 vol.% carbon fiber/Cu–Sn–Zn composites are likely to provide optimum substitutes for the leaded copper alloy under the load of 50 N.     

Preparation and properties of powder styrene-butadiene rubber composites filled with carbon black and carbon nanotubes

Carbon nanotubes (CNTs) and carbon black (CB) filled powder styrene-butadiene rubber (SBR) composites were prepared by spray drying of the suspension of CNTs and CB in SBR latex. The powders were sphere like and fine with uniform diameters of 10-15 μm. Experimental results showed that the introduction of CNTs into the matrix was beneficial to improve the security of the vulcanization of the rubber composites, and the dynamic and basic mechanical properties of the CNTs/SBR composites were better than those of CB/SBR and neat SBR composites. Observations on the microstructure of the composites indicated that CNTs were well dispersed in the matrix. Morphology of the fracture confirmed that the bonding between CNTs and rubber matrix was strong and load can be transferred to CNTs efficiently during the mechanical property tests. Moreover, the powder SBR composites containing well-dispersed CNTs could be perfect candidate as additives for other polymers.     

Recent advances in understanding the reinforcing ability and mechanism of carbon nanotubes in ceramic matrix composites

Since the discovery of carbon nanotubes (CNTs), commonly referred to as ultimate reinforcement, the main purpose for fabricating CNT–ceramic matrix composites has been mainly to improve the fracture toughness and strength of the ceramic matrix materials. However, there have been many studies reporting marginal improvements or even the degradation of mechanical properties. On the other hand, those studies claiming noticeable toughening measured using indentation, which is an indirect/unreliable characterization method, have not demonstrated the responsible mechanisms applicable to the nanoscale, flexible CNTs; instead, those studies proposed those classical methods applicable to microscale fiber/whisker reinforced ceramics without showing any convincing evidence of load transfer to the CNTs. Therefore, the ability of CNTs to directly improve the macroscopic mechanical properties of structural ceramics has been strongly questioned and debated in the last ten years. In order to properly discuss the reinforcing ability (and possible mechanisms) of CNTs in a ceramic host material, there are three fundamental questions to our knowledge at both the nanoscale and macroscale levels that need to be addressed: (1) does the intrinsic load-bearing ability of CNTs change when embedded in a ceramic host matrix?; (2) when there is an intimate atomic-level interface without any chemical reaction with the matrix, could one expect any load transfer to the CNTs along with effective load bearing by them during crack propagation?; and (3) considering their nanometer-scale dimensions, flexibility and radial softness, are the CNTs able to improve the mechanical properties of the host ceramic matrix at the macroscale when individually, intimately and uniformly dispersed? If so, how? Also, what is the effect of CNT concentration in such a defect-free composite system? Here, we briefly review the recent studies addressing the above fundamental questions. In particular, we discuss the new reinforcing mechanism at the nanoscale responsible for unprecedented, simultaneous mechanical improvements and highlight the scalable processing method enabling the fabrication of defect-free CNT-concentered ceramics and CNT-graded composites with unprecedented properties. Finally, possible future directions will be briefly presented.     

CNTs强化碳纤维/环氧复合材料界面过渡层及其对界面性能的影响

采用上浆的方法将碳纳米管(CNTs)引入到碳纤维表面,制备CF/CNTs/环氧多尺度复合材料。相比上浆处理前,复合材料的层间剪切强度及弯曲强度分别提高了13.54%和12.88%。采用力调制原子力显微镜及扫描电镜的线扫描功能对复合材料界面相精细结构进行分析。结果表明:CNTs的引入在纤维和基体间构建了一种CNTs增强环氧树脂的界面过渡层。该界面过渡层具有一定厚度,且其模量和碳元素含量呈梯度分布。在固化成型前对含有CNTs的复合材料进行超声处理,促使碳纤维表面的CNTs向周围树脂中分散,发现复合材料的界面过渡层被弱化,其层间剪切强度及弯曲强度较超声处理前分别下降了7.33%和5.34%,验证了CNTs强化的界面过渡层对于提高复合材料界面性能的重要作用。     

