CVD金刚石薄膜涂层整体式刀具的制备与应用

化学气相沉积(chemical vapor deposition,CVD)金刚石薄膜具有硬度高、摩擦系数低、耐磨性强以及表面化学性能稳定等优异的机械及摩擦学性能,这使其在硬质合金工模具领域具有广阔的应用前景.本文采用热丝化学气相沉积法(hot filament chemical vapor deposition,HFC...     

Inclined impact–sliding wear tests of TiN/Al2O3/TiCN coatings on cemented carbide substrates

A chemical vapor deposition (CVD) TiN/Al₂O₃/TiCN coating has been commercially used as a protective coating on cemented carbide cutting tools to improve tool life and superficial quality of the workpiece. However, the CVD coating is relatively brittle and could fail due to fatigue cracking induced wear under localized contact stresses during the milling operation. Traditional coating evaluation techniques such as tribo tests, scratch tests and impact tests only involve single movement, i.e., either sliding or impacting. In the present work, the fatigue and wear behavior of the triple-layered coatings on cemented carbide substrates was investigated using a novel impact–sliding wear tester, which simulates a repetitive movement of combined impact and sliding motions between cutting tools and workpieces during interrupted milling operations. The coatings on the surface and cross-section were studied using Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray (EDX) analysis. The results from the impact component showed that fatigue cracking increased for the coating on a harder substrate likely due to the lower toughness of the substrate. The results from the sliding component showed that the wear resistance of the coating decreased as the substrate was softer. The test results provided constructive knowledge in selection and development of coatings for impact and sliding involved applications.     

镁合金表面沉积铜钨复合涂层工艺及涂层性能研究

目的提高镁合金表面的耐蚀耐磨性。方法采用冷喷涂与化学气相沉积(CVD)相结合的方法在镁合金表面制备出Cu/W复合涂层,并对复合涂层的结构、成分、组织形貌、耐磨性、耐蚀性、结合力进行分析。结果镁合金基体沉积Cu/W复合涂层后,表面硬度提高了687.1HV,磨损率从0.032%降到0.020%,腐蚀电位正移了1.3 V,临界载荷相比直接化学气相沉积W涂层提高了120.5 N。结论Cu/W复合涂层显著提高了镁基体的耐磨、耐蚀性,涂层与基体结合力较高。     

沉积温度对化学气相沉积铼涂层性能的影响

利用五氯化铼热分解反应,采用冷壁式现场氯化化学气相法在钼基体沉积铼涂层,分析不同沉积温度对铼涂层的物相组成、沉积规律、表面形貌、密度和硬度的影响。实验结果表明:沉积所得均为纯铼涂层,晶粒生长方向均以(002)晶面为主;随着沉积温度的上升,铼涂层的沉积速率和沉积效率大幅提升,表面形貌由复杂多面体态变为六棱锥状;涂层组织致密,相对密度最高可达99.9%,维氏硬度随沉积温度升高而升高,最高达6100 MPa。     

直流PCVDTi（CxN1—X）硬质膜及其应用

对不同成分的PCVD－Ti（CXN1－X）膜的组织结构及性能进行了研究。结果表明，Ti（CN）膜的高硬度、高致密组织和膜表面因吸附氧而形成的与TiN不同的表面结构是Ti（CN）膜性能优于TiN膜的重要因素。在冷挤压模上应用结果也表明，用PCVD法制备的Ti（CN）膜和TiC膜的使用效果要比TiN膜好得多。     

Reduction of wear at hot forging dies by using coating systems containing boron

The near surface area of forging dies is exposed to high mechanical loads. Additionally thermal and chemical stresses appear during the hot forging process. Depending on the number of forged parts, several kinds of stresses occur in the near surface area, which lead to the initial failures of forging dies. Wear is the main reason for production downtimes with a ratio of 70%. Furthermore, thermal and mechanical cracks are typical causes for failures causes as well as plastic deformation. In order to reduce wear, the abrasion resistance of the forging die surface has to be increased. Hence, different methods like plasma nitriding and optional additional thin hard coatings (TiN, TiCN, TiC, TiBN and TiB₂) were successfully examined. Recently developed Ti–B–N coatings in specific multilayer designs are thermally stable, wear-resistant and anti-adhesive regarding the sticking of work piece material. This paper presents the wear reduction possibilities of boron-containing multilayer coating systems applied to forging dies by using the plasma enhanced chemical vapor deposition treatment. A basic mechanical and analytical characterization of different coating systems is realized in the first stage of the project. Best qualified multilayer coating variants were applied to forging dies for experimental investigations. As a result of the tests, wear can be reduced significantly by using thermally stable boron multilayer coatings. To receive realistic wear values under production conditions, an automated forging process was used for testing. After 3,000 forged parts, the coatings were examined by tactile measurement, SEM and EDX analyses to characterize the occurring wear.     

