The influence of thermal annealing on residual stresses and mechanical properties of arc-evaporated TiCxN1−x (x=0, 0.15 and 0.45) thin films

We report the stress relaxation behavior of arc-evaporated TiC_xN_1−x thin films during isothermal annealing between 350 and 900°C. Films with x=0, 0.15, and 0.45, each having an initial compressive intrinsic stress σ_int=−5.4 GPa, were deposited by varying the substrate bias V_s and the gas composition. Annealing above the deposition temperature leads to a steep decrease in the magnitude of σ_int to a saturation stress value, which is a function of the annealing temperature. The corresponding apparent activation energies for stress relaxation are E_a=2.4, 2.9, and 3.1 eV, for x=0, 0.15, and 0.45, respectively. TiC_0.45N_0.55 films with a lower initial stress σ_int=−3 GPa, obtained using a high substrate bias, show a higher activation energy E_a=4.2 eV. In all the films, stress relaxation is accompanied by a decrease in defect density indicated by the decreased width of X-ray diffraction peaks and decreased strain contrast in transmission electron micrographs. Correlation of these results with film hardness and microstructure measurements indicates that the stress relaxation is a result of point-defect annihilation taking place both during short-lived metal-ion surface collision cascades during deposition, and during post-deposition annealing by thermally activated processes. The difference in E_a for the films of the same composition deposited at different V_s suggests the existence of different types of point-defect configurations and recombination mechanisms.     

Enhancement of the properties of pulsed laser-deposited carbon nitride by the synchronisation of laser and N2 gas jet pulses

In surface coatings technology, especially in carbon-based materials, the deposition of energetic species is acknowledged as one of the most important factors in producing hard coatings. Pulsed laser deposition (PLD) of carbon under vacuum creates such energetic species and so carbon films with very high hardness values have been reported. However, when PLD takes place in a gas ambient, the ablated carbon species are decelerated to an extent that depends on the background pressure. As a result, during CN_x deposition, although the carbon species react effectively with N₂ at the beginning of their trajectories, when they reach the substrate they usually do not have sufficient kinetic energy to form a hard coating. In this paper we describe a new technique that combines the intense environment of an expanding N₂ jet with low-pressure PLD to produce CN_x species that travel almost free of collisions and reach the substrate with high kinetic energies. This new configuration is based on the synchronised pulsing of a N₂ jet with the laser pulse. The CN films produced are shown to have an increased film hardness without suppressing the nitrogen content. Furthermore, electron energy-loss spectroscopy shows the layers to have a very high proportion of π bonding, which can be correlated to the existence of sp-hybridised carbon in the form of –CN bonds.     

ESR bottleneck effect in dilute Gd1−xLaxT2Si2 (T=Cu, Ni) systems

The bottleneck effect observed in electron spin resonance (ESR) was removed by replacing the Gd^3. spins by non-magnetic lanthanum ions in two compounds: the most bottlenecked GdCu₂Si₂ and GdNi₂Si₂ where the bottleneck is weaker. The unbottlenecked limit was reached for very small Gd concentrations to (1 −x) = 0.0005. From these results the ν(E_F)J_Sc values have been estimated, where ν(E_F) is the electron density of states at the Fermi level and J_Sc is the exchange coupling constant between conduction electrons and Gd spins. It was found that these values are twice as large for Ni compounds (15 × 10³) as for Cu compounds (7.5 × 10³). On the basis of X-ray photoemission spectra of the valence band and theoretical calculations of ν(E_F) for LaCu₂Si₂, the density of states is estimated as 0.15 states per eV spin atom for GdCu₂Si₂ and 0.3 states per eV spin atom for GdNi₂Si₂ (for J_Sc = 0.05 eV). The relaxation processes in the investigated compounds are also discussed.     