Influence of Cu nanoparticle size on the photo-electrochemical response from Cu-multiwall carbon nanotube composites

We show that Cu metal nanoparticle-multiwall carbon nanotube (MWCNT) assemblies can act as a new hybrid photoactive layer in photo-electrochemical devices. The carbon nanotube (CNT) composites were formed by a controlled thermal deposition of copper which produced crystalline metal nanoparticles localized on the carbon tube outer walls. The photoresponse evaluated in terms of IPCE (incident photon-to-charge carrier generation efficiency) varied for different sized-Cu-MWCNT samples across all the visible and near ultraviolet photon energy range with respect to the response of bare MWCNTs. In the case of 0.2 nm Cu nominal thickness, the IPCE increased, reaching 15%, a value 2.5 times higher than that measured for bare MWCNTs. As the Cu nominal coverage thickened, the IPCE started to decrease and become totally ineffective after 1 nm deposited Cu. The IPCE increase found was interpreted as being the result of a remarkable charge transfer between the Cu metal nanoparticles and the CNTs due to the formation of a strong ionic bond at their interface. The results obtained prove that the metal nanoparticle-CNT composites have optical, electrical and structural properties that can be applied in a variety of nanoscale architectures for novel photo-electrochemical devices.     

Preparation and properties of the powder SBR composites filled with CNTs by spray drying process

Carbon nanotubes (CNTs) filled powder styrene-butadiene rubber (SBR) composites were prepared by spray drying of the suspension of CNTs in SBR latex. The powder was spherical like and uniform with an average diameter of less than 10 μm. The dispersion of CNTs in the rubber matrix was improved remarkably compared with that in the rubber composites obtained by the conventional mechanical mixing method. Further study about the effect of CNTs on the prepared SBR composites was performed by analyzing the vulcanization process of the SBR powder, thermal and mechanical properties of the vulcanized SBR composites. Differential scanning calorimeter (DSC) analysis indicated that the glass transition temperatures of SBR composites increased with the increasing ratio of CNTs. The vulcanization process showed that CNTs could decelerate the vulcanization of the SBR composites. Dynamic mechanical analysis indicated that the storage modulus of the composites was improved with the CNTs additions, especially when the CNTs addition exceeded 30 phr. Compared with pure SBR composites, the hardness, tensile and tear strengths of the composites filled with 60 phr CNTs enhanced 73.9%, 327.7% and 191.1%, respectively, which should be ascribed to the excellent mechanical properties of CNTs and uniform dispersion of CNTs in the rubber matrix.     

GNP-Ni/Cu复合材料的界面调控和强化机理

采用粉末冶金法,通过“湿法混合”、放电等离子烧结和热挤压相结合的三步工艺分别制备了石墨烯纳米片(GNP)增强铜基复合材料(GNP-Cu)和GNP-Ni增强铜基复合材料(GNP-Ni/Cu)。通过物相组成和显微组织表征,并结合致密度、电导率和力学性能测试,结果表明：GNP和Ni的含量(质量分数)分别为0.2%和1.5%的GNP-Ni/Cu复合材料,其显微硬度和屈服强度比纯Cu分别提高了38%和50%、比0.2GNP/Cu复合材料分别提高了14.0%和11.6%。这些结果表明,Ni的添加改善了GNP与Cu的界面结合,使GNP-Ni/Cu复合材料的力学性能显著提高。GNP的载荷传递强化和热失配强化以及Ni的固溶强化,是材料力学性能提高的主要原因。     

Effect of copper content on the thermal conductivity and thermal expansion of Al–Cu/diamond composites

