类富勒烯结构对含氢碳膜摩擦学性能的影响

目的研究类富勒烯结构含氢碳膜的摩擦学性能及润滑机理。方法采用闭合场非平衡反应磁控溅射技术,通过调节靶电流制备出类富勒烯结构含氢碳膜(FL-C:H)与非晶含氢碳膜(a-C:H)。通过扫描电子显微镜、原子力显微镜观察薄膜表面与断面的形貌,通过傅里叶红外光谱仪表征了碳膜的碳氢键结构,通过纳米压痕仪、划痕仪、摩擦磨损实验评价薄膜的力学及摩擦学性能,通过透射电子显微镜分析磨屑结构,并通过光学显微镜及三维轮廓仪对磨斑及磨痕形貌进行分析。结果类富勒烯结构对薄膜的机械力学性能影响不大,但是对其大载荷下的摩擦学性能有影响。与a-C:H碳膜相比,小载荷下(5 N),FL-C:H碳膜的摩擦系数较高,大载荷下(20 N),FL-C:H碳膜具有较低的摩擦系数(0.03)和磨损率(4.8×10-8 mm~3/(m·N)),并且其摩擦界面形成了类球状纳米结构颗粒。随着载荷的增加,FL-C:H碳膜的摩擦系数和磨损率先降低,后基本不变,在载荷大于15 N时,摩擦界面形成了类球状纳米结构颗粒。结论类球状纳米结构颗粒的形成能降低薄膜的摩擦系数和磨损率,而FL-C:H碳膜比a-C:H碳膜更易在摩擦界面形成类球状纳米结构颗粒。这种类球状纳米结构的形成还依赖于载荷的大小(大载荷时更易形成),因此类富勒烯碳膜在大载荷下更易保持低的摩擦系数及磨损率。     

类富勒烯薄膜的载荷依赖摩擦滞后行为研究

目的研究类富勒烯薄膜(FL-C:H)的载荷相关性摩擦滞后行为。方法采用直流等离子体化学气相沉积技术(DC-PECVD)在硅基底上制备了FL-C:H薄膜,通过场发射扫描电镜(FE-SEM)、X射线光电子能谱(XPS)、高分辨透射电镜(HRTEM)和拉曼光谱仪分别表征了薄膜的厚度、元素结合能状态以及微观结构,利用纳米压痕仪测定了薄膜的硬度及弹性恢复,借助往复摩擦磨损试验机考察了不同频率时变载荷条件下的摩擦滞后行为。结果以CH4和H2为前躯体制备的FL-C:H薄膜具有良好的机械性能,硬度和弹性模量分别为23.42 GPa和162.27 GPa,弹性恢复高达~82%。所制备薄膜与GCr15球配偶摩擦时,表现出良好的摩擦学性能,在循环载荷条件下表现出摩擦滞后行为。结论 FL-C:H薄膜在循环载荷条件下的摩擦滞后现象与所对应的频率有关。主要是由于大气环境下,摩擦界面处H2O、O2吸附造成氧化反应和磨损的共同作用。     

硅烷流量对钛合金双极板表面改性碳膜性能的影响

目的通过对钛合金基底进行表面改性,提高其作为质子交换膜燃料电池(PEMFC)金属双极板的耐蚀导电性能。方法通过等离子体增强化学气相沉积法(PECVD),调控不同的Si H4流量(0～10 mL/min),在钛基底表面制备了含硅非晶碳膜。利用电化学工作站、界面接触电阻测量仪、水接触角测量仪、纳米压痕仪,分别测试了薄膜的耐蚀性、导电性、疏水性和力学性能。通过拉曼光谱分析了腐蚀前后薄膜内部杂化比变化,并结合扫描电子显微镜和高分辨透射电子显微镜研究了薄膜厚度、腐蚀形貌和内部结构。结果 SiH4流量为8m L/min时,制备的含硅非晶碳膜具有最佳耐蚀性和导电性,该含硅非晶碳膜水接触角为102.91°,硬度为9.28 GPa,弹性模量为60.34 GPa,厚度为2.822μm。其动电位腐蚀电流密度为0.017μA/cm2,相比钛基底提升3个数量级(80.51μA/cm~2),在1.4 MPa压力下,其界面接触电阻为47.06 mΩ·cm~2。结论硅的引入诱导非晶碳膜生成类石墨烯结构,提高了非晶碳膜的导电性能和耐蚀性能,提升了薄膜的力学性能及疏水性。用含硅非晶碳膜对钛双极板进行表面改性,有望显著提高极板的燃料电池性能。     

