PIII技术制备c-BN硬化层

采用一种新型的等离子体浸没式离子注入技术(PIII)在渗硼后的50Mn钢试样上制备出了厚度为0.15~0.2mm的立方氮化硼(c-BN)表面硬化层。经X光电子能谱(XPS)和X光衍射分析(XRD),发现硬化层中的组织有立方氮化硼(c-BN)、六方氮化硼(h-BN)、B2O3、FeB和Fe2B。在表层60nm的深度范围内,c-BN的含量较高。采用球盘式无润滑滑动摩擦试验和维氏显微硬度试验分别对渗硼+PIII复合处理以及单独渗硼的50Mn钢试样的性能进行了对比试验。结果表明,与单独渗硼的试样相比,渗硼+PIII复合处理的试样具有高得多的硬度(高达Hv0.1N44GPa)和耐磨性。该项技术在电缆压模上进行了应用试验,获得了较好的应用效果。     

脉冲偏压下沉积的立方氮化硼膜的断面结构研究

采用自行研制的磁增强活性反应离子镀系统 ,在脉冲偏压条件下成功地合成了高品质立方氮化硼 (c BN)薄膜。用傅立叶变换红外谱 (FTIR)分析沉积膜的相结构 ,用透射电镜 (TEM)及高分辨率透射电镜 (HRTEM)分析膜的断面结构。FTIR结果表明 :c BN的纯度强烈地受基片负偏压的影响 ,当基片负偏压为 15 5V ,c BN膜的纯度高达 90 %以上。TEM及HRTEM对膜的断面结构分析表明 ,在膜与基片的界面处存在很薄的非晶氮化硼和六方氮化硼 (h BN)层 ,h BN(0 0 0 2 )晶面垂直于基片表面 ,在界面层之上生长着单相c BN层     

Cubic boron nitride based metastable coatings and nanocomposites

Various PVD and plasma-assisted CVD methods presently used for the deposition of cubic boron nitride (c-BN) thin films demand adequate conditions relating to ion bombardment of growing films, growth temperature, film stoichiometry, etc. The deposition conditions, often appearing rather apparatus-dependent, can be well categorized according to the fundamental parameters of bombarding ions as well as condensing neutral particles, including their energy and flux ratio, and a few of others like ion mass and incident angle. According to these parameters, various surface kinetic processes and their consequences are discussed particularly in connection with the resulting film phases and stress. Typical c-BN films are known for their extremely high compressive stress and poor adhesion as a result of intensive ion bombardment during deposition. Individual measures attempting to relieve this detrimental stress are briefly summarized. The present paper focuses on magnetron-sputtered, c-BN-based metastable films and nanocomposite films with considerably reduced internal stress in comparison to the usual “pure” c-BN films. Two examples will be shown, namely c-BN/a-C nanocomposite and c-BN:O metastable films, including their deposition details, structure and composition characterization, and mechanical properties. Also illustrated is a growth scheme tailored for the deposition of thick, adhered, cubic-phase dominated, superhard c-BN:O films above 2 µm on silicon substrates.     

New approach in depositing thick, layered cubic boron nitride coatings by oxygen addition—structural and compositional analysis

Cubic boron nitride (c-BN) can be produced by PVD and PA-CVD techniques by intensive ion bombardment leading to highly stressed films limiting its use in industrial applications. Various attempts have been undertaken to reduce the compressive stress of c-BN thin films. A significant reduction in compressive stress and a substantially improved adhesion was achieved by a new coating concept consisting of a two-step adhesion-promoting base layer, a compositional-graded nucleation layer obtained by a stepwise decrease of the oxygen content in the Ar/N₂/O₂ atmosphere and a low-stressed c-BN:O top layer with controlled oxygen addition. The four-layer c-BN:O film with a thickness of 3 μm was deposited by unbalanced radio frequency magnetron sputtering of a hot-pressed hexagonal boron nitride target on silicon substrates. The adhesion layer was deposited in a mixed Ar/O₂ atmosphere of 0.26 Pa with a stepwise increased nitrogen gas flow and a subsequent increase of the ion energy by increasing the substrate bias from 0 to − 250 V. The c-BN nucleation was gradually initiated by decreasing the O₂ gas flow. The present study was focused on the investigation of the morphology, the microstructure on the nanoscale, and the bonding structure using scanning electron microscopy (SEM), Fourier-Transmission infra-red spectroscopy (FTIR), high-resolution transmission electron microscopy (HRTEM) and electron energy loss spectroscopy (EELS) employing analytical scanning transmission electron microscopy (ASTEM). The HRTEM images revealed a four-layer coating consisting of a gradual nucleation of t-BN, on which a gradual nucleation of c-BN was achieved by decreasing the oxygen gas flow.     

