原位生长的气相生长碳纤维增强C/C复合材料的制备及其弯曲性能

以丙烯为碳源, FeCl₃·6H₂O为催化剂, 采用化学气相沉积法(CVD)在碳毡和不同密度的C/C复合材料上原位气相生长碳纤维(VGCFs) , 并以含原位生长VGCFs的碳毡和不同密度的C/C复合材料为基体制备VGCFs-C/C复合材料。研究了反应压力、基体密度对VGCFs生长情况的影响, 借助扫描电镜(SEM)、光学显微镜观察原位生长VGCFs的形貌及基体原位生长VGCFs后热解炭形貌的变化, 并对比研究了C/C复合材料和VGCFs-C/C复合材料的弯曲性能。研究结果表明, 反应压力为3700 Pa, 基体密度低的情况更有利于VGCFs的生长; 原位生长的VGCFs改变了纤维表面热解炭的沉积形貌, 使得热解炭和碳纤维的结合面之间形成具有铆钉作用的球状结构, 增强了界面结合力, 从而提高了原位生长的高VGCFs含量样品的弯曲强度。     

Structural changes in fibrous carbon nanomaterials produced by adding sulfur during chemical vapor deposition

Vapor-grown carbon fibers (VGCFs), platelet graphite nanofibers (PGNFs), turbostratic carbon nanofibers (CNFs), and carbon spheres were continuously produced by the thermal decomposition of ethanol in the presence of an Fe catalyst and a sulfur promoter at 1100 degrees C under a nitrogen/hydrogen atmosphere in a vertical chemical vapor deposition reactor. The sulfur concentration dramatically affected the morphology and microstructure of the carbon materials produced. A large amount of sulfur in the catalytic precursor led to the direct pyrolysis of hydrocarbons and the formation of carbon spheres (Fe:S = 1:10) while a lower amount of sulfur led to the formation of fibrous carbon materials, including VGCFs (Fe:S = 1:0.2), PGNFs (Fe:S = 1:2), and turbostratic CNFs (Fe:S = 1:5). The degree of poisoning of the catalysts determined the precipitation of the graphene layers, allowing the different types of carbon material to form.     

Silica coating of vapor grown carbon fibers

Silica coatings have been applied to vapor grown carbon fibers (VGCFs) by a liquid phase deposition process. Unlike the coating of single walled carbon nanotubes, the addition of a surfactant to “solubilize” the VGCFs results in an extremely non-uniform coating consisting of spherical silica aggregated around the tubes. As was observed for fullerenes, hydroxylation of the surface of the VGCF appears to be key to the formation of a uniform silica coating. Irrespective of the type of VGCF, heating a suspension of VGCFs in nitric acid to dryness (Type II) gave us the best results in terms of silica growth around the VGCF and there is a correlation between the percent of hydroxyls present on the VGCF surface and on the type of growth that occurs on the VGCF. Nitric acid treatment of VGCFs for 1 day in solution were precipitated with acetone (Type III treatment), and then coated with silica. This acid treatment made the coated fibers highly soluble in EtOH.     

气相生长碳纤维增强水泥基复合材料的制备及性能

研究了脱油沥青(De-oiled asphalt)基气相生长碳纤维(VGCFs)增强水泥基复合材料的制备方法及其性能。以脱油沥青作原料,采用化学气相沉积法(CVD)制备出气相生长碳纤维,以此纤维制备水泥基功能复合材料。结果表明:低含量VGCFs的碳纤维增强水泥基复合材料具有良好的抗压强度和导电性能,在VGCFs的掺量由0增至0.6 %范围内,随着VGCFs掺量的增加,碳纤维增强水泥基复合材料的电阻率下降,抗压强度提高。当VGCFs为0.4 %时,VGCFs水泥基复合材料电阻率降低2个数量级,从3.25 ×105 Ω·cm 降为1.49 ×103 Ω· cm ,抗压强度提高28.8 %,为最佳掺量。      

Single wall nanotube and vapor grown carbon fiber reinforced polymers processed by extrusion freeform fabrication

Single wall carbon nanotubes (SWNTs) and vapor grown carbon fibers (VGCFs) were compounded with poly(acrylonitrile-co-butadiene-co-styrene) (ABS) to create composite materials for use with Extrusion Freeform Fabrication (EFF). The composite materials possessed homogeneously dispersed fibers that were oriented with EFF processing. The VGCF and SWNT reinforced materials processed by EFF displayed improved tensile modulus compared to similarly processed ABS and composite material with isotropic fiber orientation, and the SWNT reinforced material displayed the highest properties, strength and modulus, of the materials studied. The materials containing oriented VGCFs and SWNTs showed modulus improvements of 44 and 93%, respectively.     