Effect of sintering temperature on the structure and properties of cerium-doped 0.94(Bi0.5Na0.5)TiO3–0.06BaTiO3 piezoelectric ceramics

Phase structure, microstructure, dielectric and piezoelectric properties of 0.4 wt% CeO₂ doped 0.94(Bi_0.5Na_0.5)TiO₃–0.06BaTiO₃ (Ce-BNT6BT) ceramics sintered in the temperature range from 1120 to 1200 °C have been investigated as a candidate for lead-free piezoelectric ceramics. Tetragonal phase played an important role in improvement of electrical properties and the density of the ceramics. Dielectric constant decreased slightly with the increase of sintering temperature in ferroelectric region but a reverse phenomenon occurred in antiferroelectric and paraelectric regions, suggesting that interfacial polarizations were improved with the increase of sintering temperature and domain walls of ferroelectricity became active after depolarization. At room temperature, Ce-BNT6BT ceramics sintered at 1180 °C showed good performances: dielectric constant was 914 at 1 kHz, thick coupling factor k_t was 0.52, and the ratio of k_t/k_p was 2.3. The ceramics were suitable for narrowband filters and ultrasonic transducers in commercial applications.     

Martensitic transitions and mechanical spectroscopy of Ni50.8Ti49.2 alloy containing hydrogen

Hydrogen additions [n_H=H/(Ni+Ti)=0.003; 0.008; 0.013; 0.021; 0.029; 0.045 at.] to a Ni_50.8Ti_49.2 alloy produce several effects in the elastic and anelastic properties of the material. At temperatures between 100 and 150 K hydrogen atoms act as fixed pinning points for dislocations, as they cancel a newly observed dislocation relaxation. At low H contents (0<n_H≤0.008) the internal friction peak P_AM (P_RM) associated with austenite/martensite (A→M) or R-phase/martensite (R→M) transitions dramatically increases with increasing the H content, while the dip occurring in the Young's modulus (E) vs temperature curves becomes gradually wider and shallower. The enhancement of peak P_AM (P_RM) can be accounted for in terms of a mechanism involving the excitation of collective vibration modes (dyadons) of twin boundaries interacting with H or the stress-induced motion of parent/product interfaces. The widening of the dip in the Young's modulus is due to the introduction by H of a two-step transition (A→R→M). With increasing the H content n_H from 0.008 to 0.045 the height of peak P_AM (P_RM) decreases and a higher temperature peak (P_H) appears and progressively grows becoming the only internal friction feature for n_H=0.045. With increasing H content the thermal hysteresis in the E(T) curves occurring over the coexistence region of the A and M (R and M) phases decreases due to the inhibition caused by H of the martensitic transition. Peak P_H is most likely associated with stress-induced motion of H in solid solution within the R-phase or within a hydride.     

Internal friction of Cu–CuAlO alloys

Polycrystalline internal oxidize copper alloy with CuAlO particles has been studied by isothermal mechanical spectrometry, above room temperature. The frequency range was 10⁻⁴ to 30 Hz and the maximum strain 2×10⁻⁵. Experiments were carried out on a sample after 18% cold-rolling and successive annealings at various temperatures. The internal friction spectra obtained between 290 and 400 K exhibit only a low frequency background superimposed to a non thermally activated maximum. After annealing at 400 K, the background decreases, a relaxation peak appears and its maximum rises progressively as temperature increases. The relaxation parameters, obtained from the frequency shift of the maximum with temperature, leads to E_a=0.9 eV, and τ₀=6.9×10⁻¹⁰ s. These values are similar to those described in the literature for a relaxation peak assigned to dislocation motion inside grains.     

镍基合金激光熔覆-离子渗硫复合改性层组织性能

利用激光熔覆和离子渗硫技术在45钢表面制备复合改性层,采用SEM,EPMA,XRD等手段对比研究激光熔覆层和渗硫层的组织形貌、成分分布及相组成;并测试渗硫前后涂层的耐磨性和耐蚀性.结果表明,镍基合金涂层主要由γ-（Fe,Ni）,Fe_0.64Ni_0.36,M₂₃C₆,WC,M₇C₃和Fe₂B等物相组成,显微硬度达到740 HV0.2.渗硫后在激光熔覆层表面形成了以FeS为主的渗硫层,表面疏松多孔,由微纳米级的尖岛状颗粒堆砌而成.与熔覆层相比,复合改性层的摩擦系数和磨损量都显著降低,减摩和耐磨效果明显.渗硫后镍基合金激光熔覆层自腐蚀电位下降,腐蚀电流密度增大,耐蚀性略微降低.     