Mechanism of nucleation and growth of cubic boron nitride thin films

The mechanism and the crystallography of the nucleation and growth of cubic boron nitride (c-BN) films deposited on 〈100〉-oriented silicon substrate by RF bias sputtering have been studied by means of cross-sectional high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy. Both methods provide experimental information showing no sp²-bonded BN layer formation in the subsurface region of c-BN phase. This is clear evidence for layer-by-layer homoepitaxial growth of cubic boron nitride without graphitic monolayers in the near-surface region of the film. The turbostratic boron nitride (t-BN) consists of thin sub-layers, 0.5–2 nm thick, growing in such a way that a sub-layer normal is almost parallel to the growth direction. t-BN also comprises a large volume fraction of the grain boundaries with high interface energies. The present result and the finding by Shtansky et al. [Acta Mater. 48, 3745 (2000)], who showed that an individual sub-layer consists of parallel lamellae in both the hexagonal +h-BN) and rhombohedral (r-BN) configurations, demonstrate that high intrinsic stress in the films is due to the complex structure of sp²-bonded BN. The crystallography of c-BN films indicates heteroepitaxial nucleation of cubic phase on the graphitic BN structural precursor. The present results are consistent with stress-induced c-BN formation.     

Mechanism of nucleation and growth of cubic boron nitride thin films

The mechanism and the crystallography of the nucleation and growth of cubic boron nitride (c-BN) films deposited on 100-oriented silicon substrate by RF bias sputtering have been studied by means of cross-sectional high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy. Both methods provide experimental information showing no sp²-bonded BN layer formation in the subsurface region of c-BN phase. This is clear evidence for layer-by-layer homoepitaxial growth of cubic boron nitride without graphitic monolayers in the near-surface region of the film. The turbostratic boron nitride (t-BN) consists of thin sub-layers, 0.5–2 nm thick, growing in such a way that a sub-layer normal is almost parallel to the growth direction. t-BN also comprises a large volume fraction of the grain boundaries with high interface energies. The present result and the finding by Shtansky et al. [Acta Mater. 48, 3745 (2000)], who showed that an individual sub-layer consists of parallel lamellae in both the hexagonal (h-BN) and rhombohedral (r-BN) configurations, demonstrate that high intrinsic stress in the films is due to the complex structure of sp²-bonded BN. The crystallography of c-BN films indicates heteroepitaxial nucleation of cubic phase on the graphitic BN structural precursor. The present results are consistent with stress-induced c-BN formation.     

Influence of Tool Coating,Tool Material,and Cutting Speed on the Machinability of Low-Leaded Brass Alloys in Turning

The influence of tool coating and material on the machinability of low-leaded brass alloys (Pb < 0.2%) was analyzed in external turning. Carbide tools with various coatings as well as polycrystalline diamond (PCD) tools were applied. As workpiece materials, three low-leaded brass alloys CuZn38As, CuZn42, and CuZn21Si3P were used. Their machining behavior was compared to the leaded (Pb < 3.32%) brass CuZn39Pb3. CuZn38As showed the worst machinability in terms of process forces, chip formation, and workpiece quality. This is due to the high volume fraction of α-phase with face-centered cubic lattice structure. The machining problems were reduced by the use of tool coatings, in particular by a diamond-like carbon coating. The latter is characterized by high hardness, diamond-like cubic-crystalline lattice structure, and low chemical affinity to brass, which reduced friction in the secondary shear zone. CuZn42 exhibited an improved machinability compared to CuZn38As due to the lower volume fraction of α-phase. The positive influence of the tool coating was similar to CuZn38As. Main machining problem of CuZn21Si3P is tool wear because of the hard silicon-rich κ-phase. In tool life tests, PCD showed higher performance than uncoated and coated carbide tools due to its high abrasive wear resistance and low adhesion tendency.     

