Development of oxide based diffusion barrier coatings for CFC components applied in modern furnaces

Carbon fibre reinforced carbon (CFC) materials show a high potential for usage in furnaces as sample carriers for example, which is due to their excellent thermal stability compared to steel carriers. Only their tendency to react with different metals at high temperatures by C-diffusion is a disadvantage, which can be solved by application of diffusion barriers. In order to enable the utilization of CFC-carriers for e.g. brazing furnaces, within the frame of this study thermally sprayed diffusion barrier coatings were developed. Coatings of mullite and ZrO₂-7%βY₂O₃ (YSZ) were prepared by air plasma spraying (APS). The coatings were investigated in terms of their microstructure and thermal shock behaviour. In order to prove the suitability of the coatings for the application in brazing furnaces, the wettability of the coating surfaces by a Ni-based brazing alloy was investigated. The results showed that both mullite and YSZ could be deposited on CFC substrates with a bond coat of W or SiC. Both coatings exhibited good thermal shock behaviour and an excellent non-wetting behaviour against the used Ni-based braze alloy.     

Preparation and characterization of nanocrystalline ZrO2-7%Y2O3 powders for thermal barrier coatings by high-energy ball milling

High-energy ball milling is an effective method to produce nanocrystalline oxides. In this study, a conventional ZrO₂-7%Y₂O₃ spray powder was ball-milled to produce nanocrystalline powders with high levels of crystalline disorders for deposition of thermal barrier coatings. The powder was milled both with 100Cr6 steel balls and with ZrO₂-3%Y₂O₃ ceramic balls as grinding media. The milling time was varied in order to investigate the effect of the milling time on the crystallite size. The powders were investigated in terms of their crystallite sizes and morphologies by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that under given milling conditions the powder was already nanostructured after 40 min milling. The crystallite size decreased significantly with increasing milling time within first 120 min. After that, a further increase of milling time did not lead to a significant reduction of the crystallite size. Ball-milling led to lattice microstrains. Milling with the steel balls resulted in finer nano-sized crystal grains, but caused the contamination of the powder. The nano-sized crystal grains coarsened during the heat-treatment at 1250°C.     

Vibration monitoring in sliding wear of plasma sprayed ceramics

Dry frictional contact between two surfaces, one made of plasma sprayed ceramic coatings of Al₂O₃ and Al₂O₃---TiO₂ combination and the other made of steel, is analyzed. The experiments were conducted using a pin-on-disc set-up in the load range of 5–35 N and for sliding distances up to 14 km. The interactions between friction, wear and vibrations due to influence of normal load, sliding speed and system dynamics are investigated in the present paper. Two vibration parameters of pin in the load direction (vertical) are monitored, namely the r.m.s. acceleration and the kurtosis, which seem to be influenced considerably by the wear process and indicate correlation with wear mechanisms taking place such as stick-slip and grain pull-out, as evidenced by scanning electron microscopy of worn surfaces. The study shows that a range of frequency is to be utilized for vibration monitoring to include natural frequencis of the system consisting of pin in contact with disc. This could be estimated by a standard impulse hammer test. The pin acceleration decreases with increase in load and sliding distance, but with respect to sliding speed, the vibration level intially decreases but increases beyond the sliding speed of 1.5 m s⁻¹. Among the three ceramic coatings, TiO₂ is found to be most wear resistant, exhibiting the lowest friction coefficient and a low vibration level. Variation in kurtosis with run-in wear indicates smoothing of Al₂O₃ due to grain pull out.     

Effects of a second phase on the tribological properties of Al2O3 and ZrO2 ceramics

The tribological properties of four different materials are investigated, tetragonal zirconia (Y-ZTP), Al₂O₃ dispersed in Y-TZP (ADZ), ZrO₂ dispersed in Al₂O₃ (ZTA) and Al₂O₃ (with 300 ppm MgO). These materials are used as a cylinder sliding against a plate of Y-TZP (TZ-3Y)). Compared to Y-TZP, the wear resistance of ADZ composites is increased by a factor of 4–10. At a contact pressure of 230 MPa, a wear transition for Y-TZP is observed from plastic deformation to microchipping and microfracture due to the high interfacial temperature (450°C–550°C) generated by frictional heating. Because of the higher elastic modulus, hardness and fracture toughness at high temperature, ADZ composites show better wear resistance and a higher transition contact pressure (over 400 MPa) under the present conditions. For Al₂O₃, the transition from mild to severe wear occurs when the contact pressure is changed from 250 to 400 MPa. For ZTA ceramics, the wear behaviour does not change because of the presence of a compressive layer due to the zirconia phase transformation during sliding.