贵金属化学气相沉积的研究进展

简要介绍了贵金属薄膜和涂层材料化学气相沉积(CVD)技术的研究进展,包括贵金属的CVD制备方法、沉积贵金属的各种前驱体化合物以及CVD制备的贵金属薄膜和涂层的应用状况等。     

The Principles and Applications of Chemical Vapour Deposition

Chemical vapour deposition (CVD) is a technique that relies on the formation of a gaseous species containing the coating element within a coating retort or chamber. Alternatively, the gaseous species may be generated external to the coating retort and introduced via a delivery system. These gaseous species (eg, chromous chloride) are then allowed to come into contact with the surfaces that require coating. The retort is held at a high temperature, normally in excess of 800°C. The application of this thermal energy and the presence of a reducing atmosphere results in the decomposition of the molecules containing the coating element which are subsequently deposited onto the surface of the substrate.

Using the CVD method a wide variety of coatings may be formed, ranging from soft, ductile coatings to those with hard, ceramic like properties. Coating thicknesses can vary from a few micron to over 200 mm, with hardnesses in the range 150–3000 HV (0.1Kg). Coatings formed by the CVD method are currently being used to combat the severe attrition of components used in a variety of industrial situations where corrosion, oxidation or wear is experienced.

The methods commonly used to apply CVD coatings will be discussed and their advantages and limitations examined. Several case studies will be highlighted, where CVD coatings have been used to solve specific industrial problems.     

CVD diamond coating for erosion protection at elevated temperatures

Small solid particles entrained in a gas-fluid turbomachinery flow can cause degradation of the component surfaces containing the flow by erosion and corrosion processes. As diamond is the hardest known material, much work has been done to use polycrystalline diamond (PCD) as a protective coating on parts operating in a hostile and abrasive environment. Little attention is given in the literature to the high-temperature erosion behavior of chemical vapor deposition (CVD) diamond on different substrates. The objectives of this research were to develop CVD diamond erosion barriers for surface protection of cemented tungsten carbide at high temperatures and to study the erosion behavior of the coatings. Microwave plasma chemical vapor deposition (MPCVD) was used to apply diamond films on WC-6%Co. The erosion behavior of the coated specimens was investigated experimentally by exposing them to abrasive particle-laden flow in a high-temperature wind tunnel. The obtained results show the effects of impingement angle, temperature, and particle dose on the erosion rate. The data demonstrate that uncoated substrates suffer 6–7 times higher wear compared to diamond-coated samples at elevated temperatures up to 538 °C when exposed to alumina particle flow. This study indicates that polycrystalline diamond is emerging as a promising erosion protective coating for high-temperature applications. Paper presented at Materials Solutions Conference & Exposition 2000, St. Louis, MO.     

化学气相沉积制备硬质合金刀具涂层研究进展

化学气相沉积技术(CVD)广泛应用于硬质耐磨涂层的生产中,该类涂层可大大提高硬质合金工具的耐磨性和寿命。综述了CVD涂层技术在硬质合金切削刀具中的应用研究进展,首先介绍了CVD涂层技术的原理及其发展历程;其次阐述了模拟计算方法(相图计算、流体力学计算、第一性原理计算、相场模拟、机器学习等)在CVD涂层中的应用;再次介绍了CVD涂层的沉积实验及结构和性能表征方法;最后列举了几种典型的硬质合金刀具用CVD涂层,以期为高性能涂层的智能设计、智能集成和智能研发提供新的思路:即把多尺度计算模拟、科学数据库和关键实验集成到硬质涂层开发的全过程中,通过对成分-工艺-结构-性能进行关联分析,将耐磨涂层的研发由传统经验或者半经验方式提升到科学的微结构智能设计上,以实现基体与涂层微结构调控和性能的协同优化,获得最佳的综合性能。     