自配对含氢类石墨碳薄膜超滑性能

采用等离子体增强化学气相沉积与原位渗氮复合技术在硅片和轴承钢球上制备了类石墨碳薄膜,将两者组成摩擦配伍对,并讨论自配对类石墨薄膜在氮气中摩擦学行为。利用往复摩擦机、扫描电子显微镜、三维表面轮廓仪考察自配对类石墨碳薄膜在不同载荷下摩擦磨损性能;采用高分辨透射电镜、拉曼光谱和红外吸收谱分析类石墨碳薄膜摩擦前后结构变化。摩擦测试结果表明：在载荷4 N时,薄膜摩擦因数为0.01;在8 N时,薄膜摩擦因数降低到0.005。这种变化归因于摩擦诱导薄膜结构进一步有序化以及沿滑动方向形成更加有序且更长石墨烯以及片状磨屑。证实了采用自配对碳薄膜方案是实现固体超滑一种有效途径。     

氮气流量对类富勒烯碳氮薄膜结构及力学性能的影响

目的在9Cr18钢表面制备类富勒烯碳氮薄膜,提高9Cr18钢表面强度。方法采用非平衡直流磁控溅射技术,在沉积温度为300℃的Ar和N2混合气氛中溅射C靶,制备类富勒烯CNx薄膜。利用XPS、Raman光谱、SEM研究了类富勒烯CNx薄膜的微观结构,利用纳米压痕仪和球盘摩擦试验机研究了CNx薄膜的力学性能和摩擦学性能。结果类富勒烯CNx薄膜中存在sp2 C—C、sp2 N—C和sp3 C—N化学键,类富勒烯结构的CNx薄膜的ID/IG比值较高且G峰向低峰位移动。随着氮气流量的增加,薄膜的硬度和弹性恢复系数先增大后减小,薄膜的硬度和弹性恢复系数越高,其磨损率越低。结论氮气流量为10 m L/min时制备的CNx薄膜具有较高的硬度和弹性恢复系数以及较低的摩擦系数和磨损率。在9Cr18钢表面制备类富勒烯碳氮薄膜能显著提高其表面强度。     

316L不锈钢表面沉积类金刚石膜的拉曼光谱分析及润湿性研究

采用等离子体辅助化学气相沉积(PECVD)法,在316L不锈钢基体表面以不同的沉积气压和射频功率制备出类金刚石(DLC)薄膜.拉曼光谱分析结果表明:所沉积的DLC膜具有典型的类金刚石膜结构,薄膜中sp#键含量随工艺参数的不同而不同,射频功率100 W时,sp#键含量随沉积气压增高而降低.接触角测试结果表明:DLC膜沉积...     

非晶含氢碳薄膜本征结构对退火行为的影响

目的 为在高温工况下服役的含氢碳(a–C:H)薄膜的制备提供新思路。方法 首先利用DP–PECVD和BiP–PECVD两种方法分别在Si基底上制备了两种本征结构不同的a–C:H薄膜,分别在350、450、550、650 ℃下进行退火处理。通过纳米硬度、X射线光电子能谱、傅里叶转变红外光谱、激光共聚焦拉曼光谱、场发射扫描电镜及CSM摩擦试验机等,分别评价了未退火和不同退火温度下两种不同结构a–C:H薄膜的结构、表面形貌、力学及摩擦学等性能。研究了不同本征结构a–C:H薄膜对退火行为的影响。结果 DP–PECVD方法在制备a–C:H薄膜(A薄膜)的过程中具有更高的沉积速率,是BiP–PECVD法(B薄膜)的1.52倍。随着退火温度的增加,两种方法制备的a–C:H薄膜均发生H脱附,但是A薄膜的脱H转变点为450 ℃,B薄膜的脱H转变点为350 ℃。DP–PECVD法制备的a–C:H薄膜在H脱附过程中更容易形成sp³–C,而BiP–PECVD法制备的a–C:H薄膜在此过程中形成sp³–C和sp²–C杂化键的概率基本相同。BiP–PECVD法制备的a–C:H薄膜在退火过程中更容易失去H,且在450 ℃以上出现大面积剥离,摩擦失效。而DP–PECVD法制备的碳薄膜则表现出更好的热和摩擦学稳定性,在350~650 ℃均可保持薄膜的完整性,并且在350~ 550 ℃退火后保持低至约0.06的摩擦因数。结论 DP–PECVD方法制备的a–C:H薄膜具有更好的热稳定性、力学稳定性及摩擦学稳定性。     

