TiN/CrN多层薄膜微观结构与力学性能的研究

近些年来,TiN/CrN多层薄膜由于其优良的力学性能被广泛应用于表面防护,提高零部件性能和使用寿命等方面。为了研究TiN/CrN多层薄膜微观结构与力学性能的关系,本文采用磁控溅射技术制备了TiN、CrN单层薄膜和三种不同调制周期的TiN/CrN多层薄膜。通过原子力显微镜和X射线衍射分析了膜的表面形貌和相结构。使用纳米压痕仪测试薄膜的硬度和压入塑性,曲率法测定薄膜的残余应力。结果表明,TiN/CrN的多层薄膜是由TiN和Cr2N两相组成,随着调制周期的增大TiN层与CrN层之间的界面区域变小,界面平滑且明显。力学性能方面,多层薄膜的硬度和压入塑性比单层膜好,并且多层薄膜随调制周期的减小硬度和压入塑性越大,残余应力随周期性的增加而逐渐增大。综上可见,TiN/CrN多层薄膜的力学性能的改善取决于界面区域的大小和形貌,即调制周期,该结论与Hall–Petch理论相吻合。     

直流溅射沉积CrAlN和CrN薄膜微观结构与摩擦性能分析研究

采用直流反应溅射在304不锈钢表面沉积CrAlN和CrN薄膜。利用X射线衍射仪（XRD）,扫描电子显微镜（SEM）,X射线光电子能谱仪（XPS）,原子力显微镜（AFM）等表征Al元素的加入对CrN薄膜成分与组织结构的影响。采用摩擦磨损试验机和3 mm的Si3N4作为对偶球测试其在不同环境下的摩擦性能,并利用Nanomap 500LS三维轮廓仪表征磨痕轮廓。研究结果表明,CrN薄膜主要物相是CrN和Cr2N相,CrAlN薄膜主要物相是CrAlN和Cr2N相。CrN薄膜的（200）晶面的CrN相呈择优取向,而CrAlN薄膜的（200）晶面的CrAlN相也呈择优取向。在CrAlN沉积的过程中,部分的Cr原子被Al原子替代形成有利于细化晶粒和提高薄膜的综合性能。因此,在所有的实验环境中,CrAlN薄膜都比CrN薄膜具有更好的抗磨损性能和低的磨损率。     

磁控溅射制备的Cr/CrN和Cr/CrN/CrAlN涂层耐腐蚀性能对比研究

目的比较Cr/CrN/CrAlN涂层和Cr/CrN交替涂层的耐腐蚀性能。方法利用电化学极化曲线、阻抗谱和中性盐雾试验进行测量,结合扫描电子显微镜(SEM)和原子力显微镜(AFM)表征微观形貌,分析两种涂层耐腐蚀性能的差异。同时,为研究涂层在服役中的损伤工况,分析了预制划痕对Cr/CrN/CrAlN涂层耐腐蚀性能的影响。结果Cr/CrN/CrAlN涂层的自腐蚀电流密度较Cr/CrN交替涂层和TC4基体低2个数量级,腐蚀速率较小。无损伤的Cr/CrN/CrAlN涂层的极化电阻Rp为868.7 kΩ·cm^2,预制1条损伤划痕涂层的极化电阻为792.0 kΩ·cm^2,而带有5条损伤划痕涂层的极化电阻Rp仅为77.2 kΩ·cm^2,减小至原始涂层的8%。Cr/CrN/CrAlN涂层经288 h连续盐雾腐蚀后增重仅为0.1 mg/cm^2,远小于CrN涂层和TC4基体,且增重速率趋于平缓。CrN涂层在连续盐雾腐蚀24 h后,腐蚀增重速率明显增加。结论由于Cr/CrN/CrAlN涂层结构增加了微裂纹和位错运动的界面阻塞,避免孔隙的连通,阻碍了腐蚀介质进入基体,因此涂层的耐腐蚀性能提高。对于表面预制划痕的Cr/CrN/CrAlN涂层,首先发生涂层的局部腐蚀,通过阴极极化加速后,腐蚀凹坑延伸到涂层/基体界面,加剧涂层的局部剥离。     

