PIIID复合强化处理轴承钢表面TiN膜层的XPS表征

用等离子体浸没离子注入与沉积(PIIID)复合强化新技术在AISI52100轴承钢基体表面成功合成了硬而耐磨的氮化钛薄膜。膜层表面的化学组成和相结构分别用X射线衍射(XRD)和X射线光电子能谱(XPS)表征;膜层表面的原子力显微镜(AFM)形貌显示出TiN膜结晶完整,结构致密均匀。XRD测试结果表明,TiN在(200)晶面衍射峰最强,具有择优取向。Ti(2p)的XPS谱峰泰勒拟合分析揭示出,Ti(2p_1/2)峰和Ti_2p3/2峰均有双峰出现,表明氮化物中的Ti至少存在不同的化学状态;N(1s)的XPS谱峰在396.51, 397.22和399.01 eV附近出现了三个分峰,分别对应于TiNO_y,TiN和N—N键中的氮原子。结合O(1s)的XPS结果,证实膜层中除生成有稳定的TiN相外,还有少量钛的氧化物和未参与反应的单质氮。整个膜层是由TiN,TiO₂,Ti—O—N化合物和少量单质氮组成的复合体系。     

Laser removal of TiN coatings from WC micro-tools and in-process monitoring

Current environmental challenges require sustainable and extended use and re-use of materials. For example, the service life of engineering tooling can be extended by using thin film coatings such as titanium nitride (TiN). However, when errors arise in the coating process or when the tooling needs to be re-used it is necessary to remove the coating. Decoating is also useful when a large batch of cutting tools needs to be re-directed for a different application, which requires a new generation of coating. Existing technology uses chemical methods which are not environmentally friendly or ideal for selective removal. In this work, excimer laser striping of TiN from coated tungsten carbide (WC) micro-tools has been demonstrated as a viable alternative to chemical methods. Also, in order to raise the integrity of the decoating process and to make the process more accurate and reliable, two online monitoring systems were developed exploiting probe beam reflection (PBR) and laser plume emission spectroscopy (PES). The online monitoring system facilitated a simultaneous prediction of surface elements as coating layers are progressively removed and ensures better control over the laser irradiation process so as to avoid under or over stripping of the coating.     

Synthesis of TiN thin films by a new combined laser/sol-gel processing technique

In this work a novel method for synthesising TiN coatings is reported. A high-power diode laser at different powers and traverse speeds was applied to a mild steel substrate, coated with a slurry of titania sol-gel, urea and graphite. The reaction chemical thermodynamics was investigated to estimate the compositions, temperature range, and the required reaction enthalpy for producing TiN. A one-dimensional heat transfer model was used to optimise the processing parameters. Surface morphology and microstructure of the deposited coatings and substrate surface layers were examined using optical microscopy, scanning electron microscope, and field emission gun scanning electron microscope which reveals deposition of very thin layer about 0.3 μm of pure TiN and the presence of sub-micron crystalline structure of TiN forming a metal matrix composite inter-layer with the substrate below the film which suggest a good metallurgically bonding with the substrate. Chemical composition was determined by energy dispersive X-ray analysis. The phases were identified by X-ray diffraction which confirms the synthesis of TiN film for all the samples. Results of nano-hardness measurements revealed a hardness value of the order of 22-27 GPa.     

Formation of Ti and TiN ultra-thin films on Si by ion beam sputter deposition

Ultra-thin titanium and titanium nitride films on silicon substrate were obtained by ion beam sputtering of titanium target in vacuum and nitrogen atmosphere, using argon ions with energy of 5 keV and 15 μA target current. Elemental composition and chemical state of obtained films were investigated by X-ray photoelectron spectroscopy with using Mg-Kα X-ray radiation (photon energy 1253.6 eV). It was shown that it is possible to form both ultra-thin titanium films (sputtering in vacuum) and ultra-thin titanium nitride films (sputtering in nitrogen atmosphere) in the same temperature conditions. Photoelectron spectra of samples surface, obtained in different steps of films synthesis, detailed spectra of photoelectron emission from Si 2p, Ti 2p, N 1s core levels and also X-ray photoelectron spectra of Auger electrons emission are presented.     

Effects of intermediate zinc pulses on properties of TiN and NbN films deposited by atomic layer epitaxy

The reasons for the improvements gained by using intermediate zinc pulses in atomic layer epitaxy growth of TiN and NbN films were examined by a comprehensive characterization and comparison of films prepared from TiCl₄ or NbCl₅ and NH₃ with and without zinc. The characterization techniques used comprise time-of-flight elastic recoil detection analysis, secondary ion mass spectrometry, Rutherford backscattering spectrometry, nuclear resonance broadening, proton backscattering spectrometry, deuteron induced reactions, proton induced X-ray emission, atomic force microscopy, scanning electron microscopy, X-ray diffraction, and Hall effect and reflectance measurements. The effect of zinc was found to be manifold: both compositional and structural changes were observed. In the case of TiN the major improvement gained by using zinc was significantly decreased oxygen contamination whereas a marked increase of grain size was the dominant effect observed with NbN. A clear correlation between the compositional and structural changes and the improvements of the electrical properties was established.     