基底温度对掺氟类金刚石碳膜摩擦学性能的影响

以CF4,CH4和H2作为前驱气体,改变基底温度,通过直流脉冲等离子气相沉积法(PECVD)制备掺氟类金刚石碳膜,用傅里叶红外光谱仪分析薄膜的键合结构,用拉曼光谱仪分析薄膜中杂化碳的sp2和sp3的存在状态,用纳米压痕仪和UMT-2MT摩擦磨损实验机分别测量了薄膜的硬度、摩擦因数等机械性能。结果表明,F主要以C-F3,C-Fx(x=1,2,3)基团的形式存在于薄膜中;基底温度从不加热到500℃的范围,薄膜能够保持较低于0.020的摩擦因数;且基底温度为400℃时薄膜具有0.016的最低摩擦因数,但当基底温度超过600℃时,会破坏薄膜的内部结构而使机械性能下降。     

非平衡磁控溅射沉积类石墨碳膜结构及其摩擦学性能

利用非平衡磁控溅射技术在单晶硅基底上沉积了类石墨非晶碳膜。利用X射线光电子光谱、Ram an光谱、高分辨透射电子显微镜及原子力显微镜对沉积薄膜的微观结构进行了详细表征;利用纳米压痕仪和球盘摩擦试验机分别对其力学性能和摩擦学性能进行了测试。结果表明,当前制备的非晶碳膜中sp2杂化碳占主导呈现出类石墨特征,但薄膜硬度可达14.2 GPa。大气环境中的摩擦性能测试表明,所制备的类石墨非晶薄膜具有优异的摩擦学性能:其承载能力高达2.8 GPa,同时具有较低摩擦因数(~0.05)和磨损率(~10-11cm3/Nm)。类石墨碳膜优异的摩擦学性能主要归因于其独特的结构、较低的内应力及良好的热稳定性。     

高速工具钢W6Mo5Cr4V2表面不同DLC处理后的性能探讨

设计了过渡层和梯度膜结构,采用PVD磁控溅射工艺和PVD磁控溅射+PECVD(脉冲等离子增强化学气相沉积)复合工艺在高速工具钢W6Mo5Cr4V2表面制备不同的类金刚石(Diamond-like Carbon,DLC)膜:Ti过渡层+DLC膜以及CrN+CrNC+CrC+DLC(掺杂Cr)硬质膜.对这两种膜层的成分、结构、形貌和力学性能的对比分析发现,前者表面粗糙度小,但是后者的综合力学性能更好.     

Investigation of nitrogen mass transfer within an industrial plasma nitriding system I: The role of surface deposits

It has been proposed that in plasma nitriding, sputtering of material from biased components within the chamber assists in the nitrogen mass transfer process. Here, we investigate the effects of this sputter deposition process on the nitriding response of biased and unbiased AISI P20 steel samples mounted in a large-scale plasma nitriding system operated at 520 °C. Films with nanostructured morphologies resulting from Volmer-Weber film growth were observed on Si substrates placed adjacent to AISI P20 steel substrates after nitriding experiments. Auger depth profiling revealed that the films on the Si substrates had a stoichiometric ratio of 4:1 Fe:N. This suggested that the particles consisted largely of Fe₄N and it was concluded that they were formed from atoms and small clusters sputtered from biased components in the chamber. Despite the deposition of these films, no significant improvement in surface hardness was observed in the steel samples unless bias was applied to them. Furthermore, the maximum hardness achieved in biased P20 samples after the nitriding process occurred in the samples positioned adjacent to the Si samples supporting the thinnest deposited films. These findings do not support the proposition that in plasma nitriding, nitrogen mass transfer occurs predominantly by sputter deposition of iron nitride.     

Plasma-enhanced chemical vapor deposition of polyperinaphthalene thin films

Plasma-enhanced chemical vapor deposition (PECVD) has been used to grow corrosion-resistive, semiconducting thin films of the graphite-like polymer polyperinaphthalene (PPN) from 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA). Unlike thermal chemical vapor deposition of PPN from PTCDA, where thin film growth is catalyzed by a transition metal substrate, PPN films have been grown by PECVD for the first time on non-catalytic substrates: indium tin oxide (ITO)-coated glass, aluminum and silicon. Films with the same morphology and molecular characteristics have also been grown on steel substrates, where iron functions as a growth catalyst. Potentiodynamic corrosion measurements in pH 5 water show that PPN films on steel provide an effective corrosion protection layer.     