Electro-Optics and Band Gap Energies of Nanosilver-Coated TiO_2 Nanotubes on Titanium Metal

TiO_2 nanotubes on Ti metal surface were prepared by the electrochemical anodization method. Then, nanosilver was deposited onto the nanotubes by the electroless dip coating and the anodization. The obtained TiO2 nanotubes were examined by using scanning electron microscopy, atomic force microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, cyclic voltammetry, and UV–Vis. The electrochemical band gap(E_g~(CV)) of the nanosilver-coated TiO_2 nanotubes prepared by the anodization was found as 1.54 eV. Using the UV–Vis measurements, the optical band gap energy(E_g~(op).) was calculated as 1.51 eV for the Ag/TiO_2 nanotubes obtained by electroless dip coating. The electrical conductivity of the TiO_2 nanotubes also increased from 3.0 9 10-4 to 34.7 S/cm after nano Ag deposition by the anodization method.These Ag/TiO_2 nanotubes with low band gap and high electrical conductivity are desirable for the applications in electronics, Li-ion batteries, and solar cells.     

脉冲激光对6106铝合金表面形貌及氧含量的影响

研究了脉冲激光清洗在不同的清洗速度以及不同的脉冲重复频率下铝合金表面形貌以及表面氧元素含量的影响。试验结果表明,在清洗速度较低时(0.1~0.6 m/min),铝合金激光清洗过的表面呈溅射重叠的状态,当清洗速度大于0.8 m/min时,脉冲激光在铝合金表面的形成的冲击坑逐渐变得分散、独立;铝合金表面氧元素整体的含量随清洗速度的增减呈先下降后增加的趋势,在清洗速度较小或者较大时,氧元素含量均接近母材表面氧元素含量水平,氧元素含量分布具有明显的区域性,脉冲激光冲击坑的位置氧元素含量明显高于周围未冲击位置。随脉冲重复频率的增加,铝合金表面形貌由独立冲击坑逐渐过渡为溅射重叠的状态,表面氧元素整体含量明显下降,约为母材氧含量的1/2,氧元素的分布也逐渐变为弥散。     

Effect of thermal cycling through the martensitic transition on the internal friction and Young’s modulus of a Ni50.8Ti49.2 alloy

The internal friction (IF) and Young’s modulus (E) of a Ni_50.8Ti_49.2 is affected by thermal cycling. With increasing the number n of thermal cycles, the IF peak P_AM (P_MA) occurring at the austenite/martensite transition temperature decreases to disappear almost completely. Meanwhile the associated E(T) minimum at the beginning (n<250) deepens and then becomes progressively shallower and wider (3×10³≤n<18×10³). The strong sensitivity of P_AM (P_MA) to thermal cycling and to impurity (hydrogen) contents suggests that this peak is predominantly associated with stress-assisted collective motions of twin boundaries located inside the martensite platelets embedded within the austenite phase, rather than with the martensitic transition itself. However, as the high temperature tail of P_AM starts at temperatures appreciably higher than the martensite start-temperature M_s, a premartensitic contribution to damping is also present. The widening of the E(T) minimum indicates that, for n≥3×10³, the direct transformation is to some extent hindered by the dislocation network introduced by thermal cycling. A not thermally activated IF peak P_TWM, which is believed to be due to stress-assisted motions of (001) compound twin boundaries in the homogeneous martensite state, grows with increasing n.     

A laser spectroscopic study of Nd-doped zirconia

High-surface-area rare-earth (RE) modified zirconia powders prepared by solution methods can be used as catalytic support of noble metals and as electrolyte oxygen sensors in an automobile exhaust-emission-control system. A previous neutron-scattering study showed that substituting zirconium with trivalent RE ions not only stabilizes the cubic and tetragonal phases over a wide range of temperatures, but also creates oxygen vacancies in the RE–Zr oxide solid solution. This work focuses on the fluorescence of Nd in Nd_0.1Zr_0.9O_1.95 powders under laser excitation of the Nd³⁺ ground state to the ⁴G_7/2 states. Distinct features were observed at 8 K in the ⁴I_9/2→⁴G_7/2 excitation and ⁴F_3/2→⁴I_9/2 emission spectra using two sets of incident and emission frequencies, respectively. The results are discussed in terms of site-sensitive local structures surrounding the Nd ions in the two-phased oxide structure.     

