使用磁过滤阴极弧法以CO_2和N_2为反应气体制备Ti(C,N,O)纳米复合薄膜的研究（英文）

使用磁过滤阴极弧法(FCVA)以CO_2和N_2为反应气体在Si(100)和304不锈钢衬底上沉积Ti(C,N,O)纳米复合薄膜,CO_2和N_2流量比为1;1。薄膜的成分、结构和性能分别采用XPS、XRD、Raman、SEM、摩擦磨损试验机和电化学实验站检测得出。当混合气体流量从10 mL/min增加到50 mL/min时,薄膜中的C和N含量有明显增加,而O和Ti含量有小幅下降;当混合气体流量从50mL/min增加到80 mL/min时,薄膜中的C和N含量下降,而Ti含量有小幅上升,O含量急剧上升。薄膜由nc-Ti(C,N,O)纳米晶结构转变为nc-Ti(C,N,O)/a-CN x,a-TiO_2/a-CN x和N-doped a-TiO_2/a-C纳米复合结构。N-doped a-TiO_2/a-C纳米复合结构薄膜具有最低的摩擦系数(0.34),nc-Ti(C,N,O)/a-CN x和N-doped a-TiO_2/a-C纳米复合结构薄膜在Hanks溶液中均表现出良好的抗腐蚀能力。     

N_2流量对HIPIMS制备TiSiN涂层结构和力学性能的影响

采用高功率脉冲磁控溅射(HIPIMS)技术在N2流量为10~50 mL/min下沉积TiSiN涂层,利用台阶仪,XRD,XPS,SPM,SEM,HRTEM和纳米压痕仪对涂层的沉积速率、相结构、成分、形貌和力学性能进行了分析,并研究了不同N2流量对等离子体放电特性的影响.结果表明,在不同N2流量下,TiSiN涂层均具有非晶Si3N4包裹纳米晶TiN复合结构,涂层表面粗糙度Ra为0.9~1.7 nm;随N2流量的增加,等离子体的放电程度减弱,离化率降低,TiSiN涂层沉积速率降低,其Ti含量逐渐降低,Si含量逐渐增加,但变化幅度较小;涂层择优取向随N2流量的增加发生改变,晶粒尺寸逐渐增大,硬度和弹性模量逐渐降低,涂层硬度最高为(35.25±0.74)GPa.     

Ti-Si-N纳米复合薄膜的结构与性能

用工业型脉冲直流等离子体增强化学气相沉积技术,在高速钢(W18Cr4V)表面沉积了Ti-Si-N复合薄膜,研究了Ti-Si-N复合薄膜的微观组织和力学性能.结果显示,薄膜相结构为纳米晶TiN和纳米晶或非晶TiSi2以及非晶相Si3N4;在Si含量为5.0 at%～28.0 at%范围内,薄膜的晶粒尺寸逐渐变大;Ti-Si-N薄膜的显微硬度相对于TiN有明显增加,最高硬度可达40 GPa;高温退火后,Ti-Si-N纳米复合薄膜的显微硬度与晶粒尺寸在800℃高温下仍然保持稳定.     

脉冲直流PCVD制备新型Ti-Si-C-N纳米复合超硬薄膜

用工业型脉冲直流等离子体化学气相沉积（PCVD）设备，在高速钢（W18Cr4V）基材表面沉积新型四元Ti-Si-C-N复合超硬薄膜。结果表明：Ti-Si-C-N薄膜是由面心立方结构的TiN和TiC纳米晶、Ti（C，N）固溶体及存在于晶界的非晶Si3N4和α-C组成，形成TiN／TiC／Ti（C，N）／α-C／α-Si3N,复相结构，这种复相结构存在着[111]，[220]和[200]混合择优取向。SiCl4和CH4流量变化是影响薄膜相组成和硬度变化的主要工艺参数。随Si含量的增加，薄膜的显微硬度先升后降，表面形貌由致密的细颗粒状变为粗大的枝条状；C元素的加入能抑制柱状晶的形成，对硬度影响较小。     