In water the wear resistance for ADZ and ZY5 is almost two orders of magnitude higher than the results under dry conditions. Reduction of the interfacial temperature by using water and the formation of a hydroxide layer at the contact surface by the tribochemical reaction of water with the ceramic, as observed by XPS, gives a positive effect on wear resistance.     

Y2O3改性石墨/CaF2/TiC/镍基合金复合涂层微观组织与摩擦学性能研究

为提高石墨/CaF₂/TiC/镍基合金（GCTN）复合涂层的力学性能和摩擦学性能,运用等离子喷涂技术在45钢表面制备了Y₂O₃改性GCTN复合涂层,研究了Y₂O₃对复合涂层的微观组织、显微硬度、断裂韧性和摩擦磨损性能的影响。结果表明：Y₂O₃改性GCTN复合涂层主要由γ-Ni、CrB、Cr7C₃、TiC、CaF₂和石墨等物相组成。Y₂O₃在等离子火焰加热作用下与C元素反应生成活性元素Y,Y净化了复合涂层的微观组织,并细化了CrB、Cr₃C7等硬质相晶粒,提高了其致密性。当Y₂O₃质量分数为0.5%时,复合涂层的显微硬度和断裂韧性分别为593.3MPa和6.82MPa·m^1/2,比不含Y₂O₃的复合涂层分别增大了8%和22%,其机理主要是Y₂O₃细化了CrB、Cr₃C₇等硬质相晶粒,起到了细化强化作用。由于GCTN-0.5Y₂O₃复合涂层的显微硬度和断裂韧性显著提高,减少了其黏着磨损和微观断裂磨损,因而GCTN-0.5Y₂O₃复合涂层的摩擦因数和磨损率最小,分别为0.085和0.39×10-3mm3/m。     

Adhesion, friction and wear of thin hard coatings

Chemically vapour-deposited and physically vapour-deposited coatings of hard and wear-resistant materials such as TiC, TiN, Ti(C, N), Cr₇C₃, Al₂O₃, SiO₂ and TiO₂ as well as other carbides, nitrides, borides, oxides and combinations thereof are increasingly used in industrial applications to protect metal, ceramic and in certain cases polymer parts against mechanical and chemical attack, sometimes with a decorative purpose also. Some relevant examples of coated products are cemented carbide throwaway cutting tips (TiC, TiN, Ti(C, N), Al₂O₃ etc.), high speed steel drills and milling cutters (TiN), hobs, deep drawing tools, ball-bearing elements, gears, machine elements, electrical contacts, body implants, surgical instruments and tools, cutlery, fuel pins and armatures especially for helium- and sodium-cooled nuclear reactors, low Z sputter-resistant protective coatings on parts (limiters, antennae etc.) and walls of the torus in fusion reactors (tokamak) and gold- or silver- or black-coloured watch cases and jewelry pieces. The life of such coated tools or machine elements as well as their performance are considerably increased, provided that the adhesive strength of the coating to the base material and the intrinsic cohesion of the coating are sufficient. Bad adhesion leads to flaking (adhesive failure) while poor cohesion causes chipping (cohesive failure).     

Effect of lubricants on the friction and wear of Al2O3 against gray cast iron

The tribological behavior of ceramic Al₂O₃ coupled with gray cast iron (PHT) with different lubricants was investigated using a ring-on-block wear tester. In the wear test, air, distilled water, emulsion and oil were used as lubricants respectively in order to check the lubricating effectiveness of lubricants and the friction mechanism of solid graphite in the cast iron. Wear testing of 0.8% C steel (T8) sliding with Al₂O₃ was also carried out to compare with the test using gray cast iron. From these data the tribological behavior of graphite in the iron can be evaluated. The results show that the friction and wear of tested couples are decreased using different lubricants in the following order: air, distilled water, emulsion and oil. When lubricating with air and water, graphite in the iron as solid lubricant can decrease the friction and wear of the couples. However, when lubricating with emulsion and oil, graphite does not show the advantage of decreasing friction and wear.     