CrN和CrAlN薄膜的微观结构及在不同介质中的摩擦学性能

采用中频非平衡反应磁控溅射技术在单晶硅P(111)和不锈钢(1Cr18Mn8Ni5N)基材上制备了CrN和CrAlN薄膜.利用X射线衍射仪(XRD)、X射线光电子能谱仪(XPS)、原子力显微镜(AFM)、场发射扫描电子显微镜(FESEM)和纳米压痕仪对薄膜的相结构、化学组成、表面形貌、断面结构和力学性能进行了测试分析.利用球-盘式摩擦磨损试验机(CSM)考察了两种薄膜在不同介质(空气、自来水、oil-1 (TAO-40)及oil-2 (150BS))中和Al2O3球对磨的摩擦学性能.结果表明:CrN薄膜中Al元素的掺杂并未改变薄膜晶体结构,但却降低了薄膜的表面粗糙度、增强了薄膜的致密性、提高了薄膜的力学性能、改善了水润滑和油润滑条件下薄膜的摩擦学性能.由于CrN和CrAlN薄膜的摩擦磨损性能显著依赖于测试介质,因此重点讨论了它们在不同介质中的摩擦磨损机理.     

Cr基金属氮化物涂层改善冷冲模性能的研究

采用非平衡磁控溅射法在硬度分别为56HRC和62HRC的Cr12MoV冷作模具钢表面制备Cr/CrN/CrTiAlN涂层,综合分析了涂层的表面性能,并进行了应用试验。实验结果和应用试验表明：Cr/CrN/CrTiAlN涂层能显著提高Cr12MoV钢基体的表面硬度（2550HV25）及承载能力,并与基体较好地结合,从而显著减少了Cr12MoV钢基体的磨粒磨损,耐磨性提高,对于高的基体硬度这一效果更为明显。经Cr/CrN/CrTiAlN涂层的翻边精整冷冲模,较未表面处理模具其使用寿命提高了两个数量级以上。     

磁控反应溅射沉积CrN薄膜的抗氧化性研究

通过磁控反应溅射在H1模具钢表面沉积了CrN薄膜.用扫描电镜(SEM)、X射线衍射仪(XRD)观察了试样的表面形貌,进行了物相分析,研究了CrN薄膜的抗氧化性能,讨论了膜层的抗氧化行为和机制.结果表明:在500℃以下,CrN膜层具有良好的抗氧化性,能大大提高基体的抗氧化性能.当温度超过600℃时,由于膜层产生剥落而失去使用性能.     

磁控溅射Cr/CrN和Cr/CrN/CrAlN涂层的抗高温氧化性能

为了提高航空紧固件涂层的高温工况防护能力,采用磁控溅射技术在钛合金表面分别制备 Cr/ CrN 交替涂层和 Cr/ CrN / CrAlN 涂层,研究氧化时间和氧化温度对涂层高温氧化性能影响。 利用 SEM、EDS 和 XRD 进行微观形貌和物相成分分析,采用热重法分析氧化增重量( w) 和氧化速率常数( k) ,使用显微硬度计测试涂层高温氧化后硬度。 结果表明:随着氧化时间和氧化温度的增加,涂层硬度均降低,但 Cr/ CrN / CrAlN 涂层下降趋势更缓; 两种涂层的 w 和 k 均上升,其中 Cr/ CrN / CrAlN 涂层 w 和 k 增幅均低于 Cr/ CrN 交替涂层,950 ℃ 氧化 96 h 后 Cr/ CrN / CrAlN 涂层和 Cr/ CrN 交替涂层的 w 值分别为 40 mg / cm ² 和 135. 7 mg / cm ² ,其对应的 k 分别为 0. 1996 和 0. 4092,说明 Cr/ CrN / CrAlN 涂层抗高温氧化性更好。 Cr/ CrN / CrAlN 涂层活化能 E_a 值比 Cr/ CrN 交替涂层高 48. 5%,Cr/ CrN / CrAlN 涂层在高温下产生 Cr₂O₃ 和 Al ₂O₃ 的混合氧化物,结构更致密,Cr/ CrN / CrAlN 涂层抗高温氧化性能高于 Cr/ CrN 交替涂层。     