脉冲偏压电弧离子镀C-N-Cr薄膜的成分、结构与性能

用脉冲偏压电弧离子镀设备在保持偏压一致和工作气压恒定的条件下,控制不同氮(N)流量,在硬质合金基体上制备了不同成分的C-N-Cr薄膜.用SEM,XPS,GIXRD,激光Raman谱和纳米压入等方法分别研究了薄膜的表面形貌、成分、结构与性能.结果表明,随着N流量增加,薄膜中N含量先是线性增加然后趋于平缓,Cr含量先是基本保持不变然后线性减少.在N流量不超过20 mL/min时,薄膜保持较高的硬度(＞30 GPa)与弹性模量(＞500 GPa);当N流量超过20 mL/min时,薄膜硬度与弹性模量急剧下降,在N流量为100 mL/min时硬度与弹性模量仅为13.6与190.8 GPa.     

COMPOSITION, MICROSTRUCTURE AND PROPERTIES OF C–N–Cr FILMS DEPOSITED BY PULSED BIAS ARC ION PLATING

用脉冲偏压电弧离子镀设备在保持偏压一致和工作气压恒定的条件下, 控制不同氮(N)流量,在硬质合金基体上制备了不同成分的C--N--Cr薄膜. 用SEM, XPS, GIXRD, 激光Raman谱和纳米压入等方法分别研究了薄膜的表面形貌、成分、结构与性能. 结果表明, 随着N流量增加, 薄膜中N含量先是线性增加然后趋于平缓, Cr含量先是基本保持不变然后线性减少. 在N流量不超过20 mL/min时,薄膜保持较高的硬度(>30 GPa)与弹性模量(>500 GPa); 当N流量超过20 mL/min时, 薄膜硬度与弹性模量急剧下降, 在N流量为100 mL/min时硬度与弹性模量仅为13.6与190.8 GPa.     

Si含量对电弧离子镀Ti-Al-Si-N薄膜组织结构和力学性能的影响

利用磁过滤电弧离子镀技术在高速钢基体上制备了不同Si含量的Ti-Al-Si-N薄膜,研究了Si含量对薄膜组织结构以及力学性能的影响.结果表明,Ti-Al-Si-N薄膜主要由晶态TiAlN和非晶态的Si₃N₄组成,随着Si含量的增加,XRD衍射峰强度减弱,晶粒尺寸减小;薄膜的显微组织也由明显的柱状晶转变为致密的纳米晶结构.利用纳米硬度仪对薄膜的硬度和弹性模量进行了分析,结果表明,薄膜的硬度和弹性模量有着相似的变化趋势,随着Si含量的增加,两者都先增加,当Si含量达到一定程度时.它们会逐渐稳定在一定范围内,而后又随Si含量的继续增加呈下降趋势.通过划痕测试对薄膜结合强度进行了分析,结果表明,薄膜与基体的结合强度随Si含量的增加先减小而后增加.     

PCVD法制备的Ti-Si-C-N纳米复合超硬薄膜的高温氧化行为

用脉冲直流等离子体辅助化学气相沉积(PCVD)方法在高速钢基体上沉积出Ti-Si-C-N超硬薄膜.XRD,XPS及HRTEM等测试表明,薄膜由纳米晶/非晶复合结构组成(nc-Ti(C,N)/a-Si3N4/a-C-C或nc-Ti(C,N)/h-Si3N4/a-Si3N4/a-C-C).Ti(C,N)显示(200)晶面择优取向.高温氧化实验显示:随Ti含量降低和Si含量增大,Ti-Si-C-N薄膜的抗氧化温度逐步提高;当Ti含量为8.7%、Si含量为17.8%时,薄膜中出现少量晶化的密排六方结构的h-Si3N4,弥散分布在非晶基体中,薄膜抗氧化温度达到900℃.Ti-Si-C-N薄膜的氧化过程分为增重和失重两个阶段,进入失重阶段后薄膜很快失效.     