FeCl3催化生长脱油沥青基气相生长炭纤维

以脱油沥青（DOA）为碳源,氯化铁为催化剂,在氩气和氢气的混合气氛下利用化学气相沉积法（CVD）制备了不同形貌的气相生长炭纤维（VGCFs）。讨论了在温度为1100℃时,不同的反应时间（分别为10min,20min,25min,30min和40min）对产物形貌和结构的影响。利用场发射扫描电镜（FE-SEM）、高分辨透射电镜（HRTEM）、X-射线衍射（XRD）和拉曼（Raman）光谱,对不同工艺参数下合成的产物进行了结构表征。结果表明：随着反应时间的增加,气相生长炭纤维的形貌由弯曲变得相对平直,进而相互贯穿;当反应时间为10min和20min时,气相生长炭纤维的直径分布在1.0μm～1.2μm之间;当反应时间为25min,30min和40min时,气相生长炭纤维的直径分布范围分别为250nm～300nm,350nm～400nm,700nm～800nm。另外,还观察到了V型的气相生长炭纤维。     

沉积条件对CVD碳纤维生长的影响

用CH4、H2或包含NH3的混合气体为反应气体,利用负偏压增强热丝化学气相沉积方法在沉积有过渡层(Ta或Ti)和催化剂层(NiFe)的Si衬底上制备碳纤维,并用扫描电子显微镜研究了它们的生长和结构,结果发现不同的沉积条件对碳纤维的生长和结构有很大的影响。在无辉光放电的条件下,衬底温度较低时碳纳米管或纤维生长困难;提高衬底温度,能够弯曲生长;在辉光放电的条件下,则呈现定向生长的特点。     

气相生长碳纤维在水泥基材料中的分散性研究

以脱油沥青(DOA)为原料,采用化学气相沉积法(CVD)制备出气相生长碳纤维(VGCFs).利用硬化试件电阻测试法和硬化试件断面形貌法.测试了VGCFs增强水泥的电阻率、变异系数和断面扫描电镜形貌,考察了3种不同制备工艺下VGCFs在增强水泥复合材料中的分散性.结果表明,先将分散剂、消泡荆、VGCFs在水中预分散再加入超细矿粉和水泥的搅拌工艺分散效果最好,干混法与湿混法较差.采用合理的制备工艺(预分散法),当VGCFs掺量为0.2%(体积分数)时可制得纤维均匀分散、电阻率小、变异系数小的VGCFs增强水泥.     

Y-junction multibranched carbon nanofibers

Multibranched carbon nanofiber (CNF) is produced by a thermal chemical vapor deposition method using camphor as precursor. Nickel and cobalt catalyst was deposited on silicon substrate by e-beam evaporation and used as substrate for the growth of carbon nanomaterials. Branched carbon nanofibers were grown on the nickel thin film at 900 degrees C, whereas spherical carbon beads formed on the cobalt thin film. These fibers followed base growth mechanism devoid of any catalyst particle at the tip of fibers.     

Continuous synthesis of carbon nanotubes using a metal-free catalyst by CVD

This study demonstrates the first example of the use of a metal-free catalyst for the continuous synthesis of carbon nanotubes (CNTs) by chemical vapor deposition (CVD). In this paper silica nanoparticles produced from the thermal decomposition of PSS-(2-(trans-3,4-Cyclohexanediol)ethyl)-Heptaisobutyl substituted (POSS) were used as catalyst and ethanol was served as both the solvent and the carbon source for nanotube growth. The POSS/ethanol solution was nebulized by an ultrasonic beam. The tiny mists were continuously introduced into the CVD reactor for the growth of CNTs. The morphology and structure of the CNTs have been investigated by scanning electron microscopy, high-resolution transmission electron microscopy, and Raman spectroscopy. The obtained CNTs have a multi-walled structure with diameters mainly in the size range from 13 to 16 nm. Detailed investigations on the growth conditions indicate that the growth temperature and POSS concentration are important for achieving high-quality nanotubes, and that the existing of small amount of water in ethanol is effective to remove amorphous carbon species during the formation of CNTs. The mass production of CNTs without any metal contaminant will provide a chance for investing and understanding the intrinsic properties of CNTs and applications particularly in nanoelectronics and biomedicines.     