Al基准晶薄膜/涂层研究进展∗

准晶材料固有脆性限制其作为结构性材料的应用,广泛用于表面薄膜/ 涂层,而得到高纯度准晶相与控制准晶相变仍是应用难点。 围绕 Al 基准晶在表面薄膜/ 涂层应用方面,介绍真空蒸镀、溅射镀膜、热喷涂、激光熔覆等常用制备工艺,总结各工艺的特点。 分析准晶薄膜/ 涂层的成分、冷却速度、热处理对准晶相变的影响,合理的制备工艺和适当的后续热处理对薄膜/ 涂层中形成高纯度准晶有显著提升。 讨论相变对薄膜/ 涂层的力学性能、疏水性、摩擦性、耐腐蚀性和抗氧化性的影响,分析准晶薄膜/ 涂层在减磨耐磨涂层、热障涂层、太阳能选择性吸收薄膜等领域的应用前景。 综述了近 30 年准晶薄膜/ 涂层的制备技术及改性研究的重要结果和研究现状,提出了准晶薄膜/ 涂层应用方面存在的问题并进行了展望。     

Deposition and properties of high-velocity-oxygen-fuel and plasma-sprayed Mo-Mo2C composite coatings

Molybdenum thermal-spray coatings, dispersion strengthened by molybdenum oxides and molybdenum carbides, play an important role in industrial tribological applications. Traditionally, they have been prepared by plasma and wire flame spraying. High porosity and lower cohesion strength limit their application in situations where both galling and abrasion wear is involved. In this study, high-velocity-oxygen-fuel (HVOF) deposition of molybdenum and molybdenum carbide coatings was attempted. Deposition was achieved for all powders used. Composition, microstructure, mechanical, and wear properties of the HVOF synthesized coatings were evaluated and compared with plasma-sprayed counterparts. The HVOF coatings possessed a very good abrasion resistance, whereas plasma deposits performed better in dry sliding tests. Measurements showed a close relationship between the coating surface hardness and its abrasion resistance. Results also suggested correlation between molybdenum carbide distribution in the molybdenum matrix and the sliding friction response of Mo-Mo₂C coatings.     

ALD沉积HfO_2薄膜生长行为及其调控

采用原子层沉积(ALD)的方法,选择四二乙基氨基铪(TDEAH)和水作为反应前驱体,在p型(100)单晶硅衬底上制备了HfO_2高介电质薄膜。系统研究了前驱体流量、反应气压、反应温度等工艺参数对HfO_2薄膜生长质量的影响。通过工艺调控,发现存在两种薄膜生长模式:类CVD(化学气相沉积)生长模式和ALD生长模式。发现薄膜的生长模式主要依赖于制备工艺参量:脉冲参量M和冲洗参量Q,通过优化工艺参数,可实现薄膜生长由类CVD生长模式向ALD生长模式的转变,并获得了0.1 nm/周次的最优薄膜生长速率。同时,薄膜微结构与表面形貌的表征结果表明:薄膜的非晶晶态转变受温度和膜厚两个因素共同控制。     

Chemical Vapor Deposition of Iridium and Rhodium Coatings from Hydridotetrakis(trifluorophosphine) Complexes

Chemical vapor deposition (CVD) of iridium and rhodium coatings using hydridotetrakis(trifluorophosphine) complexes as the precursor is presented. These inorganic, volatile, carbon- and oxygen-free compounds undergo a decomposition reaction to form highly pure iridium and rhodium metallic films on molybdenum substrates in the CVD reactor at growth temperatures as low as 450°C. The dependences of the deposition process and characteristics of the iridium and rhodium coatings have been investigated.     

Hot-filament chemical vapor deposition of polycrystalline diamond coatings to interlayered steel

Zr-based nitride and carbide coatings have been deposited on high-speed steel by the cathodic arc method. Hot-filament chemical vapor deposition (CVD) has been used to deposit diamond films onto a treated steel surface. The films deposited by CVD were characterized using scanning electron microscopy, x-ray diffraction, and Raman spectroscopy to determine the surface morphology, roughness, crystal structure, and bonding characteristics. This paper was presented at the fourth International Surface Engineering Congress and Exposition held August 1–3, 2005 in St. Paul, MN.     