直流溅射沉积CrN薄膜组织结构与摩擦性能分析（英文）

采用直流反应溅射在304不锈钢表面沉积CrN薄膜。利用X射线衍射仪(XRD),扫描电子显微镜(SEM),原子力显微镜(AFM),显微硬度计,磨损试验机与三维轮廓仪等表征氮气流量对CrN薄膜组织结构与摩擦性能的影响。结果表明,随着氮气流量的增加,CrN(200)晶面呈择优取向,薄膜的沉积速率随着氮气流量的增加逐渐降低。另外,薄膜的表面粗糙度随着氮气流量的增加呈先降低后增加的趋势。随着氮气流量从15 cm~3/min增加至30 cm~3/min时,薄膜的显微硬度HV先从5273 MPa增加至10422 MPa,当氮气流量再增加至35 cm~3/min时,薄膜的显微硬度却降低至9180 MPa。磨损试验表明,当氮气流量为30 cm~3/min时薄膜具有最小的摩擦系数0.93和磨损率2.02×10-15 m~3·(N·m)~(-1),显示最佳的磨损性能。     

新型Ti-Si-C-N纳米复合超硬薄膜的高温热稳定性

用脉冲直流等离子体辅助化学气相沉积（PCVD）方法在高速钢基体上沉积出新型Ti—Si—C—N超硬薄膜．Ti—Si—C—N薄膜为纳米晶／非品复合结构（nc—Ti（C，N）／a-Si3N4／a-C—C），当薄膜中Si和C含量较高时，Ti（C，N）转变为TiC，晶粒尺寸减小到2—4nm．薄膜晶粒尺寸和硬度的高温热稳定性均随沉积态薄膜中的原始晶粒尺寸减小而提高，当原始晶粒尺寸在8—10nm之间时，晶粒尺寸和硬度热稳定性可达900℃；当原始晶粒尺寸在2—4nm之间时，晶粒尺寸和硬度热稳定性可达1000℃．薄膜硬度和晶粒尺寸表现出同步的高温热稳定性．分析认为由调幅分解形成的纳米复合结构中的非晶相强烈地抑制晶界滑移与晶粒长大，从而使Ti—Si—C—N薄膜的热稳定性显著提高．     

不同掺杂对类金刚石薄膜的影响

目的研究单掺Si和共掺Ag、Si对类金刚石薄膜的结构、摩擦学性能和耐腐蚀性能的影响。方法以高纯石墨靶、石墨与金属复合靶、Si靶作为靶材,采用射频增强磁控溅射技术制备不同掺杂种类的薄膜。通过XPS、拉曼光谱仪对薄膜的化学组成和结构进行分析,通过纳米压痕仪、摩擦磨损试验机、电化学工作站等,对薄膜的力学性能、摩擦学性能及耐腐蚀性能进行了系统研究。结果 Si元素单掺DLC会引起薄膜中sp~3C含量增加。Ag、Si共掺DLC后,由于Ag以金属相分布在薄膜中,并促进sp~2相的形成,导致sp~3C含量降低。掺杂元素后的DLC薄膜,硬度下降,但韧性提高,其中Ag、Si共掺的DLC薄膜的弹性恢复系数达到79%。此外,Ag、Si共掺DLC薄膜在多种气氛(Ar、O_2、N_2)中都具有优异的摩擦学性能,磨损寿命均超过30 min,其中在N_2气中的摩擦系数最低(0.1),并在NaCl溶液中的腐蚀电流密度比304不锈钢基体降低了近2个数量级,具有良好的耐腐蚀性。结论 Si与Ag共掺DLC薄膜较Si单掺薄膜具有更好的摩擦环境适应性和耐腐蚀性能。     

Effects of N-doping on the microstructure, mechanical and tribological behavior of Cr-DLC films