Effects of the size of nano-copper catalysts and reaction temperature on the morphology of carbon fibers

In this study, carbon fibers with different morphologies, including coiled carbon nanofibers and straight carbon fibers, were obtained by the chemical vapor deposition using a Cu-catalytic pyrolysis of acetylene at 250 °C. The influences of nano-copper catalyst particle size and the reaction temperature on the morphology of carbon fibers were investigated. Under the same reaction condition, coiled carbon nanofibers generally were synthesized using nano-copper catalyst with smaller particles size, and bigger copper particles are apt to produce straight carbon fibers. With decreasing of reaction temperature to 200 °C, straight carbon fibers were obtained, instead of coiled carbon nanofibers at 250 °C. The product was characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and X-ray powder diffraction (XRD).     

Growth of carbon nanofibers on carbon fabric with Ni nanocatalyst prepared using pulse electrodeposition

The pulse electrodeposition (PED) technique was utilized to deposit nanosized (≤10?nm) Ni catalysts on carbon fabric (CF). Via an in?situ potential profile, the PED technique can control the Ni catalyst loading, which is an important parameter for the growth of carbon nanofibers (CNFs) on CF. The preparation of CNF-coated CF (carpet-like CF) was carried out in a thermal chemical vapor deposition system with an optimum loading of Ni catalysts deposited in the PED pulse range from 20 to 320 cycles. CNFs grown at 813?K using different pulse cycles had a narrow diameter distribution, around 15 ± 5?nm to 29 ± 7?nm; they have a hydrophobic surface, like lotus leaves. Transmission electron microscopy images confirmed the graphene structural transformation of CNFs with the growth temperature. Solid wire CNFs were initially grown at 813?K with graphene edges exposed on the external surface. At elevated growth temperatures (1073 and 1173?K), bamboo-like CNFs were obtained, with herringbone structures and intersectional hollow cores.     

二维树状分叉碳纤维的浮动催化法制备

采用两段加热卧式浮动催化法合成了二维树状分叉碳纤维。讨论了制备条件如:催化剂(二茂铁)、催化促进剂(噻吩)以及它们在碳源溶液中的含量、苯／氢的比例、氢气的流量等对生长二维树状分叉碳纤维的影响。二维树状分叉碳纤堆的分叉纤堆相互平行排列,直径与母体纤维接近,部分分叉碳纤维与其它碳纤维交叉相连。提出了二维树状分叉碳纤维的生长机理和交叉结构可能的生长模式;二维树状分叉碳纤维的生长符合气相生长碳纤堆的生长机理,是纳米碳纤维在反应管高温区继续生长的结果。可以预测,控制一定的条件,可以用两段加热卧式浮动催化法合成二维碳纤维网状结构,在复合材料等领域有潜在的应用价值。     

Study on the synthesis of carbon fibers and CNF using potassium iodide catalyst

Most catalysts used in preparing carbon materials by chemical vapor deposition were transitional metals such as Fe, Co, Ni and only a few references were about the synthesis of carbon materials using water-soluble catalysts until now. Compared with metals, water-soluble catalysts can be conveniently removed from products. In our present works, water-soluble salt potassium iodide (KI) was found to be an efficient catalyst to grow carbon fibers and CNF under suitable conditions. Various structures of carbon fibers were synthesized by chemical vapor deposition using KI as the catalyst. And the experimental results showed that the nanostructure evolution of the fibers is strongly dependent on the temperature and history of the catalyst.     

Tensile properties of VGCF reinforced carbon composites

Carbon composites based on vapor grown carbon fibers prepared by a fixed catalyst method were fabricated using a pitch infiltration technique. The composites have both unidirectional and bi-directional fiber reinforcement, and different fiber volume fractions ranging from 25% to 56%. Specimens were prepared from these composites for tensile testing at room temperature, and tensile modulus and strength were determined. The composite modulus was then used to estimate the fiber modulus.     