基于氮化钛薄膜表面等离子体共振特性的双芯光子晶体光纤温度传感器

提出一种基于表面等离子体共振的双芯光子晶体光纤温度传感器,其中双芯光子晶体光纤为折射率导光型,其中心圆孔表面镀氮化钛薄膜,内部填充具有较大热敏系数的乙醇和氯仿的混合液体,其纤芯模与表面等离子体激元耦合的共振波长偏移可反映液体混合物的温度或折射率.利用全矢量有限元法分析了不同因素对传输损耗谱及其共振波长的影响.仿真结果表明:外包层空气孔直径增大,以及最内层包层空气孔直径和空气孔间距减小可以提高耦合效率,从而增强共振峰.对比分析发现在-20℃～120℃温度范围内,氮化钛薄膜比传统金膜表现出更好的等离子传感特性,随着膜厚增加,其共振波长偏移量增加,温度灵敏度提高,灵敏度最高可以达到6.22 nm/K.     

RHEED studies during growth of TiN/SiNx/TiN trilayers on MgO(0 0 1)

TiN/SiN_x/TiN(0 0 1) trilayers have been deposited on MgO(0 0 1) substrates using ultra-high vacuum based reactive magnetron sputtering and studied by in situ reflection high energy electron diffraction (RHEED). Depositions were carried out at 500 °C and 800 °C, with SiN_x layer thicknesses between 3 and 300 Å. Here, we find that SiN_x(0 0 1) layers grown at 800 °C exhibit 1 × 4 surface reconstructions along orthogonal 〈1 1 0〉 directions up to a critical thickness of ∼9 Å, where an amorphous phase forms. Growth of TiN overlayers on the reconstructed SiN_x(0 0 1) layers yield RHEED patterns indicating the growth of (0 0 1)-oriented epitaxial layers with a 1 × 1 reconstruction. For the case of amorphous SiN_x layers the TiN overlayers grow polycrystalline.     

A self-consistent method for the determination of neutral density from X-ray impurity spectra

A new method for the determination of neutral densities and the electron lifetime from X-ray line spectra through charge exchange processes is proposed. The non-equilibrium population of neutrals and the charge exchange from their excited states in plasma regimes of high density and temperature have been calculated in a self-consistent manner through the introduction of an “effective diffusion rate”.     

Deposition of titanium nitride and hydroxyapatite-based biocompatible composite by reactive plasma spraying

Titanium nitride is a bioceramic material successfully used for covering medical implants due to the high hardness meaning good wear resistance. Hydroxyapatite is a bioactive ceramic that contributes to the restoration of bone tissue, which together with titanium nitride may contribute to obtaining a superior composite in terms of mechanical and bone tissue interaction matters.The paper presents the experimental results in obtaining composite layers of titanium nitride and hydroxyapatite by reactive plasma spraying in ambient atmosphere. X-ray diffraction analysis shows that in both cases of powders mixtures used (10% HA + 90% Ti; 25% HA + 75% Ti), hydroxyapatite decomposition occurred; in variant 1 the decomposition is higher compared with the second variant. Microstructure of the deposited layers was investigated using scanning electron microscope, the surfaces presenting a lamellar morphology without defects such as cracks or microcracks. Surface roughness values obtained vary as function of the spraying distance, presenting higher values at lower thermal spraying distances.     

New interpretations of XPS spectra of nickel metal and oxides

A current interpretation of XPS spectra of Ni metal assumes that the main 6 eV satellite is due to a two hole c3d⁹4s² (c is a core hole) final state effect. We report REELS observation in AES at low voltages of losses (plasmons and inter-band transitions) corresponding to the satellite structures in Ni metal 2p spectra. The satellite near 6 eV is attributed to a predominant surface plasmon loss. A current interpretation of Ni 2p spectra of oxides and other compounds is based on charge transfer assignments of the main peak at 854.6 eV and the broad satellite centred at around 861 eV to the cd⁹L and the unscreened cd⁸ final-state configurations, respectively (L is a ligand hole). Multiplet splittings have been shown to be necessary for assignment of Fe 2p and Cr 2p spectral profiles and chemical states. The assignments of Ni 2p states are re-examined with intra-atomic multiplet envelopes applied to Ni(OH)₂, NiOOH and NiO spectra. It is shown that the free ion multiplet envelopes for Ni²⁺ and Ni³⁺ simulate the main line and satellite structures for Ni(OH)₂ and NiOOH. Fitting the NiO Ni 2p spectral profile is not as straightforward as the hydroxide and oxyhydroxide. It may involve contributions from inter-atomic, non-local electronic coupling and screening effects with multiplet structures significantly different from the free ions as found for MnO. A scheme for fitting these spectra using multiplet envelopes is proposed.     