We report on the effects of nitrogen doping on Cr-containing diamond-like carbon (Cr-DLC) films. DLC, Cr-DLC and N-doped Cr-DLC films were deposited on (100) Si substrates using a hybrid plasma-assisted CVD/PVD process. Film microstructure, composition and chemical state of elements were studied using transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Mechanical and tribological properties were investigated using microhardness testing and pin-on-disc experiments. Analysis by TEM and XPS shows that the Cr-DLC films contain a dispersion of amorphous, Cr-rich nanoparticles. In the N-doped films, N combines with C and partly transforms the Cr-rich nanoparticles into chromium carbon nitrides, CrC(N), dispersed in the amorphous DLC matrix. Also, a significant portion of N is incorporated into the C network. The N-doped Cr-DLC films were found to possess higher hardness, lower intrinsic stresses and somewhat higher coefficient of friction and wear rate than Cr-DLC and DLC films. Such influence of the N-doping on the properties is attributed to the formation of CrC(N) nanoparticles and C-N bonds in the DLC matrix.     

Chemical structure and mechanical properties of Si-containing a-C:H and a-C thin films and their Cr- and W-containing derivatives

Si-containing a-C:H and a-C thin films with nitrogen, oxygen and transition metal (Cr and W) additives were deposited on polished single crystalline silicon substrates at room temperature by plasma activated CVD, magnetron-sputtering PVD and also by combined PACVD-PVD techniques.In particular Si-, Si-O- and Si-N-containing a-C:H films (denoted as a-C-Si, a-C-Si-O and a-C-Si-N) were deposited respectively from tetramethylsilane (TMS), hexamethyldisiloxane and hexamethyldisilazane vapourised precursors in He carrier gas by electron cyclotron wave resonance RF plasma. Cr-containing a-C:H films, further denoted as a-C-Si-Cr, were deposited with combined PVD-PACVD by sputtering chromium and carbon targets in argon and introducing TMS vapour. Wcontaining a-C films (denoted as a-C-Si-W) were deposited by PVD with simultaneous sputtering of the constituents in Ar. Detailed characterisation of the composition and chemical state of the elements present in the films were done by X-ray photoelectron spectroscopy (XPS) and X-ray induced Auger electron spectroscopy. Mechanical properties, hardness (H), reduced modulus (E) and scratch behaviour were studied by depth-sensing nanoindentation and scratch tests.In the a-C:H films, the C/Si ratio varied between 1.5 and 3.5 showing a significant deficiency of C as compared to the composition of the precursors. The Cr and W content in the a-C-Si-Cr and a-C-Si-W films varied in a very broad 2-50 at.% range.The chemical state of carbon was primarily of sp² and partly of sp³ type C-C with XPS chemical shifts for C 1s at 284.3 eV and 285.0 eV, respectively. The Si in the films is bonded predominantly to carbon (Si 2p at 100.8 eV BE) or to nitrogen in N-containing films (Si 2p at 101.3 eV BE). In the a-C-Si-Cr films Cr-C bonding states were determined (Cr 2p_3/2 at 574.5 eV and C 1s at 282.8 eV). Si formed predominantly Si-C and also Si-Cr bonds. In the a-C-Si-W, films C-Si and C-W (W 4f_7/2 at 32.3 eV) chemical bonds could be identified.It was discovered that the modified Auger parameter for silicon, α_Si (derived from the Si 2p electron and Si KLL Auger line energy), sensitively reflects the entire chemical structure of these films, including crosslinking and densification. These spectroscopic data, supported further by the increase of the bulk plasmon loss energy of the C 1s peak, were directly connected with the mechanical properties of these films. The amorphous nature of the films was deduced from the chemical state analysis and was verified also by transmission electron microscopy (TEM) and electron diffraction (ED) studies.Hardness and elastic modulus of the a-C-Si-(O,N) films could be adjusted in a wide range of approx. 5-15 GPa and 40-140 GPa, respectively. Systematic alteration of these values with the composition (C/Si, O/Si and N/Si atomic ratio) and with the chemical structure (α_Si?) was established and their interrelations are discussed. Whilst incorporation of Cr does not alter the mechanical properties, the addition of W increases H and E up to 19 GPa and 210 GPa, respectively.     

