多元物理场CVI制备C/C复合材料过程优化

采用普通碳毡作为增强体, 丙烯作为碳源气体, 氢气作为稀释气体, 在自制的化学气相沉积炉中使用多元物理场化学气相渗透工艺(MFCVI)制备了C/C复合材料。根据不同的工艺条件设计了一组正交实验, 以最终密度和石墨化度为指标对材料的制备过程进行了优化。结果表明, 在沉积控制温度650 ℃、丙烯分压12 kPa、总气流量为40 mL/s、总压力为20 kPa条件时, 在15 h沉积时间内可以获得较好的综合性能指标。验证实验结果表明, 在上述实验条件下, 材料的密度达到1.70 g/cm³, 石墨化度可达67.1%, 密度分析结果表明, 其密度分布呈现两边高中间低的特征, 材料的密度分布可以满足应用要求。     

Highly stable nanocarbon supported Pt catalyst for fuel cell via a molten salt graphitization strategy

Proton exchange membrane fuel cells (PEMFCs) durability has been severely hindered by carbon support poor stability in the cathodic Pt-based catalyst. Herein, a high-surface-area nitrogen-doped graphitic nanocarbon (N-G-CA) with mesopores is developed as Pt support to address PEMFCs durability challenge. Resorcinol-formaldehyde aerogel pyrolyzed carbon aerogel is selected as N-G-CA raw material. Nitrogen atoms are introduced into carbon aerogel via NH₃ heat treatment. Then, nitrogen-doped carbon aerogel is transferred into N-G-CA via heating together with transition-metal salts (one of FeCl₃, FeCl₂, CoCl₂, or MnCl₂, etc.) at 1200 °C. As ORR catalyst, Pt/N-G-CA half-wave potential only lost 10 mV, after 30, 000 cycles accelerated aging test in the rotating-desk-electrode. Only 12 mV voltage loss at 1.5 A/cm2 is observed, after 5, 000 cycles for membrane electrode. Pt/N-G-CA exhibits superior durability and activity than commercial Pt/C. High durability of Pt/N-G-CA is due to N-G-CA high graphitization extent, as well as the interactions between doping nitrogen and Pt. N-G-CA is promising as stable support for durable Pt-based catalysts in PEMFCs, thanks to enhanced carbon corrosion resistance, uniformly dispersed Pt, and strong support-metals interaction.     

高温法处理铝电解废阴极的机理

高温法是目前国内处理铝电解废阴极的主要研究方向。系统研究了焙烧温度、焙烧时间、样品粒度等对氰化物、氟化物及其它元素脱除效率的作用规律,研究了石墨碎石墨化度、真密度、粉末电阻率与焙烧温度的关系。研究表明,在600℃焙烧时氰化物可以完全分解,在1 000℃以上可以脱除氟及其其它成分(不含碳),氟及其它成分的脱除率主要和焙烧温度有关,焙烧温度越高,氟及其它成分的脱除率越高;石墨碎的石墨化度和真密度随焙烧温度的升高而提高,焙烧温度达到2 600℃时石墨碎的石墨化度达到98.4%、真密度达到2.270 3 g/cm³;石墨碎的粉末电阻率随焙烧温度的升高而降低;焙烧所得石墨碎具有较高的应用价值。     

Effect of matrix content on the performance of carbon paper as an electrode for PEMFC

Porous conducting carbon fiber‐based composite paper is used as an electrode backing in the fuel cell assembly. It not only acts as a channel through which the reactant and product gases pass to and from the bipolar plate and the catalyst site but also helps in the flow of electrons. In order to perform its role efficiently, it should have sufficient strength, high electrical conductivity, and ideal porous structure. Carbon paper has been fabricated, which builds up the required composite properties. Studies have been conducted to optimize the fiber/matrix ratio in the carbon paper, while ensuring the perfect combination of porosity, mechanical strength, and electrical conductivity for an electrode in a proton electrolyte membrane fuel cells. Detail physico‐mechanical and electrochemical characterizations further ascertain that the fiber/matrix ratio plays an important role in tuning the composite properties. The polarization curve of the unit proton exchange membrane (PEM) fuel cell (with an effective electrode area 4 cm²) shows a peak power density of 916 mW/cm² for the sample with fiber/matrix ratio of 65:35, which is almost the same as the commercially available sigracet gas diffusion layer (SGL) carbon paper tested under similar conditions. Further, proportionally enlarging the electrode area to 100 cm² shows that the carbon paper not only shows almost repeatable results in a given set up but also scales up.     