Friction and wear properties of UHMWPE/Al2O3 ceramic under different lubricating conditions

Friction and wear behavior of ultra-high molecular weight polyethylene (UHMWPE) sliding against Al₂O₃ ceramic under dry sliding, and lubrication of fresh plasma, distilled water and physiological saline were investigated with a self-made pin-on-disk apparatus at 37±1°C. The worn surfaces were examined with a scanning electron microscope (SEM). The results show that the friction behavior of UHMWPE is very sensitive to its water absorption state. The wear rate of UHMWPE under dry sliding is the highest and under plasma lubrication is the lowest. The wear mechanisms are different under dry friction and various lubricating conditions.     

Effect of a surface film on the friction and wear properties of plasma-sprayed Al2O3---40%ZrO2 coatings

In order to provide the replenishment of a surface film in high temperature lubrication, an in situ formed graphite film is very useful. In this work, five synthetic lubricants were employed to evaluate the effectiveness of graphite film generation on a ceramic coating under extreme conditions of high pressure and 320 °C. Combined lubrication of the liquid and solid film occurs, and a carbonaceous polymer is generated on the Al₂O₃---40%ZrO₂ coating. Because of combined lubrication, the friction coefficient decreases to 0.04 from about 0.5 for dry friction. The main wear mechanisms involved smearing and breaking off of the ceramic coating for high temperature lubrication. Zin dialkyldithiophosphate (ZDDP) plays an important role in the anti-wear performance of oils, and mainly smearing wear is observed on the coatings lubricated with ZDDP-containing oils.     

大尺寸单晶金刚石衬底抛光技术研究现状与展望

近些年来,化学气相沉积（Chemical vapor deposition,CVD）单晶金刚石在电子学领域的应用令人瞩目,这得益于CVD单晶金刚石在生长技术和半导体掺杂技术上的进展。一直以来,成熟的衬底加工技术是半导体材料得以应用的基础,其中超精密抛光作为晶圆衬底加工的最后一道工序,直接决定了晶圆表面粗糙度和亚表面损伤程度。可以预见,超精密抛光技术将会在制备大尺寸高质量金刚石衬底中发挥重要作用。对目前国内外现有的单晶金刚石抛光方法进行综述,以制备大尺寸高质量单晶金刚石衬底为目标,从加工设备、工艺参数、加工精度、加工效率和材料去除机理等方面进行分析,总结各种抛光方法的优势和缺点,展望未来大尺寸单晶金刚石衬底抛光技术的发展趋势。目前鲜有针对大尺寸单晶金刚石抛光技术的综述,本文为国内学者展开单晶金刚石抛光相关工作的研究提供综述资料。     

Counterface effects on the wear of a composite dry-bearing liner

Plastics-based dry-bearing liners used for flight control bearings in aircraft are usually mated against counterfaces of 440C stainless steel hardened to about 700 HV and finished to R_a ≈ 0.05 μm. In this paper experiments to examine the possibility of reducing liner wear by modifications to the counterface are described. Accelerated (pin-on-disc) tests were made against 440C stainless steel of varying hardness and roughness, electroplated with copper and cadmium, ion implanted with nitrogen, copper and cadmium, vacuum deposited with TiN and TiC, diffusion treated with nitrogen, boron, sulphur, Sn-Cu and Sn-Sb and coated with ceramics-cermets (Al₂O₃, Cr₂O₃, (Cr₂C₃)-Ni-Cr and WC-Co). The most important counterface properties influencing liner wear are the hardness and surface roughness, and for ceramic and cermet coatings, the harder and smoother the surface, the lower is the liner wear. No evidence was found to indicate that the chemical nature of the counterface has a major affect on the liner wear.     