Si_3N_4/CrN nanostructured multilayers grown by RF reactive magnetron sputtering

1　INTRODUCTIONInrecentyears ,ceramicsuperhardnesscomposi tionally modulatedmultilayerfilmshavebeenactivelyinvestigated[18] .Theresearchresultsshowthatmul tilayerscancombinethepropertiesoftheconstituentmaterialsandhavemoreexcellent propertiesthanthoseofthesingle layerfilm .Alargenumberofin ternalinterfaceswhichare paralleltothesubstratesurfacecanretardcrackpropagationandprovidebar rierstodislocationmovement.Multilayerswithopti mizedinterfaceareasseemtobemostpromisingwithrespecttoanoptimum…     

nc-(Ti,Al)(C,N)/a-SiNx纳米复合薄膜的制备及性能研究

目的 研究Si、C单元素掺杂及其共同掺杂TiAlN涂层对涂层性能的影响.方法 基于阴极电弧+辉光放电技术,在SUS304不锈钢基体及硬质合金刀具上分别制备nc-(Ti,Al)N、nc-(Ti,Al)N/a-SiNx、nc-TiAlCN及nc-TiAlCN/a-SiNx/a-C纳米复合薄膜,通过SEM观察涂层的微观组织形貌,并借助EDS表征涂层的元素成分,用XRD分析涂层的物相构成,探究C、Si元素对涂层生长的影响.采用纳米硬度仪测试涂层的硬度,采用二维轮廓仪及三维形貌仪表征涂层的表面粗糙度及表面形貌,通过滑动摩擦磨损试验测定涂层的耐磨性,用纳米划痕仪表征涂层的摩擦系数及涂层与基体的结合强度,用铣削实验表征涂层的切削性能.结果 该技术制备的TiAlN涂层,内部晶相结构复杂,硬度为29.57 GPa,主要归因于Ti2AlN、Ti2N等硬质相及TiN0.3相的形成降低了涂层的晶格常数.此为首次报道通过物理气相沉积方法制备含TiN0.3相的涂层.TiAlSiN涂层的硬度最高,为37.69 GPa,且耐磨性最好,主要原因是Si的添加起到了细晶强化和晶界强化的作用.C掺杂TiAlN使涂层析出更多非晶相,涂层硬度降低.C、Si元素共同掺杂,使得nc-TiAlCN/a-SiNx/a-C涂层表现出较低的摩擦系数及表面粗糙度,但与基体的结合性能最差,nc-(Ti,Al)N/a-SiNx薄膜的结合强度最好.结论 涂层均提高了基体表面的显微硬度,Si、C元素的掺杂可使涂层的某些性能得以大幅提升,但在实际应用中,还需根据应用需求选择合适的涂层.     

Si含量对CrSiN涂层结构和性能的影响

目的在室温条件下,采用物理气相沉积(PVD)磁控溅射沉积方法,通过控制Si靶功率制备具有不同Si含量的CrSiN涂层,以探究Si元素对涂层结构和性能的影响。方法通过X射线衍射、能谱仪测试、纳米压痕测试、维氏硬度压痕测试和摩擦磨损实验,分别评价CrSiN涂层的结构、硬度、韧性和耐磨性能,并通过扫描电子显微镜对压痕形貌进行分析。结果所有CrSiN涂层均呈(111),(200)取向的Na Cl结构。随着Si含量增加,XRD峰呈宽化趋势,晶粒细化效果明显。随Si元素的加入,CrSiN涂层硬度、模量和韧性均呈先增加后降低的趋势。相比Cr N涂层,Si的原子数分数为3.2%时,CrSiN涂层的硬度由21.4 GPa增至35.7 GPa,模量由337.7 GPa增至383.9 GPa,塑性指数由0.5增至0.55,实现了强韧一体化。加入Si元素,CrSiN涂层的耐磨损性能得到改善,且Si的原子数分数为3.2%,磨损率最低,为1.0×10~(-17)m~3/(N·m),提高了约一个数量级。结论 Si元素的加入可以有效改善CrSiN涂层的结构,提高CrSiN涂层的硬度、韧性和磨损性能,但需加入适量的Si,才可实现性能最优化。     

