Reactive plasma cladding of TiC/Fe cermet coating using asphalt as a carbonaceous precursor

A new process of preparing Ti-Fe-C composites powder for reactive plasma cladding, precursor carbonization-composition process, was developed. TiC/Fe cermet coatings were synthesized by reactive plasma cladding of the composite powder. XRD and SEM were employed to analyze the phase composition and microstructure of the composite powder and coating. The hardness and wear resistance of the coating was tested. Results show that: The compound powder prepared by precursor carbonization-composition process has very tight structure, which can avert the question of raw powder breaking-up in cladding process. The TiC/Fe cermet coating by reactive plasma cladding consists of alternate, laminated layers as following: the layers in which the round nanoscale TiC particles are dispersed within the α-Fe matrix and the layers of TiC accumulation. The TiC/Fe cermet coating by reactive plasma cladding shows superior hardness and wear resistance: The surface hardness of the TiC/Fe cermet coating is 68 ± 6 (HR30 N). In the same fretting conditions, the wear resistance of Ni60 coating is twelve times than that of the TiC/Fe cermet coating.     

Temperature-dependent texture, stress and resistivity in melt spun Cu0.95Co0.05 ribbon

Ribbon samples of Cu_0.95Co_0.05 were prepared by melt spinning method to perform systematic investigations on structure and transport properties as a function of annealing temperature. X-ray diffraction study shows that the ribbon is polycrystalline with a strong 2 0 0 texture along the surface normal of the as-quenched Cu_0.95Co_0.05 ribbon and the degree of texture is enhanced upon annealing. The compressive stress, which relaxes upon annealing, is observed in as-quenched ribbon. The resistivity, which is higher in as-quenched ribbon, decreases toward the bulk value of Cu upon annealing. The compressive stress and higher resistivity in as-quenched ribbon are attributed to the incorporation of Co atoms/particles in Cu matrix. The decrement of the stress and resistivity upon annealing is due to the precipitation of Co atoms from the Cu matrix, segregating as Co or Co-rich Cu grains as observed from the transmission electron microscopy measurements.     

Microstructure evolution in Pr-Co-C-Ti nanophase magnets

The microstructures of nanophase Pr-Co-C-(Ti) materials, which have improved magnetic properties, were investigated by means of transmission electron microscopy (TEM) to reveal their phase assemblage and grain-boundary structure. The phase assemblage was carefully controlled by the introduction of TiC nanoparticles and annealing. The optimal nanostructure contained uniformly distributed PrCo₅ and PrCo₂ nanophases without any magnetically soft phases, resulting in high coercivity and the characteristics of a single, hard magnetic phase. TEM analysis confirmed the presence of an amorphous grain-boundary phase surrounding the grains in alloys without TiC. In contrast, alloys with added TiC showed no amorphous phase and also showed higher coercivity compared to Co-Pr-C. Therefore, the variation of the grain boundary phases may be effective in changing the degree of exchange coupling. Controlling the formation of a uniform nanoscale microstructure, leading to improved magnetic properties, is discussed. Received: 5 September 2002 / Accepted: 10 September 2002 / Published online: 22 January 2003 RID="*" ID="*"Corresponding author. Fax: +1-630/252-7777, E-mail: ytang@anl.gov     

Ti6Al4V合金表面激光沉积复合涂层的组织和性能

为了增强Ti6Al4V钛合金的耐磨性,采用激光沉积制造方法在其表面上制备了以原位生成的TiC颗粒和直接添加的WC颗粒为增强相的耐磨涂层,观察了各涂层的微观组织,并测量了涂层的显微硬度和涂层在室温大气条件下的摩擦磨损性能。结果表明各涂层和基体呈现冶金结合,原位自生的TiC和部分熔化的WC颗粒均能够均匀弥散分布于基体上,由于增强相颗粒的弥散强化及激光沉积组织的细晶强化作用,基材的硬度和耐磨性均得到了提高。原位自生的TiC涂层比WC涂层硬度梯度分布平缓,但耐磨性稍差。     