Mechanical loss of cubic zirconia

Cubic zirconia can be stabilized by doping with lower valent oxides such as Y₂O₃ or CaO. Oxygen vacancies are then created as charge compensating defects. Mechanical loss measurements were performed in the temperature range 300–1600 K using both free decaying (3 Hz, 3 kHz) and forced vibrations (10⁻²–10 Hz). The influence of Y₂O₃ (10–24 mol%) and CaO (10–16 mol%) on the loss spectra was studied. The low temperature spectra (<1000 K) show a composite loss maximum which can be decomposed into two peaks, I and I_A (I′, I_A′). Both peaks, with activation enthalpy values between 1 and 2 eV, rely on local jumps of oxygen vacancies which are trapped by dopant cations. Submaxima I (I′) are assigned to defect pairs of oxygen vacancies and dopant ions (Y or Ca) forming elastic (electric) dipoles. These are oriented parallel to 111 (trigonal symmetry) with the vacancies on nearest neighbor sites. Maxima IA (I_A′) are assigned to relaxation of vacancies within larger clusters and interaction effects (Y or Ca). The high temperature loss spectra (≥1000 K) show various relaxation phenomena. In Y₂O₃ stabilized ZrO₂ we observe around 1400 K a loss peak with frequency independent temperature position which is assigned to a structural phase transition. ZrO₂–CaO shows a high temperature peak of Debye type (H=4.0±0.5 eV) which is related to local diffusional jumps of cations via vacancies.     

CVD金刚石膜激光平整化效率和粗糙度

对化学气相沉积(CVD)多晶金刚石膜进行激光平整化的正交试验,使用场发射环境扫描电子显微镜(SEM)进行形貌分析,激光共聚焦扫描显微镜测量线粗糙度R_a、面粗糙度S_a和切缝锥度,分析激光参数对CVD膜平整化的影响。结果表明:影响切缝锥度的因素依次为脉冲宽度、脉冲频率、进给速度和激光电流,影响线粗糙度R_a的因素依次为进给速度、激光电流、脉冲频率、脉冲宽度。正交试验优化后,当激光电流为64 A、脉冲宽度为400 μs、脉冲频率为275 Hz、进给速度为100 mm/min时,可获得最佳的切槽表面形貌。采用该优化参数进行面扫描,测得面粗糙度S_a为11.7?μm;进一步增加入射角度至75°时,面粗糙度S_a降低至1.9 μm,实际去除效率达到1.1 mm3/min。      

Microstructure and mechanical properties of Cr–Si–N coatings prepared by pulsed reactive dual magnetron sputtering

Cr–Si–N thin films were deposited by pulsed DC reactive dual-magnetron sputtering using Cr and Si targets, while various currents applied to the Si target allowed one to vary the Si content (C_Si) in the films. Microstructure, composition and mechanical properties were studied as a function of C_Si using XRD, ERD-TOF and depth-sensing indentation. Three regions of C_Si were distinguished: (i) C_Si < 2.3 at.%, where the grain size (D) does not significantly change with increasing C_Si; (ii) 2.3 < C_Si < 6.7 at.%, where D decreases as C_Si increases; and (iii) 6.7 ≤ C_Si ≤ 11.6 at.%, where a relatively rapid decrease of D is observed with increasing C_Si. We found that the hardness (H) and the reduced Young's modulus (E_r) of the films reached maximum values of H ~ 24 GPa and E_r ~ 240 GPa for C_Si ~ 2.3 at.%. Based on the evolution of the microstructural and mechanical properties of the Cr–Si–N films, we propose to explain the hardening observed for C_Si < 2.3 at.% in terms of the solid solution mechanism rather than the nanocomposite formation.     