Investigation of Ti coatings on cubic boron nitride (cBN) grits by discharge treatment in spark plasma sintering system

The Ti coatings on cubic boron nitride (cBN) grits were prepared by discharge treatment on a mixture of Ti powders and cBN grits in spark plasma sintering system. The uniform and full coatings with a thickness of ～1.2 μm were prepared at 850 °C for 60 min, which were constituted with TiB₂, TiN, and Ti phases. The compressive fracture strength and toughness impact of the Ti-coated cBN grits were 11.6% and 7.4% higher than the cases of the pristine ones, respectively. With the aid of Ti coatings, the interface bonding strength between cBN grits and Fe-based matrix was improved by 335 MPa in the Fe-based matrix/cBN composites.     

立方氮化硼薄膜制备与性质研究新进展

立方氮化硼(c-BN)具有优异的物理和化学性质, 在力学、光学和电子学等方面有着广泛的应用前景. 自上世纪80年代开始, 低压沉积c-BN薄膜的研究迅速发展, 到90年代中期达到高潮, 随后进展缓慢, c-BN薄膜研究转入低潮. 近年来, c-BN薄膜研究在几方面取得了突破, 如获得与衬底粘附良好、厚度超过1μm的c-BN厚膜; 成功实现了c-BN单晶薄膜的异质外延生长; 此外, 在c-BN薄膜力学性质和过渡层微结构研究方面也取得了进展. 本文主要评述最近几年c-BN薄膜研究在以上几方面取得的最新进展.     

Materials with extreme properties: Their structuring and applications

This article is a brief review on syntheses of materials with extreme properties and their modification by plasma processes to obtain different morphological structures. First we illustrate general methodologies on preparation of polycrystalline diamond (PD), nanocrystalline diamond (ND), cubic boron nitride (cBN), diamond/cBN multilayer films by low pressure methods. Since cBN synthesis is more challenging, we place more attention to cBN including its growth, structuring and doping. The structural compatibility of cBN and diamond enables the fabrication of multilayer (superlattices); and we describe such an approach to produce composite materials with even more extreme properties. The superior hardness, extreme thermal conductivity and high chemical stability make diamond and cBN well suited for cutting tool and tribological applications. Although doping of these wide bandgap materials for p- and n-type conductivity is difficult, recent works indicate considerable advancement. The combination of high chemical stability and thermal conductivity with attractive electronic properties makes diamond and cBN suitable for construction of high power electronic devices operating in harsh environments. The development of these applications relies on the ability to design patterns and control the film conductivity. We illustrate that despite diamond and cBN are chemically stable and inert against many chemicals, film patterning and device fabrication is possible with the use of plasma processing. Further, we discuss the fundamental issues involved and demonstrate feasibility for the design of practical applications such as deep-ultraviolet (DUV) detectors and surface acoustic wave (SAW) devices. Finally we discuss the existence of other composite materials with extreme properties that have been only barely investigated, and that present promising alternatives for the future commercial applications.     

氮化物硬质涂层中Cr、Ti和Al元素对摩擦磨损特性的影响

利用四靶闭合场非平衡磁控溅射(CFUBMS)技术在石英玻璃和抛光不锈钢片两种基底上制备含有Cr、Ti和Al元素组合的各种氮化物涂层.采用摩擦磨损仪测试涂层摩擦系数,应用金相显微镜对各个涂层磨痕形态进行分析,结果表明TiN、CrN、TiAlN、CrAlN以及CrTiAlN涂层的摩擦系数依次减小,耐磨特性依次提高;结合涂层的X射线光电子能谱分析,可以得到含有Al元素涂层中形成了AlN的结构,提高涂层的硬度,增加耐磨特性;在涂层中含有Cr元素形成了氧化物Cr2O3可以提高涂层自排屑能力,减小摩擦系数,增加耐磨特性,含Ti元素形成的氧化物TiO2则不利于涂层的摩擦磨损特性;由于CrTiAlN本身具有比三元氮化物更高的涂层硬度,且含有Al和Cr元素,因此该涂层具有最好的摩擦磨损性能.     