Fe含量和粒径对Fe/Cu颗粒膜结构和磁性的影响

采用共蒸发法制备不同组分的Fe/Cu颗粒膜,将样品分两组进行退火和不退火处理. 根据测量及分析,确定了不同成分的Fe/Cu颗粒膜的相组成和晶体结构;找出了 Fe/Cu颗粒膜矫顽力与粒径的关系,利用此关系由自发形核理论可知,提高功率,快速蒸镀薄膜,可得到细密颗粒的Fe/Cu颗粒膜,从而降低矫顽力,减少磁滞损耗.     

Enhanced reactivity of nanoscale iron particles through a vacuum annealing process

A reactivity study was undertaken to compare and assess the rate of dechlorination of chlorinated aliphatic hydrocarbons (CAHs) by annealed and non-annealed nanoscale iron particles. The current study aims to resolve the uncertainties in recently published work studying the effect of the annealing process on the reduction capability of nanoscale Fe particles. Comparison of the normalized rate constants (m²/h/L) obtained for dechlorination reactions of trichloroethene (TCE) and cis-1,2-dichloroethene (cis-1,2-DCE) indicated that annealing nanoscale Fe particles increases their reactivity ~30-fold. An electron transfer reaction mechanism for both types of nanoscale particles was found to be responsible for CAH dechlorination, rather than a reduction reaction by activated H₂ on the particle surface (i.e., hydrogenation, hydrogenolysis). Surface analysis of the particulate material using X-ray diffraction (XRD) and transmission electron microscopy (TEM) together with surface area measurement by Brunauer, Emmett, Teller (BET) indicate that the vacuum annealing process decreases the surface area and increases crystallinity. BET surface area analysis recorded a decrease in nanoscale Fe particle surface area from 19.0 to 4.8 m²/g and crystallite dimensions inside the particle increased from 8.7 to 18.2 nm as a result of annealing.     

Microstructures and magnetic properties of Fe---Pt permanent magnets

We have investigated the magnetic properties of Fe---38.5Pt, Fe---39.5Pt and Fe---50.0Pt (at%) alloys after various heat treatment conditions using a vibrating sample magnetometer, and correlated these properties with the microstructures of the alloys by transmission electron microscopy. The Fe---50Pt alloy shows poor magnetic hardness regardless of the heat treatment conditions. The magnetic hardness of the Fe---39.5Pt alloy shows a maximum value after annealing for 10 h at 873 K, while it monotonically decreases after annealing at 1073 K. The alloy with the highest coercivity was composed of a single phase γ₁ with an average domain size of approximately 10 nm. The electron diffraction results indicate that the alloy is frustrated with accumulated stress, induced by a cubic → tetragonal transformation which occurs without twinning. On the other hand, when stress is relieved by twin formation after prolonged aging, the coercivity decreases. By annealing at 1073 K, the well known polytwin structure evolves. However, only poor hard magnetic properties are observed when this polytwin structure appears. Hence, the highest coercivity is attributed to the formation of nanoscale L1₀ ordered antiphase domains which is expected to be a highly anisotropic single domain magnetic particle.     