Al–Cu matrix composites reinforced with diamond particles (Al–Cu/diamond composites) have been produced by a squeeze casting method. Cu content added to Al matrix was varied from 0 to 3.0 wt.% to detect the effect on thermal conductivity and thermal expansion behavior of the resultant Al–Cu/diamond composites. The measured thermal conductivity for the Al–Cu/diamond composites increased from 210 to 330 W/m/K with increasing Cu content from 0 to 3.0 wt.%. Accordingly, the coefficient of thermal expansion (CTE) was tailored from 13 × 10⁻⁶ to 6 × 10⁻⁶/K, which is compatible with the CTE of semiconductors in electronic packaging applications. The enhanced thermal conductivity and reduced coefficient of thermal expansion were ascribed to strong interface bonding in the Al–Cu/diamond composites. Cu addition has lowered the melting point and resulted in the formation of Al₂Cu phase in Al matrix. This is the underlying mechanism responsible for the strengthening of Al–Cu/diamond interface. The results show that Cu alloying is an effective approach to promoting interface bonding between Al and diamond.     

AlN-CNTs/聚酰亚胺复合材料的制备与性能

为了研究氮化铝(AlN)和碳纳米管(CNTs)对聚酰亚胺(PI)的导热、热学、力学性能的协同效应,采用湿法球磨和热压成型法制备了AlN/PI和CNTs-AlN/PI复合材料。利用X射线衍射仪、扫描电子显微镜对复合材料进行了物相分析和断面形貌表征,分别考察了AlN及其与CNTs协同对PI复合材料的导热、热学、力学性能的影响。结果表明,AlN和CNTs在PI基体中分散均匀且接触界面良好,AlN的加入可以显著地提高复合材料的导热性能,且对复合材料的热稳定性和力学性能有一定的提高;固定AlN的含量为10%,加入少量的CNTs可以提高复合材料的导热性能,但对复合材料的力学性能有一定的负面影响。     

Thermal Conductivity Behavior of Carbon Nanotubes Reinforced Copper Matrix Composites

Carbon nanotubes (CNT) exhibit excellent thermal conductivity.Therefore they are potential reinforcements in composites materials for thermal management applications,where high thermal conductivity and low coefficient of thermal expansion (CTE) are required.In the present study,CNT/Cu composites containing CNTs varying from 0 vol.％ to 15 vol.％ were prepared,and their thermal conductivity behavior was studied in detail.The results indicated that the thermal conductivity of the composites shows no enhancement by the incorporation of CNTs.The presence of interfacial thermal resistance and high level of porosity are the main reasons for this low thermal conductivity.The well dispersed 0-10 vol.％ CNTs composites show a very close to the thermal conductivity of Cu.However,the addition of 15 vol.％ CNTs results in a rather low thermal conductivity of CNT/Cu composites due to the presence a high level of porosity induced by the formation of CNT clusters.The present paper also claims that a further substantial enhancement in thermal conductivity is only possible if the nanotubes are randomly oriented in the plane or if they are all aligned in one direction,for which the processing of CNTs-aligning in metal matrix should be developed.     

Fabrication and properties of CNTs/carbon fabric hybrid multiscale composites processed via resin transfer molding technique

Carbon nanotubes (CNTs) are effective fillers/reinforcements regarding improving the properties of polymer. In the present paper, carboxylic acid functionalized CNTs were used to modify epoxy with intent to develop a nanocomposite matrix for hybrid multiscale composites combining benefits of nanoscale reinforcement with well-established fibrous composites. CNTs were dispersed in epoxy by using high energy sonication. At low contents of CNTs, hybrid multiscale composites specimens were manufactured via resin transfer molding (RTM) process. The processibility of CNTs/epoxy systems was explored with respect to their viscosity. The dispersion quality and re-agglomeration behavior of CNTs in epoxy were characterized using optical microscope. A CNTs loading of 0.025 wt% significantly improved the glass transition temperatures (Tg) of the hybrid multiscale composites. Scanning electron microscopy (SEM) was used to examine the fracture surface of the failed specimens. It is demonstrated that the addition of small amount of CNTs (0.025 wt%) to epoxy for the fabrication of multiscale carbon fabric composites via RTM route effectively improves the matrix-dominated properties of polymer based composites. Hybridization efficiency in carbon fiber reinforced composites using CNTs is found to be highly dependent on the changes in the dispersion state of CNTs in epoxy.