LPCVD法制备SiC-MoSi2涂层的形貌及沉积机理研究

为提高碳/碳复合材料抗氧化性能,以甲基三氯硅烷(MTS)为先驱体,利用低压化学气相沉积(LPCVD)技术在碳/碳复合材料表面制备SiC-MoSi2涂层,通过XRD和SEM分析了不同沉积温度下涂层结构、物相组成及其沉积机理。结果表明,沉积温度对涂层的成分、结构及致密度有较大影响,在1100～1250℃均可成功得到SiC-MoSi2涂层,1100℃所得涂层结构疏松多孔;1250℃制备的涂层中间部位孔隙较多,表层为致密SiC涂层;1150～1200℃之间可得到均匀致密、以MoSi2颗粒为分散相、以CVD-SiC为连续相的SiC-MoSi2双相陶瓷涂层。     

碳纳米纤维制备的研究进展

讨论了碳纳米纤维与碳纳米管的本质区别;介绍了多种碳纳米纤维制备的研究方法和化学气相沉积(CVD)法制备碳纳米纤维的研究进展;并对各种制备方法的优缺点进行了评述;同时讨论了影响气相生长碳纳米纤维的各种因素.     

CVD法制备碳纳米管中应用硫添加物的热力学研究

利用俄罗斯科学院研制的CVD (Chemicalvapordeposition)软件计算分析了CH4 H2 S体系在 10 132 5Pa、90 0～ 130 0K ,CO H2 S体系在 10 132 5Pa、90 0～ 12 0 0K下不同硫添加物含量及温度对碳沉积率的影响 ;绘制了碳沉积边界曲线 ,预测了碳沉积区 ;计算筛选出了适合于不同体系制备碳纳米管的催化剂。证明了加入硫添加物可以提高碳纳米管沉积率     

超音速等离子体喷涂MoSi2涂层工艺研究

涂层技术是C/C复合材料高温抗氧化与抗烧蚀的有效手段,单一的SiC涂层很难为C/C复合材料提供有效的长寿命保护。金属间化合物MoSi2高温时会形成一层致密的SiO2保护膜,具有特别优异的高温抗氧化性能,常作为C/C复合材料的高温抗氧化涂层。本文采用超音速等离子喷涂法在带SiC涂层的C/C复合材料表面制备了MoSi2涂层,主要研究了喷涂功率、主气(Ar)流量对粉料表面温度、飞行速度、沉积率以及对涂层表面微观结构和结合强度的影响。结果表明:喷涂功率在47.5~52.5 kW之间,既能使粒子有较高的速度和温度,还能保证粉末不过熔,在喷涂功率为50 kW时,粉料的沉积率最高,氧化不高,涂层表面致密性好,截面结合紧密,结合强度高;Ar流量为65 L/min时,能够保证MoSi2粉末有较高的表面温度与较快飞行速度,沉积率最高,氧化不高,涂层表面致密,几乎没有孔隙与裂纹。因此,调控超音速等离子体喷涂工艺参数能够在带SiC涂层的C/C复合材料表面得到致密且结合良好的MoSiO2涂层。     

SiC/MoSi2-Si-Cr-B/玻璃涂层碳/碳复合材料抗氧化行为研究

采用两步包埋法及料浆涂刷-烧结法在二维碳布叠层碳/碳复合材料表面依次制备了SiC/MoSi2-Si-Cr-B包埋涂层及磷酸盐玻璃外涂层,研究了其在950℃静态空气环境中自由状态的抗热震、防氧化性能及不同弯曲变形状态下的防氧化性能,并借助X射线衍射分析仪及扫描电子显微镜对涂层试样的组成成分及微观组织形貌进行了分析.结果表明:950℃自由状态下该涂层体系的氧化失重率为负值,抗热震、防氧化效果良好;磷酸盐玻璃层在950℃软化熔融呈粘流态,可填补涂层内的裂纹和孔洞,阻止氧的入侵,有效提高了涂层整体的抗热震及抗氧化性能;但弯曲变形状态下,涂层试样的氧化失重率随形变量的增加而提高,形变会在一定程度上降低碳/碳复合材料抗氧化涂层的保护效果,加速材料的氧化失效.     