Dry sliding wear characteristics of in situ synthesized Al-TiC composites

Abstract

Aluminum-based composites containing 0.06, 0.09, 0.12 fractions of in situ-synthesized TiC (Titanium carbide) particles have been prepared through in-melt reaction from Ai–SiC–Ti system following a simple and cost-effective stir-casting route. The TiC forms by the reaction of Ti with carbon which is released by SiC at temperatures greater than 1073 K. However, some amount of titanium aluminide (Al₃Ti) is also formed. The formation of TiC has been confirmed through X-ray diffraction studies of the composite. The hardness and tensile strength have been found to increase with increasing amount of TiC. The friction and wear characteristics of the composites have been determined by carrying out dry sliding tests on pin-on-disc machine at different loads of 9.8 N, 19.6 N, 29.4 N, 39.2 N at a constant sliding speed of the 1 m/s speed. The wear rate i.e. volume loss per unit sliding distance has been found to increase linearly with increasing load following Archard’s law. However, both the wear rate and friction coefficient have been observed to decrease with increasing amount of TiC in the composite. This has been attributed to (i) a relatively higher hardness of composites containing relatively higher amount of TiC resulting in a relatively lower real area of contact and (ii) the formation of a well-compacted mechanically mixed layer of compacted wear debris on the worn surface which might have inhibited metal–metal contact and resulted in a lower wear rate as well as friction coefficient.     

Study of deposition patterns of plating layers in SiC/Cu composites by electro-brush plating

SiC reinforced copper composite coatings were prepared by electro-brush plating with micron-size silicon carbide (SiC) ranging from 1 to 5 μm on pure copper sheet in this paper. The micro-structural characterizations of SiC/Cu composite coatings were performed by optical microscope and Scanning Electron Microscope (SEM) coupled with spectrometer, to study co-deposition mechanism of SiC/Cu. It was found that there were three different patterns of SiC deposition in plating layers during electro-brush plating process, i.e. the particles could deposit inside copper grains, in grain boundaries, or in holes of the surface. To investigate deposition mechanism of each pattern, size of SiC and copper grains was compared. By comparison of size of copper grains and hard particles, SiC were either wrapped in copper grains or deposited in grain boundaries. Moreover, electro-brush plating layers at different brush velocities and current densities were obtained respectively, to analyze the microstructure evolution of the composite coatings. The hardness of plating layers was measured. The results indicated at the current density of 3 A/dm², the SiC/Cu coating was compact with SiC content at a high level and the hardness reached a maximum.     

Annealing behaviour of nanocrystalline NiTi (50 at% Ni) alloy produced by high-pressure torsion

An equiatomic nanocrystalline NiTi alloy, deformed by high-pressure torsion (HPT), was investigated. The as-prepared bulk NiTi alloy consisted of both amorphous and nanocrystalline phases. Crystallization and structural changes during annealing were investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD) and transmission electron microscopy (TEM). DSC thermograms and X-ray analyses revealed stress relaxation and partial crystallization below 500?K, while grain growth of the nanocrystals occurred predominantly after heating to temperatures above 573?K. Along with the amorphous phase crystallization, a continuous growth of pre-existing nanocrystals that are retained after HPT was observed. The DSC signals observed during continuous heating experiments indicate an unusually large separation between the crystallization and growth stages. A detailed analysis of the evolution of the enthalpy release upon annealing revealed reproducibly non-monotonous trends with annealing temperature that cannot be explained solely by nucleation and growth of crystalline volume fractions. Instead, the results can be rationalized by assuming a reverse amorphization process occuring during annealing at 523?K. This behavior, which also caused a large variation in nanocrystal size after annealing at higher temperatures, is discussed with respect to the nanoscale microstructural heterogeneity after initial deformation processing.     

Microstructures and magnetic properties of FePt permanent magnets

We have investigated the magnetic properties of Fe38.5Pt, Fe39.5Pt and Fe50.0Pt (at%) alloys after various heat treatment conditions using a vibrating sample magnetometer, and correlated these properties with the microstructures of the alloys by transmission electron microscopy. The Fe50Pt alloy shows poor magnetic hardness regardless of the heat treatment conditions. The magnetic hardness of the Fe39.5Pt alloy shows a maximum value after annealing for 10 h at 873 K, while it monotonically decreases after annealing at 1073 K. The alloy with the highest coercivity was composed of a single phase γ₁ with an average domain size of approximately 10 nm. The electron diffraction results indicate that the alloy is frustrated with accumulated stress, induced by a cubic → tetragonal transformation which occurs without twinning. On the other hand, when stress is relieved by twin formation after prolonged aging, the coercivity decreases. By annealing at 1073 K, the well known polytwin structure evolves. However, only poor hard magnetic properties are observed when this polytwin structure appears. Hence, the highest coercivity is attributed to the formation of nanoscale L1₀ ordered antiphase domains which is expected to be a highly anisotropic single domain magnetic particle.     