调制比对Cr/CrN/Cr/CrAlN多层膜结构及性能的影响

目的 探究Cr/CrN/Cr/CrAlN多层膜的最佳调制比.方法 利用电弧离子镀技术,在TC4钛合金上制备了不同调制比的Cr/CrN/Cr/CrAlN多层膜.利用扫描电子显微镜观察膜层表面和截面形貌;用Image-Pro分析软件对表面的大颗粒进行定量分析;利用X射线衍射法表征膜层的晶体结构;采用维氏硬度计测量膜层的显微硬度;采用划痕试验仪测量膜层与基体之间的结合力(临界载荷);通过基片弯曲法测量并计算得到膜层的残余应力;利用根据ASTM G76-05标准特制的AS600-喷砂试验机进行了抗冲蚀性能测试;采用三维表面轮廓仪测量冲蚀坑深度.结果 膜层表面质量和生长取向与LCr/CrN:LCr/CrAlN调制比密切相关,随着Cr/CrN比例的增加,膜层表面质量越来越好,择优取向由(111)晶面转为(200)晶面.多层膜的硬度随Cr/CrN比例的增加,呈下降趋势,结合力、残余应力和韧性则随之呈先升后降的趋势,并在LCr/CrN:LCr/CrAlN为1:2时,达到最佳.多层膜的抗砂粒冲蚀性能变化与力学性能变化一致,在LCr/CrN:LCr/CrAlN为1:2时达到最佳,其抗冲蚀能力是TC4基材的3倍以上,多层膜呈典型的脆性断裂失效形式.结论 在调制比LCr/CrN:LCr/CrAlN=1:2时,膜层获得最佳的抗冲蚀性能.     

等离子体密度调控CrN薄膜结构改性Ti6Al4V双极板

目的 满足质子交换膜燃料电池双极板的使用要求。方法 采用热丝增强等离子体磁控溅射技术,通过改变热丝放电电流调控溅射等离子体密度,在Ti6Al4V（TC4）合金表面制备了氮化铬（CrN）薄膜。结果 随着热丝放电电流从0A增加至32A,真空腔内等离子体密度增强,-50V偏压下基体偏流密度从0.07 mA/cm²增至0.7 mA/cm²。CrN薄膜择优取向从低应变能的（111）转变成表面能更低的（200）择优取向。薄膜表面形貌由较疏松的四棱锥型转变成致密球形;无热丝时,CrN薄膜显示有铬的（110）衍射峰且铬原子数分数为52.16%,为富金属薄膜。热丝放电电流为16 A和32 A时,Cr N薄膜中的铬原子数分数分别降至50.79%和49.82%,且无Cr的衍射峰,即逐渐转变为贫铬。采用热丝辅助磁控溅射,将使氮气离化率增大,活性增强,引起薄膜贫铬。模拟双极板工作环境下,与TC4腐蚀电流密度1.5×10^-8 A/cm²相比,CrN薄膜的腐蚀电流密度由无热丝的3×10^-5 A/cm     

GNiCr40Al3Ti合金表面Cr-DLC、CrAlN和CrN薄膜在去离子水环境中的摩擦磨损性能

目的 在去离子水环境中，研究GNiCr40Al3Ti合金表面制备的铬掺杂类金刚石(Cr-DLC)、氮化铬铝(CrAlN)和氮化铬(CrN)等薄膜的摩擦磨损性能。方法 在GNiCr40Al3Ti合金表面采用离子源辅助非平衡磁控溅射制备Cr-DLC薄膜，采用多弧离子镀技术制备CrAlN薄膜和CrN薄膜。利用冷场发射扫描电镜、拉曼光谱仪和X射线衍射仪，对薄膜的微观结构和形貌进行分析。利用显微硬度计、摩擦磨损试验机、白光干涉扫描轮廓仪等，对薄膜的硬度、摩擦磨损性能、磨痕二维轮廓等进行研究。结果 在10 h连续的去离子水环境摩擦过程中，CrN薄膜的平均摩擦系数最低，仅为0.17，比GNiCr40Al3Ti合金的摩擦系数降低了54%。与GNiCr40Al3Ti合金相比，其表面制备的Cr-DLC、CrAlN和CrN薄膜在去离子水环境摩擦条件下都减小了磨损体积，其中，CrN薄膜表现出最好的耐磨性，磨损体积为0.017 mm³，仅为GNiCr40Al3Ti合金磨损体积的0.18%。Cr-DLC薄膜与CrAlN薄膜的耐磨性不及CrN薄膜，主要是由薄膜的微观结构造成的，Cr-DLC薄膜的柱状疏松结构造成薄膜过早的被磨穿，CrAlN薄膜中存在的Cr相引起薄膜硬度降低，从而降低了抗剪切的能力。结论 在去离子水环境中，CrN薄膜具有最低的摩擦系数和最佳的耐磨性。     