Detailing interfacial reaction layer products between cubic boron nitride and Cu-Sn-Ti active filler metal

In the present study,we offer an in-depth analysis over the microstructure,thickness and product composition of the interfacial reaction layer generated upon CBN/Cu-Sn-Ti active filler metal at 1223 K.Current findings demonstrate that adequate wettability and satisfactory bonding have been achieved via chemical reactions between Ti and N,B.More importantly,we report,for the first time,the formation of a three-layer juxtaposition of reaction products,namely,TiN,TiB2 and TiB,along the diffusion path of Ti.Meanwhile,we determine the average layer thickness to be 1.24 μm.Through deep etching,we unambiguously present morphologies of the newly formed TiN and TiB2,which are columnar and bulky,re spectively,and constitute the formation of a high strength metallu rgical interfacial bonding layer,and is crucial towards gaining enhanced grinding performance.Finally,we propose a possible reaction sequence and mechanism that govern the nucleation and growth of corre s ponding crystals.     

Parameter spaces for the nucleation and the subsequent growth of cubic boron nitride films

The data existing in the literature about the deposition of cubic boron nitride thin films were reviewed critically in order to establish the parameter spaces of c-BN nucleation and growth. The ion energy E_i, the flux ratio F (=incoming ions/incoming boron atoms), the ion mass m_i, (or the ratio Ar/N₂, respectively), and the substrate temperature T_s, had already been identified as the decisive parameters which are, however, interdependent. Earlier data collections on c-BN deposition had shown that, irrespective of the deposition technique used, a well-defined c-BN region exists in the F/E_i parameter space, in which the deposition of c-BN is possible. Similar regions exist in the F/m_i and F/T_s parameter spaces. The present collection extends these older diagrams considerably, especially to the low energy region. From this extention it can be concluded that the momentum transfer concepts proposed in the literature fail to explain the data. Furthermore, the older collections were considered valid for nucleation and growth likewise. However, in recent years data have been published showing that the boundaries of the c-BN regions are different for nucleation and growth. After successful nucleation, subsequent growth can occur either at reduced ion bombardment (either energy or flux ratio or ion mass) and also at reduced temperatures. The existing data for this parameter reduction have been collected in this paper. It will be shown that the growth depends in a similar way as the nucleation on the (interdependent) ion bombardment parameters but no longer on temperature. This means that the nucleation and growth of c-BN are based on different, although in both cases ion-induced, mechanisms.     

Preparation of c-BN films by RF sputtering and the relation of BN phase formation to the substrate bias and temperature

This paper deals with the deposition of cubic boron nitride (c-BN) films by radio frequency (RF) magnetron sputtering. The nearly pure c-BN films have been prepared on Si(100) substrates using hexagonal boron nitride (h-BN) targets. Argon gas mixed with nitrogen gas was used as sputtering gas. The deposited films were characterized by Fourier transform infrared (FTIR) spectroscopy and transmission electron diffraction (TED). A ‘temperature-bias' phase diagram has been worked out. It indicates that the c-BN phase prefers the relative high temperature and negative bias. An opinion was presented that the c-BN nuclei grow discontinuously with every time the ‘thermal spike' coming.     

含氟聚丙烯酸酯自分层乳胶涂料的制备与性能

为制备通过一次涂布而形成多层的自分层涂料,实现对基材的有效保护,通过种子乳液聚合制备了含氟与纯丙烯酸酯两种乳液,并将其复配成可自分层的乳胶涂料。分别用傅里叶变换红外光谱仪(FT-IR)、光学显微镜和动态力学谱仪(DMA)对涂膜进行了表征。结果表明,随共聚单体中甲基丙烯酸三氟乙酯(TFEMA)的含量增大,涂膜不透明性增大,光学显微镜表明涂膜出现分层现象;FT-IR分析表明,涂膜的上下表面—CF3的含量不同,上表面有更多的含氟单体;DMA分析表明,力学内耗峰随含氟乳液用量比例增多而变宽,也说明涂膜已产生相分离,得到了自分层涂料。     

镁合金超疏水环氧复合涂层的制备与性能EI北大核心CSCD

传统的超疏水表面的制备过程比较复杂,机械稳定性差,这严重制约了超疏水表面的实际应用。采用“黏合剂+纳米粒子”的方法,在镁合金表面制备一种无氟、持久稳定的超疏水环氧复合涂层。接触角测试结果表明,复合涂层的接触角最高可达160.2°,且在3.5%(质量分数)NaCl溶液中浸泡30天后,接触角仍然高达103°;EIS结果表明,在5个加速老化循环周期后,复合涂层的|Z|_(0.01 Hz)仍高于10^(9)Ω·cm^(2),展现出优异的耐盐雾性能和耐蚀性能;摩擦磨损实验结果显示,在19.6 N的载荷下机械摩擦8 h后,复合涂层的|Z|_(0.01 Hz)高达1.84×10^(9)Ω·cm^(2)。通过“空气垫”的屏障作用,复合涂层能够为镁合金提供高效且持久的腐蚀防护,“黏合剂+纳米粒子”策略为超疏水涂层的制备提供了新的思路。     