Carbon and glass hierarchical fibers: Influence of carbon nanotubes on tensile,flexural and impact properties of short fiber reinforced composites

Dense carbon nanotubes (CNTs) were grown uniformly on the surface of carbon fibers and glass fibers to create hierarchical fibers by use of floating catalyst chemical vapor deposition. Morphologies of the CNTs were investigated using scanning electronic microscope (SEM) and transmission electron microscope (TEM). Larger diameter dimension and distinct growing mechanism of nanotubes on glass fiber were revealed. Short carbon and glass fiber reinforced polypropylene composites were fabricated using the hierarchical fibers and compared with composites made using neat fibers. Tensile, flexural and impact properties of the composites were measured, which showed evident enhancement in all mechanical properties compared to neat short fiber composites. SEM micrographs of composite fracture surface demonstrated improved adhesion between CNT-coated fiber and the matrix. The enhanced mechanical properties of short fiber composites was attributed to the synergistic effects of CNTs in improving fiber–matrix interfacial properties as well as the CNTs acting as supplemental reinforcement in short fiber-composites.     

Low Temperature Growth of Vertically Aligned Carbon Nanotubes via Floating Catalyst Chemical Vapor Deposition Method

Synthesis of carbon nanotubes (CNTs) below 600℃ using supporting catalyst chemical vapor deposition method was reported by many research groups.However,the floating catalyst chemical vapor deposition received less attention due to imperfect nanotubes produced.In this work,the effects of varying the preheating temperature on the synthesis of CNT were investigated.The reaction temperature was set at 570℃.The preheating set temperature was varied from 150 to 400℃ at 50℃ interval.Three O-ring shape heating mantels were used as heating source for the preheater.In situ monitoring device was used to observe the temperature profile in the reactor.Benzene and ferrocene were used as the carbon source and catalyst precursor,respectively.Vertically aligned CNTs were synthesized when the preheating temperature was set at 400℃.When the preheating temperature was increased up to 400℃,both the length and the alignment of CNTs produced were improved.     

碳纳米团簇向碳纳米纤维相转变机理研究

为了能够快速且大面积生长碳纳米纤维,研究碳纳米纤维的形成、转变及在各种物理、化学环境下的反应机理,应用等离子化学气相沉积(PECVD)方法,以CH4为反应气体,FeCl2为催化剂在玻璃衬底上生长碳纳米薄膜.应用扫描电镜(SEM)观察了碳纳米纤维薄膜的表面形貌,拉曼(Raman)光谱分析了碳纳米纤维的结构组成.结果表明,无催化剂时薄膜主要由纳米团簇构成,而催化作用下薄膜呈纤维状生长,纳米纤维为典型的碳纳米管石墨特征峰.在温度,气压,催化剂等反应条件中,FeCl2催化剂对碳纳米薄膜的取向生长起决定性作用,通过调节催化剂的浓度与分布,可有效改变碳纳米纤维的密度与分布.     

THE INFLUENCE OF SYNTHESIS PARAMETERS ON THE PRODUCTION OF MULTIWALLED CARBON NANOTUBES BY THE FERROCENE CATALYZED PYROLYSIS OF TOLUENE

A high yield (∼32 wt.%) of multiwalled carbon nanotubes was obtained in an iron catalyzed reaction. This was achieved in the temperature range 800-1000°C under an atmosphere of H₂/Ar by an improved solution injection method in a horizontal reactor using toluene as carbon source and ferrocene as catalyst precursor. The pyrolysis temperature, ferrocene concentration, solution feeding rate and carrier gas flow rate all influenced the yield of carbon nanotubes and the thickness of the aligned carbon nanotube films. The carbon nanotubes was prepared in high purity using optimized pyrolysis conditions.     

Formation of carbon fiber florets using copper tartrate catalyst precursors

A novel method was investigated to synthesize carbon fiber florets using copper tartrate catalyst precursors by catalytic chemical vapor deposition at 300 °C. Samples were obtained for different growth periods. On the basis of electron microscopy and X-ray diffraction characterizations, a growth model for the formation of fiber florets was proposed as well as the branching of fibers nearby copper catalyst particles. These findings could facilitate the understanding of the catalytic growth process of different carbon materials including carbon nanotubes and graphene under different reaction parameters.