High temperature friction and wear characteristics of various coating materials for steam valve spindle application

Various coatings such as chromium carbide (deposited by plasma spraying and detonation gun techniques), chromium oxide, chromium oxide+titania+silica, NiCrAlY, and Al₂O₃+NiAl, all deposited by plasma spraying; stelliting, and surface nitriding have been applied on X20CrMo V121 steel. This steel is used for high temperature applications such as steam turbine valve spindle. Friction and wear behavior of the surface coated and treated materials have been studied at an elevated temperature of 550°C while rubbing against graphite-filled stellited steel. These studies have been carried out on SRV Optimol reciprocating tribometer. Test parameters for tribological studies have been selected with a view to simulate operating conditions encountered in operation. Additionally, the structure, porosity, hardness, bond strength, and thermal cycling behaviour of these surface coated/treated materials have been characterised. Based on these laboratory investigations, chromium carbide coating deposited by plasma spraying technique has been identified as the most suitable coating for steam turbine valve spindle application. Process parameters have been established for deposition of chromium carbide coating by plasma spraying technique on actual valve spindles. The field results obtained are found to be commensurate with the laboratory findings.     

WEAR PERFORMANCE OF MULTILAYER-COATED CARBIDE TOOLS

Three multilayer-coated carbides [two trigon-shaped inserts: Ti(C,N)/TiC/Al₂O₃ (T1), Ti(C,N)/ Al₂O₃/TiN (T2) and one 80°-rhomboid shaped insert: TiC/Al₂O₃/TiN (T3)] were used to machine a martensitic stainless steel at various combinations of cutting speed and feed rate without coolant to assess their wear performance. Significant nose wear and chipping/fracture of the cutting edge were the predominant failure modes affecting tool performance at higher speed conditions. Plucking of tool materials was the main rake face wear phenomenon observed on T1 grade insert with alumina as the top-layer coating when machining at the lower speed conditions. Attrition and plastic flow were the main wear mechanisms observed on the ceramic coating layers, with dissolution-diffusion being the probable wear mechanism of the tool grades where tungsten carbide substrate had direct contact with the flowing chip. The fitted statistical wear models revealed T3 grade insert with 80°-rhomboid shape as having the highest speed-feed capability, resulting in the highest material removal rate relative to T1 and T2 grade inserts with trigon shapes.     

Preparation of ultrafine α-AlO using precipitation-azeotropic distillation method

Ammonium aluminum carbonate hydroxide (AACH) was prepared by a precipitation-azeotropic distillation method, which uses aluminum sulfate as the Al source and ammonium carbonate as the precipitant. Then, AACH was calcined into ultrafine ?-Al₂O₃ powder. The factors that influence the dispersion property of ultrafine ?-Al₂O₃ powder are discussed in this paper, such as the methods of adding materials, surfactant, and drying methods. The changes of the structure and property of ultrafine alumina in the thermal treatment process are also studied. The morphological structure and properties of AACH are characterized by DTA/TGA, SEM, XRD, and ICP measurements. The results show that ultrafine ?-Al₂O₃ powder with a uniform particle size and well-distributed property can be synthesized only after aluminum sulfate atomizes into ammonium carbonate, proper amount of PEG1000 is added as the dispersant, and the product is treated by azeotropic distillation. The phase transformation of alumina during the calcination process can be described as amorphous Al₂O₃ → ?-Al₂O₃ → ?-Al₂O₃ → ?-Al₂O₃. The crystal grain size and density of ultrafine alumina powder increase with the increase of the calcination temperature. After AACH has been calcined at 1200°C for 2 h, the ultrafine ?-Al₂O₃ with uniform particle size, spherical shape, and more than 99.97% purity is obtained and its powder is well dispersed.     