A review on polishing technology of large area free-standing CVD diamond films

Recently, with the rapid development of chemical vapor deposition (CVD) technology, large area free-standing CVD diamond films have been produced successfully. However, the coarse grain size on the surface and the non-uniform thickness of unprocessed CVD diamond films make it difficult to meet the application requirement. The current study evaluates several existing polishing methods for CVD diamond films, including mechanical polishing, chemical mechanical polishing and tribochemical polishing technology.      

Experimental design in the deposition of BN interface coatings on SiC fibers by chemical vapor deposition

Boron Nitride (BN) coatings deposited by chemical vapor deposition (CVD) have been increasingly used as an interface material for SiC/SiC composites. In this work, the CVD of BN was investigated using a statistical design of experiments (DOE) approach. In order to determine the most significant parameters for the process a two-level screening design (Plackett-Burman) was employed. The deposition pressure, gas mixture dilution factor, deposition time, and the reaction gas flow ratios were found to be the most significant factors that influenced coating thickness. To optimize the deposition process, a three-level surface response design (Box-Behnken) was used with the aim of producing a predictive mathematical model of the process. The generated response surface modeling (RSM) showed that deposition time had the greatest effect on coating thickness while, temperature-time and temperature-NH₃/BCl₃ interactions may be large at low/high NH₃/BCl₃ ratios and high deposition time, respectively. Tensile strength was strongly influenced by the deposition temperature and deposition time. The response model showed the dependence of tensile strength on coating thickness, NH₃/BCl₃ gas flow ratios and time. The model interaction plots suggested a dependence of temperature-gas flow ratio on tensile strengths of BN coated SiC fibers.     

氧的掺入对化学气相沉积TiCN涂层的影响

本文采用X射线衍射仪(XRD)、高分辨扫描电镜(HRSEM)、显微维氏硬度计、声发射划痕仪,研究了以化学气相沉积(CVD)法制备的TiCN和TiCNO涂层。通过对比涂层的相结构、组织形貌、硬度及结合强度,分析氧的掺入对TiCN涂层显微结构和力学性能,特别是结合强度的影响。结果表明:CVD制备的TiC0.81N0.48涂层截面呈柱状结构,硬度和结合强度分别为2 063 HV及127 N。掺入氧后的TiC0.61N0.44O0.15和TiC0.52N0.25O0.1涂层没有出现新的物相,为面心立方结构的TiCNO固溶体,具有(111)织构;氧的掺入细化了晶粒,使涂层转变为致密结构;其硬度分别提高至2 207 HV和2 753 HV,但与基体结合强度分别下降至88 N和63 N。     

Preparation and cyclic oxidation of gradient NiCrAlYRe coatings on Ni-based superalloys

Arc ion plating (AIP) and chemical vapor deposition (CVD) aluminizing were combined together to produce a gradient NiCrAlYRe coating. Elements in this coating were chemically graded with Al enrichment in the outer zone and Cr enrichment in the intermediate zone. Cyclic oxidation tests were performed at 1100 °C for up to 22 cycles. The results showed that the gradient NiCrAlYRe coatings performed better resistance to spallation and Al depletion than the conventional NiCrAlYRe coatings. This favorable oxidation behavior was attributed to the high Al distribution in the near surface region of the gradient coating.     

Formation of aluminide coatings on Fe-based alloys by chemical vapor deposition

Aluminide and Al-containing coatings were synthesized on commercial ferritic (P91) and austenitic (304L) alloys via a laboratory chemical vapor deposition (CVD) procedure for rigorous control over coating composition, purity and microstructure. The effect of the CVD aluminizing parameters such as temperature, Al activity, and post-aluminizing anneal on coating growth was investigated. Two procedures involving different Al activities were employed with and without including Cr–Al pellets in the CVD reactor to produce coatings with suitable thickness and composition for coating performance evaluation. The phase constitution of the as-synthesized coatings was assessed with the aid of a combination of X-ray diffraction, electron probe microanalysis, and existing phase diagrams. The mechanisms of formation of these CVD coatings on the Fe-based alloys are discussed, and compared with nickel aluminide coatings on Ni-base superalloys. In addition, Cr–Al pellets were replaced with Fe–Al metals in some aluminizing process runs and similar coatings were achieved.