Some observations on stress graphitization in carbon-carbon composites

The in situ stress graphitization behavior of hard carbons in unidirectionally aligned carbon-carbon (C-C) composites was studied for three carbon fibers (PAN-based T-50, pitch-based PX7 and rayon-based WCA) and two carbon precursor resins [phenol-formaldehyde (SC1008) and polyarylacetylene (PAA), a high char-yielding, low shrinkage resin]. Graphitization was followed by measurements of density, transverse thermal expansion, d-spacing by X-ray diffraction (XRD) and by scanningelectron microscopy (SEM). In conjunction with xenon-ion etching, the SEM technique was found to be particularly effective in identifying localized regions of graphitized matrix. Results reveal that the graphitization of the composite is significantly greater than graphitization of fiber or matrix alone to the same temperatures. SEM observations indicate that graphitization is confined to the matrix, usually as a sheath-like structure adjacent to the fiber and 1–3 μm thick. Such localized graphitization, usually termed stress graphitization, is believed to be the result of thermally induced tensile or compressive stresses acting at the fiber-matrix interface. Debonded regions, which are believed to either initiate at heatup or grow from pre-existing cracks in the resin-matrix composite, show less stress graphitization than well-bonded regions, presumably because the debond gaps impede stress buildup at the fibermatrix interface.Studies with three different fibers and one matrix (PAA) in matrix-rich composites showed variable degrees of localized stress graphitization, suggesting that the thermal expansion stresses responsible for stress graphitization vary with different fiber-matrix combinations. One consequence of a well-oriented stress-graphitized sheath was found to be debonding of fiber and matrix. Possible reasons for such debonding are discussed briefly.     

气相生长炭纤维的物理性能及其作为复合材料增强体的研究

采用不同的测试方法,测定了气相生长炭纤维（ＶＧＣＦ） 石墨化前后的密度、元素组成、拉伸强度和模量等基本物理性能及以它们增强的环氧树脂基复合材料的力学性能。结果表明, 石墨化后ＶＧＣＦ 的综合物理性能比未石墨化的ＶＧＣＦ 有明显的提高。     

石墨化竹炭的微观结构及其复合材料的制备与性能

采用SEM及XRD技术表征经2 800℃石墨化处理的竹炭的微观结构;以石墨化竹炭为导电骨料、酚醛树脂为粘结剂、炭黑为添加剂,采用模压成型法制备石墨化竹炭/酚醛树脂复合材料;考察石墨化竹炭的粒度、酚醛树脂用量、炭黑添加方式和用量、成型压力及固化温度等工艺因素对复合材料性能的影响。结果表明:增大竹炭粉粒的粒径、增加炭黑用量和提高固化温度有利于提高复合材料的导电性,但会不同程度地影响复合材料的力学性能、显气孔率和吸水率;随着酚醛树脂用量的增加,复合材料的抗弯强度提高,导电性、吸水率和显气孔率下降;提高成型压力可同时提高复合材料的性能;制备竹炭/酚醛树脂复合材料的最佳工艺条件为竹炭粒度≤75μm、树脂用量30%(质量分数)、炭黑用量5%(质量分数)、成型压力280 MPa、固化温度180℃。     

球墨铸铁加热过程中渗碳体石墨化的原位观察

采用激光共聚焦扫描显微镜直接观察了球墨铸铁在加热过程中渗碳体的分解和石墨形态的演化。结果表明：球墨铸铁在加热过程中渗碳体逐渐溶解,加热速率越快,渗碳体的分解速率越快。加热过程中石墨形态的演变行为与加热速率有关。加热速率较慢,组织中出现了小石墨,原有石墨长大。加热速率较快,渗碳体周围的小石墨逐渐溶解变小。     

大型风电球墨铸铁件的生产实践

以轮毂为例,介绍对大型风力发电机球墨铸铁件生产工艺进行的试验研究。通过优化铸型工艺,采用适当的浇注系统和低温石墨化退火工艺,选择合理的化学成分,控制球化处理与孕育处理,可生产出各项性能指标合格的风电铸件。     

Evolution with heat treatment of crystallinity in carbons

The variation with heat treatment of the dimensions L_a and L_c of the graphite-like crystallites of graphitizable and non-graphitizable carbons is studied. The increases of L_a and L_c with heat treatment temperature (HTT) owing to three processes (crystallite growth in-plane, coalescence of crystallites along the c-axis and coalescence of crystallites along the a-axis) are functionally separated. The evolution with HTT of the number of crystallites (N_cr), the mean volume of the crystallites (v_cr) and the total volume occupied by the crystallites (V_cr) are determined in terms of the changes of L_a, L_c and d₀₀₂. Since among other characteristics the crystallites form the electrical and thermal conducting phase of the carbon, N_cr, v_cr and V_cr are important parameters in many physical properties of these materials. The developed expressions were applied to a non-graphitizable and to a graphitizable carbon.