Computer Simulation of Orthogonal Cutting using a Tool with Multiple Coatings

The development and evaluation of an orthogonal cutting simulation model for carbide tools with multiple coating layers (1 µm-TiN/3 µm-Al₂O₃/6 µm-TiC) is presented. The chip geometry, cutting forces, tool temperatures and stresses were predicted using the Finite Element Method (FEM). The results were analyzed with a focus on the understanding of the thermal influence of coating upon tool temperatures at the tool-chip interface and in the substrate. In the simulation model used, the thermal effect of tool coating was considered by using two different models: (a) use of individual coating layers defined with intrinsic thermal properties and (b) use of a composite coating layer defined with equivalent thermal properties. The proposed models were evaluated by comparing the predictions with the experimental data available in the literature under the same cutting conditions. The steady state tool temperature solution was obtained by adopting a three-step simulation scheme. It consisted of an initial Lagrangian-type simulation until a stable chip shape was formed and a subsequent Eulerian-type calculation with update of the free surface and plastic strain field of the workpiece. The predicted results indicated that for the coated tool considered the thin-film surface coatings with an Al₂O₃ intermediate layer did not significantly alter the steady state temperature gradients between the chip and the tool substrate and provided little thermal insulation effect to the tool substrate. However, the modified thermal response of the coated tool surface caused lower cutting temperatures at the tool-chip interface as compared to that for an uncoated tool under the same conditions. Although these results are consistent with similar experimental observations in the literature, further validation work needs to be conducted.     

A study of abrasive wear mechanisms using diamond and alumina scratch tests

Scratch tests using alumina (Al₂O₃) abrasive particles and Vickers diamond pyramids were employed to study material removal mechanisms in the abrasion of cobalt-base powder metallurgy alloys 6 and 19. The alloys were specially prepared to produce either fine or coarse carbides in order to study the effects of carbide size. Scanning electron microscopy was used to analyze the scratch grooves, the scratch tools and the wear debris particles.

Comparison of scratch tests with Al₂O₃ and diamond pyramids shows that many features produced by the extremely hard regularly shaped diamond tools are different from those produced by irregular Al₂O₃ particles. Except for differences produced by tool wear, multiple-pass Al₂O₃ scratch tests provide excellent reproduction of the material removal processes which occur in low stress Al₂O₃ abrasion. Al₂O₃ scratches produced both chip-like and fine irregular debris particles similar to those extracted from spent abrasive used in wear testing.

Material removal in the fine carbide alloys is facilitated by the direct removal of entire carbides within the volume of micromachining chips removed from the scratch groove. In coarse carbide alloys, machining chips from large carbides are observed, but the depth of cut in the carbide phase is less than that in the f.c.c. matrix and this leads to a decrease in the volume of material removed. Direct comparison of chips removed from fine and coarse carbide alloys by the same Al₂O₃ particle shows larger chips from the fine carbide material.

The effects of subsurface deformation and surface irregularities on material removal were studied by carrying out scratch tests on specimens subjected to prior abrasion and by investigating multiple-pass scratches in the same scratch groove.     

热障涂层折射率与厚度的太赫兹无损检测

精确提取陶瓷层（Top coat,TC）与热生长氧化层（Thermally grown oxide,TGO）层在太赫兹频段的折射率是进行热障涂层（Thermal barrier coatings,TBCs）太赫兹无损检测研究的重要条件。由于对涂层样品只能采取反射式测量,所以首先比较了反射式与传统透射式测量条件下提取样品太赫兹光学参数及厚度的结果,随后利用反射式太赫兹时域脉冲成像系统提取等离子体喷涂的8YSZ热障涂层（TBCs）中TC层与TGO层的折射率,并依据所提取折射率进一步对TC层的厚度分布进行测量及成像。试验结果表明在材料中衰减较小的有效频段下反射式测量同样可以精确提取样品的折射率以及厚度,反射式测量TC层的平均折射率为5.23,TGO层的折射率为2.91,TGO的主要成分α-Al₂O₃的折射率为2.85。TBCs样品中TC层的平均厚度为257 μm,从TC层厚度的太赫兹图像中可观察到TC与粘结层（Bond coat,BC）界面的不均匀程度。反射式太赫兹无损检测可精确提取TBCs中TC与TGO的折射率和厚度,这对于TBCs中裂纹和气泡等缺陷的识别以及TGO生长太赫兹检测具有重要意义。     