PREPARATION OF TiN FILMS BY N_2 ASSISTED Xe~+ ION BEAM ENHANCED DEPOSITION AND THEIR MECHANICAL PROPERTIES

A new method for preparation of hard TiN films has been developed by using electronbeam evaporation-deposition of Ti and bombardment with 40 keV Xe~+ ion beam ina N_2 gas environment.The synthesized TiN films were superior to PVD and CVDones in respects of improved adhesion to substrate and low preparing temperature.Theyexhibited good wear resistance and high hardness up to 2200 kg/mm~2.Some industrialapplications have been reported.     

脉冲偏压对TiAlCN薄膜结构与力学性能的影响

利用多弧离子镀-磁控溅射复合技术通过改变脉冲偏压在Si片与SS304基体表面制备了TiAlCN薄膜,研究了不同脉冲偏压对薄膜结构和力学性能的影响。薄膜成分、表面形貌、相结构及力学性能分别利用能量弥散X射线谱(EDS)、扫描电镜(SEM)、X射线衍射(XRD)和纳米压痕仪等设备进行表征。结果表明,随着脉冲负偏压的增加,薄膜中Ti元素的含量先减小后增大,而Al元素有相反的变化趋势。适当增大脉冲偏压,薄膜表面颗粒、凹坑等缺陷得到明显改善。物相分析表明TiAlCN薄膜主要由(Ti,Al)(C,N)相,Ti4N3-x相和Ti3Al相组成。薄膜平均硬度与弹性模量随脉冲负偏压的增加先增大后减小,在负偏压-200 V时达到最大值分别为36.8 GPa和410 GPa。     

CrSiN纳米复合薄膜的摩擦学性能

采用中频非平衡反应磁控溅射技术在单晶硅P(111)基材上制备了CrSiN纳米复合薄膜。利用X射线衍射仪(XRD)、X射线光电子能谱仪(XPS)、Kevex能谱仪(EDX)、高分辨率透射电子显微镜(HRTEM)和纳米压痕仪对薄膜的相结构、化学成分组成和力学性能进行了测试分析。利用球-盘式摩擦磨损试验机(UMT-2)考察了薄膜和GCr15钢球对磨的摩擦学性能并采用扫描电镜(SEM)观察磨痕形貌。结果表明:CrN薄膜中Si元素的掺杂改变了薄膜晶体结构,所制备的CrSiN复合薄膜为多相复合结构,即nc-CrN/aSi3N4所组成的纳米晶/非晶复合结构。CrSiN纳米复合薄膜的力学性能均优于CrN薄膜,其硬度均高于CrN薄膜的硬度,其中Si原子数分数为12.6%时薄膜的硬度达到最大,对应纳米晶/非晶复合强化。CrSiN纳米复合薄膜的摩擦因数低于CrN薄膜,具有很好的抗磨损性能,并具有一定的润滑作用。     

氮气辅助氙离子束增强沉积TiN薄膜及其机械性能

本文提出一个合成TiN硬质薄膜的新方法,在氮气氛中,电子束蒸发沉积Ti的同时,用40keV的氙离子束对其进行轰击而合成TiN薄膜,该方法优于PVD和CVD之处在于合成温度低,薄膜与基体结合力强,其临界载荷达4.2kg,Knoop硬度达2200kg/mm~2,具有良好的耐磨损性能,报道了所合成的TiN薄膜在工业上应用的一些结果。