化学气相渗透法制备碳/碳复合材料的研究进展

化学气相渗透(CVI)是在多孔预制体内部进行的化学气相沉积(CVD),是制备碳/碳(C/C)复合材料最重要的方法之一.介绍了CVI制备C/C复合材料的原理和近年来研究取得的进展,分析和讨论了各种CVI新工艺的特点,最后展望了CVI新工艺的研究方向.     

声电沉积透钙磷石和羟基磷灰石涂层动力学对比研究

借助声电沉积技术，在碳／碳复合材料表面制备了生物活性透钙磷石和羟基磷灰石涂层。采用分析天平称量了不同温度和时间的涂层重量，通过理论分析研究了涂层沉积的动力学规律。结果表明随时间温度增加，涂层的质量增加。透钙磷石和羟基磷灰石沉积都受扩散过程控制，并且得出羟基磷灰石的扩散活化能是7．24Kcal／mol，透钙磷石的扩散活化能很小，在本实验范围内不能求出，但通过比较分析，可知透钙磷石的扩散活化能远小于羟基磷灰石涂层，因此从理论上揭示了声电沉积工艺中，透钙磷石优先羟基磷灰石涂层沉积的本质原因。     

粉末粒度对喷涂二硅化钼涂层微观结构的影响

分别以2.5～15μm、15～30μm、30～54μm和54～74μm四种粒径的二硅化钼为热喷涂粉末,利用大气等离子喷涂技术制备了二硅化钼涂层,通过XRD和带能谱的SEM表征了涂层的微观组织结构。结果表明,喷涂过程中,喷涂粉末中部分四方相MoSi2(t)转变为六方相MoSi2(h),MoSi2中的Si含量出现了损失。随着喷涂粉末粒径的增大,MoSi2粒子在沉积过程中的氧化程度减弱,涂层中的Mo、Mo5Si3等富钼相和MoO3、MoO2等氧化产物的相对含量逐渐减少,而富硅相MoSi2逐渐增加。粉末粒度分别在30～54μm和54～74μm范围时,均可获得以MoSi2为主相的涂层。以粒径30～54μm的粉末制备的涂层组织较致密,内部出现了富钼相"网状"结构的组织。     

高温化学气相沉积法制备致密碳化钽涂层

采用高温化学气相沉积法(CVD)在高纯高密石墨基片的表面沉积了碳化钽(TaC)涂层。通过研究气化温度、气体流量及沉积温度对TaC涂层表面质量的影响,确定了高温CVD法制备TaC涂层的工艺参数,最终获得高致密度的TaC涂层。     

水热碳化法制备碳纳米材料

形态可控的碳纳米材料由于独特的结构和性能而受到研究者的普遍关注,常见的制备方法有化学气相沉积法(CVD)、乳液法和水热碳化法等。水热碳化法是一种重要的碳纳米材料制备方法,具有成本低、反应条件温和、产物粒径均匀且形态可控等特点。综述了近年来以糖类及淀粉等有机物为原料,采用水热碳化法制备各种形态可控碳纳米材料的研究现状,重点介绍了水热碳化工艺条件对合成碳微球、空心碳微球、核壳结构碳复合材料显微形貌的影响,并提出了水热碳化法制备碳纳米材料研究中存在的问题和今后可能的发展方向。     

树脂镜片抗磨加硬膜层的研究进展

树脂光学镜片以其优异的性能逐步取代玻璃镜片,占据了国内外大部分市场,但由于硬度低,耐磨损性差,所以使用寿命较短.研究发现在其表面镀制抗磨加硬膜可显著提高耐磨损性.综述了国内外近年来在树脂镜片上涂镀有机硅、石英等抗磨加硬膜的制备方法和性能研究进展,并介绍了在树脂镜片上沉积新型类金刚石(DLC)抗磨加硬膜的研究现状及发展前景.     