Many-electron effects in the XPS spectra of Cu and Ag

The L and M XPS spectra of Cu (Z = 29) and the M and N spectra of Ag (Z = 47) are measured. The lineshift and the line-width of the L, M, and N core levels are analysed in a systematic way from the viewpoint of dynamic decay processes and fluctuations of a hole. The non-relativistic diagrammatic many-body calculations give much better agreement with the measured linewidths than the conventional methods because of a consistent treatment of correlation and localization effects.     

Preparation and electrochemical performance of titanium nitride-graphene nanocomposite with high Ti contents and tailored morphology

Titanium nitride (TiN) - graphene (G) nanocomposites are promising for electrochemical charge storage where a high content of Ti species is desired. Herein, we propose an effective method for the preparation of TiN-G nanocomposites with a high concentration of Ti species. These nanocomposites can be successfully achieved through a further deposition of Ti on Ti-graphene oxide (GO) or a thermally exfoliated Ti-GO. Depending on the annealing condition employed (NH₃ and N₂), two types of TiN-G nanocomposites (NH₃ annealing for TiN/G and TiN/G-TE, TE: thermal exfoliation) and a TiO₂-G nanocomposite (N₂ annealing for TiO₂/G-TE) were prepared. These nanocomposites were then investigated for potential application as an electrochemical supercapacitor. Compare with TiO₂/G-TE, the TiN-G nanocomposites both exhibited a higher specific capacitance, although one of these nanocomposites had a lower surface area than TiO₂/G-TE. Among the nanocomposites prepared, TiN/G-TE delivered the best electrochemical performance. The relationship between the physical properties and the capacitive performance of the nanocomposites were systematically evaluated.     

A self-modeling approach to the resolution of XPS spectra into surface and bulk components

A method of resolving XPS spectra into surface and bulk component spectra for cases of moderate energy resolution is designed based on an analysis of a family of spectra acquired at different polar angles from flat specimens. Assumptions about line shapes are not required, but an analytical model of the angular dependence of the bulk and surface XPS signals is needed when the component spectra overlap in the range of binding energies of interest. Recommendations are made of the error limits of experimental variables for the successful application of the self-modeling method. The method was used successfully in the separation and quantitative analysis of the O(1s) XPS spectra of surface silanols from bulk silicon dioxide of a fully hydrated silicon dioxide surface. The surface (silanol) and bulk (oxide) components were found to be separated by 0.30 eV, and the surface component was found to be broader (1.58 eV) than the bulk component (1.15 eV).     

High-pressure phase transitions of TiN: an ab initio constant pressure study

An ab initio constant pressure molecular dynamics technique is carried out to explore the behaviour of rock salt-structured titanium nitride (TiN) under pressure. Two successive phase transformations are successfully observed in the dynamical simulations. The first one is an isostructural phase transition accompanied by an anomalous volume compression without any symmetry breaking. The second one is a reconstructive phase transformation into a CsCl-type structure. For the first time, the previously proposed two-phase transformations for TiN are confirmed through the simulations.     

TiC-和TiN-(001)表面吸附性能的密度泛函理论研究

基于密度泛函理论系统研究了碳化钛(TiC)和氮化钛(TiN)非极性(001)表面吸附气体分子和原子的性能。鉴于这些材料拥有不同的电子结构特征,发现受电子的CO分子或未饱和的O和H原子在TiC(001)和TiN(001)表面吸附于不同的活性位点,而供电子的NH3和H2O气体分子或完全饱和的O2和H2分子仅倾向与两个表面的金属原子位点结合。这些吸附特性可能与此类材料表面的电子结构有关。     

液氨中原位制备Si3N4-TiN纳米复合材料及表征

"提出了一种合成氮化钛/氮化硅(TiN/Si3N4)纳米复合材料的新方法．采用TiCl4和SiCl4作为原料,金属钠作为还原剂,以液氨为介质．在-45 ℃左右同时还原四氯化钛和四氯化硅,通过原位共沉淀获得TiN/Si3N4的纳米复合粉体．X射线衍射表明产物为非晶结构,副产物为氯化钠．产物粉末加热到1600 ℃晶化为TiN和ˉ-Si3N4．由于TiN的存在,混合粉末中的氮化硅晶化温度高于纯氮化硅的晶化温度．透射电镜照片显示粉末平均粒径在10~40 nm,扫描电镜照片表明钛、硅元素彼此均匀分布．在1500~1     