The tribological properties of YBa2Cu3O7 films in ambient environment

In the present study, high-T_c superconducting thin YBa₂Cu₃O₇ films and polysilicon films were prepared to investigate the initial sliding friction properties using a ball-on-flat tribometer when samples were moved against a sapphire ball or a steel ball in ambient environment. The surface topography was measured with atomic force microscope (AFM). After five times testing, the experimental results indicate that the friction coefficient of YBa₂Cu₃O₇ films is lower than that of polysilicon films when sliding against a sapphire ball and almost the same when sliding against a steel ball. In particular, the initial friction of YBa₂Cu₃O₇ films is more stable when sliding against a sapphire ball. However, the initial friction of polysilicon films fluctuates during a cycle period when sliding against a sapphire ball. They are both stable when sliding against a steel ball. Although, the surface profile of the YBa₂Cu₃O₇ film is rough and can be seen to be rougher than the polysilicon film, but the friction coefficient of the YBa₂Cu₃O₇ film is lower than that of polysilicon film. Also, although the topography of YBa₂Cu₃O₇ films changes during friction, the friction coefficients are stable. This clearly shows that the initial sliding friction of YBa₂Cu₃O₇ films under microfriction is stable. The observation signifies YBCO film is a good film to prevent stick–slip motion in ambient environment. The wear properties of YBa₂Cu₃O₇ films suggest that the superconducting outgrowths (CuO) are loose and they can be easily removed.     

纳米Fe-Al/Cr_3C_2复合涂层及其抗高温腐蚀性能

制备纳米金属间化合物Fe-Al/Cr_3C_2复合涂层并测试其抗腐蚀性能,为利用热喷涂技术治理火电站易损部件腐蚀问题提供有效手段。运用自主研发的造粒系统,成功对高活性的纳米Fe-Al/Cr_3C_2复合喷涂粉体实施团聚造粒;运用高速火焰喷涂方法,在结构材料表面制备出了纳米Fe-Al/Cr_3C_2复合涂层,对比测试了微米、纳米Fe-Al/Cr_3C_2复合涂层的抗高温腐蚀性能,分别采用抛物线型和幂函数型对腐蚀动力学曲线进行拟合。纳米Fe-Al/Cr_3C_2复合喷涂材料的粒径由原始的50nm团聚到最终的114~178μm,团聚后的纳米颗粒呈圆形或椭圆形,各成分比例保持原始比例,团聚颗粒内部仍然保持纳米粉体状态;纳米Fe-Al/Cr_3C_2复合涂层表面致密、铺展均匀,截面元素过渡平缓、层片细小;运用幂函数方程对腐蚀动力学曲线的拟合效果更好。通过对腐蚀动力学拟合方程进行求导运算可推算出各复合涂层的腐蚀速率。团聚后的纳米颗粒满足热喷涂材料的相关要求,纳米Fe-Al/Cr_3C_2复合涂层的抗高温腐蚀性能显著高于微米Fe-Al/Cr_3C_2复合涂层。纳米Al、Cr优先氧化生成具有保护作用的氧化膜机理解释了纳米涂层抗高温腐蚀性能优异的原因。     

Structural and tribological characterization of tungsten nitride coatings at elevated temperature

Transition metal nitrides exhibit excellent mechanical properties (hardness and Young's modulus), high melting point, good chemical stability and high electrical conductivity. However, tungsten nitrides still stand aside of the main attention. In our previous study, tungsten nitride coatings with different nitrogen content showed excellent wear resistance at room temperature. Nevertheless, many engineering applications require good tribological properties at elevated temperature. Thus, the present study is focused on the tribological behaviour (friction coefficient and wear rate) of tungsten nitride coatings at temperature up to 600 °C.

The structure, hardness, friction and wear of tungsten nitride coatings with nitrogen content in the range 30–58 at.% prepared by dc reactive magnetron sputtering were investigated. The tribological tests were performed on a pin-on-disc tribometer in terrestrial atmosphere with Al₂O₃ balls as sliding partner. The coating wear rate was negligible up to 200 °C exhibiting a decreasing tendency; however, the wear dramatically increased at higher temperatures. The coating peeled off after the test at 600 °C, which is connected with the oxidation of the coating.