冷轧和退火对V-5Cr-5Ti合金组织结构和抗辐照硬化性能的影响

钒合金(V-5Cr-5Ti)是聚变堆第一壁以及包层的重要候选结构材料。不同加工工艺会对钒合金在聚变堆中的服役性能产生影响。本文利用兰州重离子研究装置(HIRFL)提供的337 MeV的高能Fe离子对不同程度冷轧(冷变形量分别为40%、60%和80%)以及冷轧后退火(1 273 K退火1 h)的V-5Cr-5Ti合金样品进行了辐照,研究了不同的冷轧和退火处理过程对材料抗辐照硬化性能的影响。电子背散射衍射技术(EBSD)测试结果显示,随着冷变形量的增加,样品中细小破碎晶粒比例增大,晶粒平均尺寸减小。退火处理后,细小破碎晶粒出现一定程度的长大,大晶粒几乎全部消失,晶粒尺寸分布更加均匀。维氏硬度结果表明随着冷变形量的增加,硬度随之增加,退火后硬度降低。辐照之后,材料硬度升高,出现了辐照硬化效应。在冷轧样品和退火样品中都观察到了辐照硬化效应随冷变形量的增加显著减弱的现象,这表明冷变形可以显著提高材料的抗辐照硬化能力。结合EBSD和硬度数据,对冷变形和退火处理引起钒合金抗辐照硬化性能变化的机理进行了讨论。讨论结果显示,冷轧使材料总的吸收尾闾增大,引起辐照硬化程度降低,退火处理使材料中晶界密度和位错密度降低,材料的总吸收尾闾降低,辐照硬化效应增加。     

合金元素对TiC/奥氏体界面稳定性影响的第一性原理计算

界面结合强度与材料的强度、硬度、耐磨损、耐腐蚀等性能息息相关,TiC是钢中常见的析出相,研究它与铁基体的界面结合状态,探寻合理的界面强度提升方案,对提升钢的性能具有十分重要的理论意义和应用价值.本文以TiC/奥氏体基体界面为研究对象,采用基于密度泛函理论的第一性原理计算方法从原子尺度上研究TiC/奥氏体基体界面的结合状态.首先本文对界面结合强度以及电子结构进行了计算分析,之后进行高通量计算,研究过渡族金属元素(Mn、Tc、Re、Ru、Os、Co、Rh和Ir)在TiC/奥氏体基体界面的偏析行为及其对界面结合强度的影响,最后通过差分电荷密度分析并解释过渡族金属元素的作用机理.计算研究表明,掺杂Re元素可显著提升界面的强度,为实验上设计高性能钢铁材料提供了新的思路.     

Annealing effects on the plasmonic excitations of metal/metal interfaces

The effects of the annealing procedure at 400-450 K on the electronic properties of nanoscale thin films of Ca, Au and Ag grown on Cu(1 1 1) at room temperature were probed by high-resolution electron energy loss spectroscopy measurements. Ca surface plasmon underwent to a significant red-shift upon annealing, due to the oxidation of the topmost Ca layer. Water strongly interacted with the CaO interface at room temperature. Au surface plasmon disappeared upon annealing the gold film, as a consequence of the formation of an Au-Cu alloy. Ag surface plasmon red-shifted both in the annealed adlayer and with increasing temperature compared with the frequency recorded for the as-deposited silver film.     