High resolution core and valence band XPS spectra of non-conductor pyroxenes

High resolution core level and valence band (VB) X-ray photoelectron spectra (XPS) of the non-conductor pyroxene minerals, bronzite ((Mg_0.8,Fe_0.2)₂Si₂O₆) and diopside (Ca(Mg_0.8Fe_0.2)Si₂O₆) have been obtained with the Kratos magnetic confinement charge compensation which minimizes differential charge broadening. Observed Si 2p, O 1s, Mg 2p and Ca 2p total linewidths are all about 1.3 eV, very similar to those observed previously with the same instrument for SiO₂ and olivines ((Mg,Fe)₂SiO₄); and we consider that these widths are within 0.05 eV of the minimum room temperature linewidths for these samples with the experimental resolution of this instrument of 0.35 eV. These linewidths are all determined by vibrational broadening due to the M-O symmetric stretch in the ion states. The Si 2p binding energies (BE) are intermediate between the quartz and olivine Si 2p binding energies; but the O 1s spectra resolve the bridging oxygen (BO) and non-bridging oxygen (NBO) in the unit, with the NBO O 1s very close in BE to the O in olivine, and the BO very close to the BO in SiO_2. Indeed in both diopside and bronzite, it is possible to separate the three structurally inequivalent O atoms in the O 1s spectra: the BO at a BE of about 532.6 eV, a NBO peak from the MgOSi moiety (Mg in the M1 site) at about 531.3 eV, and a NBO peak at 531 eV from the CaOSi or the FeOSi moieties (Ca and Fe in the M2 site). The O 1s BE increases with the increase in the electronegativity Ca < Mg < Fe < Si. Moreover, the linewidths of these peaks increase when Fe and Mg are both present in either M1 (diopside) or M2 (bronzite) sites.The valence band spectra for the two pyroxenes are rather similar, and quite different from the VB spectra of quartz and olivines. The dispersion of the pyroxene VB spectra is intermediate between the VB spectra of quartz and olivines; the valence band spectrum of pyroxenes are more dispersed than in olivines by about 1.5 eV but less dispersed than quartz by about 1.5 eV. These VB spectra can be assigned using the previous olivine VB spectra and high quality pseudopotential density functional theoretical calculations in the generalized gradient (GGA) approximation. As for the olivine VB spectra, the Fe 3d t_2g and e_g orbitals in M1 and M2 sites of the pyroxene are located at the top of the pyroxene valence band, and the BE of the Fe 3d peaks from M1 are about 0.7 eV smaller than the Fe 3d peaks in M2. The theoretical XPS valence band spectra using the theoretical density of states and the Gelius intensity approximation are is in good semi-quantitative agreement with the experimental spectra. This intermediate dispersion of pyroxenes is due to the partial polymerization of the Si-O units in pyroxenes, and the intermediate charge on the Si atoms as indicated by the Si 2p BE.     

Synthesis and characterization of superhard Ti-Si-N films obtained in an inductively coupled plasma enhanced chemical vapor deposition (ICP-CVD) with magnetic confinement

Using a novel inductively coupled plasma enhanced chemical vapor deposition (ICP-CVD) with magnetic confinement system, Ti-Si-N films were prepared on single-crystal silicon wafer substrates by sputtering Ti and Si (5 at.%:1 at.%) alloyed target in argon/nitrogen plasma. High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), X-ray diffractometer (XRD), field emission scanning electron microscope (FESEM), atomic force microscopy (AFM) and Nano Indenter XP tester were employed to characterize nanostructure and performances of the films. These films were essentially composed of TiN nanocrystallites embedded in an amorphous Si₃N₄ matrix with maximum hardness value of 44 GPa. Experimental results showed that the film hardness was mainly dependent on the TiN crystallite size and preferred orientation, which could be tailored by the adjustment of the N₂/Ar ratio. When the N₂/Ar ratio was 3, the film possessed the minimum TiN size of 10.5 nm and the maximum hardness of 44 GPa.     

Thermal stability of titanium nitride coatings prepared by the mixing technology with laser and plasma

Titanium samples were treated by the mixing technology with laser and plasma (LPN) using different laser power densities. These nitrided samples were then annealed at 473 K, 673 K, 873 K, and 1073 K for 2 h in vacuum, respectively. The samples before and after annealing were characterized at room temperature and compared in terms of microstructure. X-ray diffraction and cross-sectional optical microscopy studies showed that the layer structure of the titanium nitride coating is preserved after annealing at 1073 K when the coating is formed using a laser power density of 8.0 × 10⁵ W/cm². Therefore, titanium nitride coatings produced by LPN demonstrate excellent thermal stability and are potential candidates for high temperature tribological applications.