High-resolution characterization of hexagonal boron nitride coatings exposed to aqueous and air oxidative environments

Hexagonal boron nitride (h-BN) is believed to offer better passivation to metallic surfaces than graphene owing to its insulating nature,which facilitates blocking the flow of electrons,thereby preventing the occurrence of galvanic reactions.Nevertheless,this may not be the case when an h-BN-protected material is exposed to aqueous environments.In this work,we analyzed the stability of mono and multilayer h-BN stacks exposed to H2O2 and atmospheric conditions.Our experiments revealed that monolayer h-BN is as inefficient as graphene as a protective coating when exposed to H2O2.Multilayer h-BN offered a good degree of protection.Monolayer h-BN was found to be ineffective in an air atmosphere as well.Even a 10-15 layers-thick h-BN stack could not completely protect the surface of the metal under consideration.By combining Auger electron spectroscopy and secondary ion mass spectrometry techniques,we observed that oxygen could diffuse through the grain boundaries of the h-BN stack to reach the metallic substrate.Fortunately,because of the diffusive nature of the process,the oxidized area did not increase with time once a saturated state was reached.This makes multilayer (not monolayer) h-BN a suitable long-term oxidation barrier.Oxygen infiltration could not be observed by X-ray photoelectron spectroscopy.This technique cannot assess the chemical composition of the deeper layers of a material.Hence,the previous reports,which relied on XPS to analyze the passivating properties of h-BN and graphene,may have ignored some important subsurface phenomena.The results obtained in this study provide new insights into the passivating properties of mono and multilayer h-BN in aqueous media and the degradation kinetics of h-BN-coated metals exposed to an air environment.     

Hydrogen adsorption,structural, electronic,and spectroscopic properties of C32, B16N16, and B8C24 by DFT calculations

We used DFT calculations at B3LYP/6-31G(d) level of theory to investigate the structural, electronic and spectral properties of C₃₂, B₁₆N₁₆, and B₈C₂₄ nanocages. The C₃₂ found as the most stable one and the bond lengths was approximately constant for the considered nanocages. We also found that B₁₆N₁₆ has greater atomic charges than C₃₂ and B₈C₂₄. Very low conductivity and reactivity of B₁₆N₁₆, and higher conductivity and reactivity of B₈C₂₄ and C₃₂ were also revealed in this research. C₃₂ is the best electron donor cage and B₈C₂₄ is the best electron acceptor among the studied fullerenes. Simple infrared spectrum of fullerenes was revealed in which a few spectral regions can be identified as fingerprints of related samples. At last the binding energy of hydrogen molecules with the fullerenes was investigated.     

Enhanced deposition of cubic boron nitride films on roughened silicon and tungsten carbide-cobalt surfaces

We report the influence of substrate surface roughness on cubic boron nitride (cBN) film deposition under low-energy ion bombardment in an inductively coupled plasma. Silicon and cemented tungsten carbide-cobalt (WC-Co) surfaces are roughened by low-energy ion-assisted etching in a hydrogen plasma, followed by deposition in a fluorine-containing plasma. Infrared absorption coefficients are measured to be 22,000 cm⁻¹ and 17,000 cm⁻¹ for sp²-bonded BN and cBN phases, respectively, for our films. For the silicon substrates, the film growth rate and the cBN content in the film increase with increasing the surface roughness, while the amount of sp²BN phase in the film shows only a small increase. A larger surface roughness of the substrate results in a smaller contact angle of water, indicating that a higher surface free energy of the substrate contributes to enhancing growth of the cBN film. For the WC-Co substrates, the film growth rate and the cBN content in the film increase similarly by roughening the surface.     

金刚石及相关薄膜制备研究进展

金刚石及相关薄膜材料指的是金刚石薄膜和立方氮化硼薄膜,它们的制备技术被称为“新金刚石技术”。评述了这类材料制备技术研究进展,指出成核及生长机理的研究将是它们走向实用化的关键。