Nanoscale combined reactions: non-equilibrium α-Co formation in nanocrystalline ϶-Co by abnormal grain growth

Electrodeposited nanocrystalline Co offers a relatively unique opportunity to study the interaction of two fundamentally different elementary solid state reactions: grain growth and ε (HCP) to α (FCC) allotropic phase transformation. Samples were isothermally annealed at temperatures above and below the equilibrium transformation temperature (T_εα?=?695?K) and quenched to ambient for subsequent characterization by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Isothermal annealing above 695?K resulted in concurrent grain growth and ε to α transformation. Unexpectedly, however, simultaneous grain growth and ε to α transformation also occurred during isothermal annealing at temperatures as low as 573?K, i.e. 122?K below the expected equilibrium T_εα. It was observed that non-equilibrium α-Co formed within a matrix of nanocrystalline ε-Co via abnormal grain growth, and is therefore fundamentally different from the ε to α transformation typically observed in conventional polycrystalline Co.     

Size and Interface Control of Novel Nanocrystalline Materials Using Pulsed Laser Deposition

We have developed a novel method based upon pulsed laser deposition to produce nanocrystalline materials with an accurate grain size and interface control. Using this method, the grain size in the case of Cu thin films was controlled by introducing a few monolayers of insoluble elements having high surface energy such as W, which increases interfacial energy and provides more nucleation sites. The grain size is determined by the thickness of Cu layer and the substrate temperature at which it transforms into islands (nanocrystalline grains) of fairly uniform size which we desgnate as self-assembling approach. Using this approach, the grain size was reduced from 160nm (Cu or Si (100) substrate) to 70–80nm for a simple W layer (Cu/W/Si (100)) to 4nm for a multilayer (Cu/W/Cu/W/Si (100)) thin film. The hardness of these films was evaluated using a nanoindentation technique, a significant increase in hardness from 2.0GPa for coarse-grained 180nm to 12.5GPa for 7nm films was observed. However, there is decrease in hardness below 7nm for copper nanocrystals. The increase in hardness with the decrease in grain size can be rationalized by Hall–Petch model. However, the decrease in slope and eventually the decrease in hardness below a certain grain size can be explained by a new model based upon grain-boundary deformation (sliding). We also used a similar materials processing approach to produce quantum dots in semiconductor heterostructures consisting of Ge and ZnO dots or nanocrystals in AlN or Al₂O₃ matrix. The latter composites exhibit novel optoelectronic properties with quantum confinement of phonons, electrons, holes and excitons. Similarly, we incorporated metal nanocrystals in ceramics to produce improved mechanical and optical properties.     

Effect of pulsed laser parameters on in-situ TiC synthesis in laser surface treatment

Commercial titanium sheets pre-coated with 300-μm thick graphite layer were treated by employing a pulsed Nd:YAG laser in order to enhance surface properties such as wear and erosion resistance. Laser in-situ alloying method produced a composite layer by melting the titanium substrate and dissolution of graphite in the melt pool. Correlations between pulsed laser parameters, microstructure and microhardness of the synthesized composite coatings were investigated. Effects of pulse duration and overlapping factor on the microstructure and hardness of the alloyed layer were deduced from Vickers micro-indentation tests, XRD, SEM and metallographic analyses of cross sections of the generated layer. Results show that the composite cladding layer was constituted with TiC intermetallic phase between the titanium matrix in particle and dendrite forms. The dendritic morphology of composite layer was changed to cellular grain structure by increasing laser pulse duration and irradiated energy. High values of the measured hardness indicate that deposited titanium carbide increases in the conditions with more pulse duration and low process speed. This occurs due to more dissolution of carbon into liquid Ti by heat input increasing and positive influence of the Marangoni flow in the melted zone.     