Mechanical and tribological properties evaluation of cathodic arc deposited CrN/ZrN multilayer coatings

Five nanostructured CrN/ZrN multilayer coatings were deposited periodically by cathodic arc evaporation. The bilayer periods of the CrN/ZrN multilayer coatings were controlled in the range of 5 to 30 nm. The structures and bilayer period of the multilayer coatings were characterized by an X-ray diffractometer. The microstructures of thin films were examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), respectively. Nanoindentation, scratch tests, Daimler–Benz Rockwell-C (HRC-DB) adhesion tests, microhardness and pin-on-disk wear tests were used to evaluate the hardness, adhesion, indentation toughness and tribological properties of thin films, respectively. It was found that the hardness and tribological properties were strongly influenced by the bilayer period of the CrN/ZrN multilayer coatings. An optimal combination of mechanical properties and excellent tribological behavior was found for a coating with a critical bilayer period of 30 nm.     

Effect of Axial Magnetic Field on the Microstructure and Mechanical Properties of CrN Films Deposited by Arc Ion Plating

CrN films were deposited on the high-speed-steel substrates by arc ion plating. The effect of an axial magnetic field on the microstructure and mechanical properties was investigated. The chemical composition, microstructure, surface morphology, surface roughness, hardness and film/substrate adhesion of the film were characterized by X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscope(SEM), surface morphology analyzer, Vickers microhardness test and scratch test. The results showed that the magnetic field puts much effect on the microstructure,chemical composition, hardness and film/substrate adhesion of the Cr N films. The N content increases and Cr content decreases when the magnetic flux density increases from 0 to 30 m T. All of the Cr N films were found to be substoichiometric. With an increase in the magnetic flux density, the film structures change in such way: Cr_2N →Cr_(2-N)+CrN→CrN+Cr_2N→CrN.The SEM results showed that the number of macroparticles(MPs) on the film surface is significantly reduced when the magnetic flux density increases to 10 mT or higher. The surface roughness decreases with the magnetic field, which is attributed to the fewer MPs and sputtered craters on the film surface. The hardness value increases from 2074 HV_(0.025) at 0 mT(without magnetic field) and reaches a maximum value of 2509 HV_(0.025) at 10 m T.The further increase in the magnetic flux density leads to a decrease in the film hardness. The critical load of film/substrate adhesion shows a monotonous increase with the increase in magnetic flux density.     

Stress Study on CrN Thin Films with Different Thicknesses on Stainless Steel

The reliability of a substrate curvature-based stress measurement method for CrN thin films on substrate with fluctuant surface was discussed. The stress error led by the ignorance of substrate thermal deformation was studied. Results showed that this error could be as large as several hundred MPa under general deposition conditions. Stress in the CrN thin films with different thicknesses ranging from 110 to 330 nm on stainless steel was studied by this method, in comparison with conventional results on silicon wafer. The thin films' morphology and structure were investigated and related to the film stress. A significant result of the comparison is that stress evolution in the thin films on steel obviously differs from that on silicon wafer, not only because the two substrates have different coefficients of thermal expansion, which provokes thermal stress, but also the considerable discrepancy in the thin films' grain coarsening rate and structure that induce different intrinsic stresses.     