ELECTROPHORETIC COATINGS FOR ADVANCED MATERIALS

We have electrophoretically deposited a variety of coatings for a number of applications. We have also worked extensively with a process for electrophoretically depositing styrene acrylate polymer coatings. These coatings provide useful corrosion protection and dielectric properties for capacitors and electrical insulation. Dielectric breakdown strengths in the order of 1000 V/micrometer have been observed for capacitors with this coating as the dielectric. Various particles have also been dispersed in the electrolyte; these mixtures yield composite coatings of unusual materials such as fissile uranium in a carbon matrix. The process can also be adapted to form very thin, free-standing styrene acrylate films or pellicles. We have also explored the feasibility of depositing a variety of colloidal inorganic particles from liquid suspensions. Our results show that isopropanol works relatively well as a dispersing medium for a large number of powders. Isopropanol slurries can be used to deposit a number of uniform ceramic or glass coatings on metal substrates. Important coating considerations with regard to whether useful coatings can be deposited using this latter type of electrophoretic process include: (1) the average size, size distribution, and shape of the particles, (2) the charge assumed by the powder particles when they are dispersed in a liquid such as isopropanol, and (3) the coefficients of thermal expansion of the substrate and the coating material from the standpoint of the heat treatment or sintering required to obtain sufficient cohesion and adhesion.     

Scalable production of ultra small TiO2 nano crystal/activated carbon composites by atomic layer deposition for efficient removal of organic pollutants

A high surface area photo-catalytic composite material is synthesized by depositing thin films of titanium dioxide (TiO₂) on activated carbon (AC) particles using atomic layer deposition (ALD). A rotary ALD reactor is developed for scalable fabrication of powder and grams of the catalyst is prepared in each batch. The processes of TiO₂ ALD are monitored by mass spectrometry. Saturated ALD surface reactions are confirmed so that the entire surface of the AC support is covered by conformal coatings of TiO₂. For composites fabricated by 3 or more ALD cycles of TiO₂, the amorphous oxide layers can be converted to crystalline films by high temperature annealing. The as-prepared TiO₂/AC composites are highly reactive in photo-catalyzed degradation of methyl orange. The excellent catalytic performance is attributed to the abundant and uniformly dispersed active phase, formation of very active ultra small (<5 nm) TiO₂ crystals, and easy accessibility of the active sites.     

Tribological behaviour of C-alloyed transition metal dichalcogenides (TMD) coatings in different environments

W-S-C films were deposited by non-reactive sputtering from a carbon target incrusted with WS₂ pellets in the eroded zone. This process allows depositing coatings with a wide range of compositions, with a precise control of their carbon content. Before the deposition, a Ti interlayer was interposed between the film and the substrate to improve the final adhesion. The carbon content in W-S-C system was varied from 29 at.% to 70 at.%, which led to an hardness enhancement from 4 GPa up to 10 GPa where the maximum hardness was reached in films with a carbon content between 40 at.% and 50 at.%. The tribological behaviour of the coatings was evaluated by pin-on-disk testing, in environments with different humidity levels. Generally, the tribological performance of W-S-C coatings in environments with moderate to high humidity is better for coatings with high carbon content. Friction coefficients, as 0.05 or lower could be reached at low humidity ranges (<7%) to all compositions. However, for higher humidity values, friction coefficient increased up to 0.30 in the W-S-C film with low carbon content whereas it was kept approximately constant for the others compositions.     

PROCESSING ASPECTS OF CHEMICAL VAPOUR DEPOSITION (CVD) FOR ADVANCED MATERIALS

Chemical vapor deposition (CVD) is an established process used to deposit thin films of advanced materials, based on chemical reactions. Three recent developments in CVD materials processing are described. Low pressure CVD is used extensively in the semiconductor, microelectronics, and optoelectronics industries for depositing stabilized oxides to protect graphite composites, and hard coatings of titanium compounds for cutting tools. Metallorganic CVD is the primary process for depositing the III-V group elements for advanced epitaxial semiconductor designs. Plasma-enhanced CVD is based on the ionization of chemical species and is growing rapidly in importance in areas such as the deposition of diamond films in a microwave plasma.     