刻蚀工艺对四面体非晶碳膜生长及其性能的影响

目的研究不同等离子体刻蚀工艺对基体和四面体非晶碳膜(ta-C)的影响,并进一步考察不同电弧等离子体刻蚀时间对ta-C薄膜结构的影响。方法采用自主设计研制的45°单弯曲磁过滤阴极真空电弧镀膜设备,进行不同等离子体刻蚀以及ta-C薄膜的沉积。使用等离子体发射光谱仪表征离子种类及其密度,使用椭偏仪表征薄膜厚度,原子力显微镜表征刻蚀后的基体粗糙度,拉曼光谱仪和XPS表征薄膜结构,TEM分析薄膜的膜基界面结构。结果辉光刻蚀工艺中,作用的等离子体离子以低密度的Ar离子为主;而电弧刻蚀时,作用的等离子体离子为高密度的Ar离子和少量的C离子,并且能够在基体表面形成约15 nm的界面层,并实现非晶碳膜(a-C)的预沉积。随电弧等离子体刻蚀时间增加,ta-C薄膜的sp3含量有所降低。结论相比于辉光刻蚀,电弧刻蚀利于制备较厚的ta-C薄膜。这主要是因为电弧刻蚀时,基体表面形成良好的界面混合层,并预沉积了非晶碳膜,形成a-C/ta-C的梯度结构,有助于增强膜基结合力。     

Deuterated Diamond Like Carbon films (DDLC): Mechanical properties in relation with microstructure

The aim of this work is to study the mechanical properties of Deuterated Diamond Like Carbon (DDLC) in comparison with Diamond Like Carbon (DLC), to clarify the influence of hydrogen in amorphous carbon thin film (a-C:H) of DLC type. For this purpose we substitute hydrogen (H) in the film by its isotope deuterium (D) by replacing CH₄ by CD₄ and their mixture 1:1 in the plasma. To investigate the deuterium role in the film structure, both hydrogenated and deuterated carbon films are deposited onto silicon wafer and glass substrates using a radio frequency PECVD device. All the amorphous carbon thin films are prepared with a negative self-bias voltage in the range of 50 V to 600 V. We obtain thus a wide variation of chemical composition. Single layer is produced with a constant thickness of 200 nm, controlled by X-ray reflectivity. The effects of deposition parameters on mechanical and adhesion properties of the DLC films are investigated using nano-hardness and nano-scratch tests. Chemical compositions are determined by ions and electrons spectroscopies (RBS, ERDA, XPS). We find, among other results, that replacing hydrogen by deuterium in amorphous carbon structure enhanced hardness properties for low self-bias voltage.     

PECVD OF HARD AND ELASTIC BCN COATINGS

Compounds of the B-C-N system are very promising to produce superhard coatings with good tribological, chemical and thermal properties. Consequently, BCN films were prepared by plasma enhanced chemical vapor deposition (PECVD). The films were deposited from gaseous mixtures of BCl3-C2H4-N2-H2-Ar in different unipolar and bipolar pulsed glow discharges at 550℃ and analyzed with respect to composition, electronic structure and mechanical properties. The micro structure and composition of the BCN films were determined by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and reflection electron energy loss spectroscopy (REELS). Mechanical properties were characterized using both the traditional Vickers method and nanoindentation. The films, that were deposited using a bipolar pulsed generator, were weak and had a sponge-like structure, whereas the films prepared using an unipolar generator were well adherent, had a hardness of more than 11GPa and very high e     

OES monitoring of sequential deposition of C/W layers by PECVD/magnetron sputtering techniques

An innovative sequential plasma deposition method suitable for deposition of carbon/metal nanocomposite or multilayer films is presented. The method is based on cyclic exposure of a substrate, for predefined time intervals, to two totally independent plasma deposition sources, working in alternative sequences: magnetron sputtering (MS) for metal deposition and Plasma Enhanced Chemical Vapor Deposition (PECVD) for hydrogenated amorphous carbon (a-C:H) deposition. This paper presents a study of the a-C:H/W nanocomposite deposition method by optical emission spectroscopy (OES), focusing on identifying the useful wavelengths for optical monitoring of the process. On the basis of optical monitoring, the optimal pumping out and precursor gas admission conditions are established.