基体材料对Cr/CrN多层涂层在海水环境中磨蚀性能的影响

目的 讨论海水环境下不同基体材料对Cr/CrN交替的多层复合涂层磨蚀性能的影响,为海水环境下耐磨蚀材料基体的选择和应用提供参考。方法 采用多弧离子镀技术在316L不锈钢和TC4钛合金基体上沉积Cr/CrN多层复合涂层,通过XRD、SEM等技术对涂层材料的微观结构进行表征,通过硬度测试、结合力测试、电化学分析、摩擦磨损试验等技术对涂层材料的力学性能、电化学性能以及摩擦学性能进行分析,比较不同基体对Cr/CrN多层涂层在海水环境中磨蚀性能的影响。结果 以TC4钛合金为基体的Cr/CrN多层涂层的硬度为1727.2HV0.3,虽略小于以316L不锈钢为基体的涂层硬度（2241.5HV0.3）,但其在膜-基结合力、海水环境下电化学性能和摩擦学性能等方面均优于以316L不锈钢为基体的涂层。结合力测试中,以TC4为基体的多层涂层初始裂纹出现在31 N,扩展裂纹出现在42 N,大于316L基体涂层的22 N和35 N。电化学测试中TC4基体涂层的腐蚀电位为?0.20 V,大于316L基体涂层的腐蚀电位（?0.21 V）。海水环境下TC4基体涂层的平均摩擦系数和磨损率分别为0.35和2.9950×10?5 mm3/(N?m),均小于316 L基体涂层的平均摩擦系数（0.36）和磨损率（4.9895×10?5 mm3/(N?m)）。结论 TC4钛合金更适合作为海水环境用Cr/CrN多层涂层耐磨蚀材料的基体材料。     

Tribological behavior of CrN/WN multilayer coatings grown by ion-beam assisted deposition

CrN monolayer coating and CrN/WN multilayer coatings were deposited on the silicon (100) substrate by ion-beam assisted deposition process. The bilayer period of these coatings was controlled at 8 nm and 30 nm. The cross-sectional morphology of nanoscaled multilayer coatings was characterized by scanning electron microscopy and transmission electron microscopy. The wear resistance of CrN/WN multilayer coatings and CrN monolayer coating was investigated using a pin-on-disc tribometer. The surface roughness (Ra) of the coatings was evaluated by atomic force microscopy, and that of CrN and WN monolayer coating was 6.7 and 5.9 nm, respectively. The employment of multilayer configuration in CrN/WN coating with bilayer period of 8 nm and 30 nm effectively reduced the surface roughness down to 1.9 and 2.2 nm, respectively. The friction coefficient of CrN monolayer coating and CrN/WN multilayer film with a bilayer period of 30 nm was 0.63 and 0.31, respectively. Owing to the high hardness/elastic modulus ratio, as well as the dense structure and the smooth surface roughness, the CrN/WN multilayer coatings exhibited better wear resistance in the consideration of friction coefficient and the worn surface morphology.     

直流和高功率磁控溅射制备氮化铬薄膜及其结构性能比较

目的 比较直流磁控溅射（DCMS）和高功率磁控溅射（HiPIMS）两种沉积技术制备的氮化铬（CrN）薄膜的结构和性能。方法 采用DCMS和HiPIMS沉积技术,在金属镍（Ni）基底上沉积CrN薄膜,采用X射线衍射（XRD）、扫描电镜（SEM）和显微硬度计等仪器,分析CrN薄膜的晶相结构、表面以及截面形貌、基底与薄膜复合硬度、摩擦性能等。结果 XRD晶体测量显示DCMS制备的CrN薄膜在(111)晶面择优生长,内应力大;而HiPIMS制备的CrN薄膜为(200)晶面择优生长,内应力小。SEM显示两种方法制备的CrN薄膜都呈柱状晶体结构生长,但HiPIMS沉积的CrN薄膜颗粒尺寸较小,柱状晶体结构和晶粒更致密。硬度测量得到HiPIMS制备的CrN薄膜显微硬度为855.9HV,而DCMS制备的CrN薄膜显微硬度为501.5HV。此外,DCMS制备的CrN薄膜平均摩擦系数为0.640,而HiPIMS制备的CrN薄膜摩擦系数为0.545,耐磨性也好。HiPIMS制备的CrN薄膜的腐蚀电流比DCMS制备的CrN薄膜低1个数量级。结论 HiPIMS沉积技术制备的CrN薄膜颗粒尺寸小,结构更致密,且缺陷少、硬度高、防腐蚀性好,薄膜各项指标都优于DCMS沉积的CrN薄膜。