2.7 Deposition methods for dielectric films and their electrical properties

The various methods of depositing thin (<1 ωm) dielectric films are summarized. This summary is followed by a brief survey of the basic electrical properties and also of the applications of thin dielectric films with particular reference to deposition techniques. It is concluded that it is not possible to give a ‘best buy’ for a preparation method, as so much depends on the electrical studies to be made or the applications which are envisaged.     

Antireflecting coating from Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> and SiO<Subscript>2</Subscript> multilayer films

Sol-gel method is important for depositing antireflective coating that allows control over thickness as well as the index of refraction. Antireflective coatings which are produced from Ta₂O₅ and SiO₂ multi-layer thin films using sol-gel spin coating method are presented. The refractive index and the thickness are controlled by the composition and the concentration of the solution respectively. The thickness, refractive index and extinction coefficient of the films were calculated through transmission and reflection measurement by an NKD analyser. Mechanical properties of the films were checked by the cross tape test and dry sun test at 760 W/m². The result shows that the sample heat treated at 450^∘C for 15 min approaches a reflectance with less than 0.5% at around 840 nm.     

电流密度和衬底处理方式对CaMoO4薄膜电化学制备的影响

主要研究了利用恒电流电化学技术制备CaMoO4薄膜的工艺中,电流密度和衬底处理方式对薄膜制备的影响.研究发现,增大阳极氧化电流密度会加快薄膜的生长速度,但会加剧晶粒团簇生长的趋势、减弱薄膜与衬底的附着力和薄膜的均匀性;衬底的不同处理方式对薄膜晶粒的生长速度、沉积方式、均匀性等有较大的影响,在抛光衬底上薄膜的沉积速度比酸腐蚀和粗磨的衬底要快,且不易造成晶粒的团簇生长.结果表明,CaMoO4薄膜的电化学沉积,应在抛光衬底上进行;电流密度控制在0.5mA/cm2附近比较好.     

Si(111)衬底上多层石墨烯薄膜的外延生长

利用固源分子束外延(SSMBE)技术, 在Si(111)衬底上沉积碳原子外延生长石墨烯薄膜, 通过反射式高能电子衍射(RHEED)、红外吸收谱(FTIR)、拉曼光谱(RAMAN)和X射线吸收精细结构谱(NEXAFS)等手段对不同衬底温度(400、600、700、800℃)生长的薄膜进行结构表征. RAMAN和NEXAFS结果表明: 在800℃下制备的薄膜具有石墨烯的特征, 而 400、600和700℃生长的样品为非晶或多晶碳薄膜. RHEED和FTIR结果表明, 沉积温度在600℃以下时C原子和衬底Si原子没有成键, 而衬底温度提升到700℃以上, 沉积的C原子会先和衬底Si原子反应形成SiC缓冲层, 且在800℃沉积时缓冲层质量较好. 因此在Si衬底上制备石墨烯薄膜需要较高的衬底温度和高质量的SiC缓冲层.     

Mechanical properties of carbon-modified silicon oxide barrier films deposited by plasma enhanced chemical vapor deposition on polymer substrates

Cohesive and adhesive properties of silicon oxide barrier coatings deposited from an oxygen/hexamethyldisiloxane gas mixture by plasma enhanced chemical vapor deposition, with controlled incorporation of carbon on 12 μm thick polyethylene terephtalate films were investigated. The reactor was equipped with a 2.45 GHz slot antenna plasma source and a 13.56 MHz-biased substrate holder. The two plasma sources were operated separately or in a dual mode. It was found that no or negligible internal stresses were introduced in the silicon oxide coatings as long as the increase of energy experienced by the film was compensated by the densification of the oxide. For a range of process parameters and carbon content on the changes of the crack onset strain, adhesion, and cohesion were found to be similar. Generally a high crack onset strain or good adhesion and cohesion were measured for films with an increased carbon content, although this was obtained at the expense of the gas barrier performance. Promising approaches towards high-barrier thin films with good mechanical integrity are proposed, based on coatings with a gradient in the carbon content and in the mechanical properties, on nano-composite laminates, and on organo-silane treatments.