High-resolution transmission electron microscopy study of crystallography and morphology of TiC precipitates in tempered steel

In spite of the significance of NaCl-type transition-metal carbides in steels, their crystallography and morphology have not been understood on an atomic scale. High-resolution electron microscopy was employed in the present work to examine the crystallography and morphology of TiC particles that precipitated in the quenched and tempered 0.05?wt%?C–0.20?wt%?Ti–2.0?wt%?Ni steel. Plate-like TiC precipitates with a thickness ranging from a couple of atomic layers to 20?nm were observed in steels by tempering at 550, 600 and 800°C. It was found that the Baker–Nutting orientation relationship is always satisfied with the ferrite matrix within about 5° for both the nanosized and the coarse TiC particles. The habit plane of the TiC precipitate is the (100) ferrite plane. A moderate tendency for the faceting of lateral interfaces on the {001} and {011} ferrite planes was found. The presence of interfacial misfit dislocations was revealed by examining the excess lattice fringes terminating at the interfaces between the TiC platelet and the ferrite matrix. The location and number of the excess lattice fringes terminating at the broad plane and the lateral interface were consistent with the mismatch in the atomic arrangement between the Baker–Nutting orientation relationship related TiC and ferrite.     

Production, structure, and microhardness of nanocrystalline Ni-Mo-B alloys

Radiography, differential scanning calorimetry, luminescence and high-resolution electron microscopy are used to study the production, nanocrystalline structure, stability, and microhardness of alloys from the Ni-Mo-B system containing from 27 at. % to 31.5 at. % Mo and 10 at. % B. All studies of these alloys indicated that annealing at 600 °C leads to the creation of a granular phase consisting of FCC nanocrystallites with average grain sizes of 15–25 nm, depending on the chemical composition of the alloy. Annealing these nanocrystalline samples isothermally at a temperature of 600 °C has no appreciable effect on the grain size. Structurally, the nanocrystalline phase consists of grains of an FCC solid solution of Mo and B in Ni, dispersed in an amorphous matrix that isolates them from one another. The lattice parameters of the FCC nanocrystallites depend on the alloy composition and the duration of their isothermal anneal. Within this latter time, molybdenum and boron atoms diffuse from the FCC solid-solution lattice into the surrounding amorphous matrix. The stability of the nanocrystalline structure is determined by the thermal stability of the amorphous matrix, whose crystallization temperature increases with the isothermal annealing time due to enrichment by boron and molybdenum. As the structure forms, the alloy becomes harder as the nanocrystalline grains grow in size. This relation between hardness and grain size, which is opposite to the Hall-Petch law, is explained by hardening of the amorphous matrix due to changes in its chemical composition. Fiz. Tverd. Tela (St. Petersburg) 40, 10–16 (January 1998)     

Effect of the dispersibility of ZrO2 nanoparticles in Ni-ZrO2 electroplated nanocomposite coatings on the mechanical properties of nanocomposite coatings

ZrO₂ nanoparticles was uniformly co-deposited into a nickel matrix by electroplating of nickel from a Watts bath containing particles in suspension which were monodispersed with dispersant under DC electrodeposition condition. It was found that morphology, orientation and hardness of the nanocomposite coatings with monodispersed ZrO₂ nanoparticles had lots of difference from the nanocomposite coatings with agglomerated ZrO₂ nanoparticles and pure nickel coatings. Especially, the result of hardness showed that only a very low volume percent (less than 1 wt.%) of monodispered ZrO₂ nanoparticles in Ni-ZrO₂ nanocomposite coatings would result in higher hardness of the coatings. The hardness of Ni-ZrO₂ nanocomposite coatings with monodispersed and agglomerated ZrO₂ nanoparticles were 529 and 393 HV, respectively. The hardness value of the former composite coatings was over 1.3 times higher than that of the later. All these composite coatings were two-three times higher than that of pure nickel plating (207 HV) prepared under the same condition. The strengthening mechanisms of the Ni-ZrO₂ nanocomposite coatings based on a combination of grain refinement strengthening from nickel matrix grain refining and dispersion strengthening from dispersion state of ZrO₂ nanoparticles in the coatings.