Wet routes of high purity BaTiO3 nanopowders

High purity BaTiO₃ nanopowders were prepared in wet routes through stearic acid gel (SAG) and acetic acid gel (AAG) techniques, respectively. BaTiO₃ samples were characterized by X-ray diffraction, transmission electron microscope, Fourier transform infrared spectrometry, X-ray fluorescence spectrometry, and thermal gravimetric analysis. The present results indicate that both methods have a similar reaction process during calcination, while BaTiO₃ crystallites were initially formed at 550 °C by SAG and 800 °C by AAG. Both methods could produce BaTiO₃ powders with a cubic perovskite structure, while they had different grain size distributions within 25–50 nm for SAG and 50–80 nm for AAG. BaTiO₃ samples prepared by SAG had a lower agglomeration than those by AAG. SAG has shown many distinctive advantages in the preparation of high purity BaTiO₃ nanopowders, without Ba and Ti losses and hazardous wastes.     

Metal–insulator transition in Fe-substituted SrRuO3 bad metal system

The effect of Fe substitution in the bad metal SrRuO₃ perovskite was studied by resistivity, magnetic susceptibility and Mössbauer spectroscopic measurements. The conduction behavior changed from metallic for x_Fe≤0.1 to non-metallic for x_Fe>0.26. In the intermediate concentration range, 0.1<x_Fe<0.26, a resistivity minimum was observed as a function of temperature. The magnetic properties showed a change from ferromagnetic to paramagnetic for x_Fe≥0.3. There was an enhancement in quadrupole splitting deduced from ⁵⁷Fe Mössbauer spectra in going from compositions x_Fe<0.3 to x_Fe≥0.3 suggestive of a change in screening of ionic charge at this composition. These observations show that the change in conduction behavior of this system may be related to the initial small mean free path of the bad metal system as well as a change in conduction electron density brought about by substitution of trivalent Fe for quadruvalent Ru.     

Spectroscopic and 1.06 μm laser properties of Nd-doped K–Sr–Al phosphate and fluorophosphate glasses

Optical absorption, fluorescence and decay curves for the ⁴F_3/2 level of Nd³⁺ ions in phosphate (P₂O₅–K₂O–SrO–Al₂O₃) and fluorophosphate (P₂O₅–K₂O–SrO–Al₂O₃–AlF₃ and P₂O₅–K₂O–SrO–Al₂O₃–BaF₂) glasses doped with three concentrations (0.1, 1.0 and 2.0 mol%) of Nd³⁺ ions have been investigated. The Judd–Ofelt (JO) theory has been applied to the absorption spectra of 1.0 mol% Nd³⁺-doped glasses to derive JO intensity parameters which are in turn used to calculate the radiative properties of the Nd³⁺ ion fluorescent levels. The assigned energy level data of Nd³⁺ (4f³) ions are analysed in terms of a parametrized free-ion Hamiltonian model that consists of 20 interaction parameters of atomic nature. The stimulated emission cross section and branching ratios have been calculated using the emission spectra. The relatively higher branching ratio for ⁴F_3/2 → ⁴I_11/2 transition shows the suitability of these glasses for laser application. It is interesting to note that the measured decay curves of the ⁴F_3/2 level remain nearly single exponential even for higher Nd³⁺ ion concentration but with shortening of lifetime.     

Effect of addition of Cu into ZrOx film on its properties

The article reports on the effect of addition of Cu into the ZrO₂ film on its structure, physical and mechanical properties. The ZrO₂ and Zr–Cu–O films were reactively sputtered using a dc unbalanced magnetron from Zr (99.9) and ZrCu (90/10 at.%) targets in Ar + O₂ mixture at the substrate temperature T_s = 300, 400 and 550 °C and total sputtering gas pressure p_T = 1 Pa on steel, Si(100) and glass substrates. The structure of films was characterized by an X-ray diffraction (XRD) and mechanical properties, i.e. microhardness H, effective Young's modulus E* = E / (1 − ν²) and elastic recovery W_e, were measured using a microhardness tester; E and ν are the Young's modulus and the Poisson ratio, respectively. The film brittleness was characterized by the formation of cracks during the diamond indenter impression into it. 5 μm thick ZrO₂ films prepared in the oxide mode of sputtering are crystalline (m-ZrO₂) and exhibit relatively (i) high hardness H≈16 GPa and (ii) low ratio H³ / E*²≈0.11 GPa. The Zr–Cu–O films with low (≤ 2 at.%) Cu content exhibit (i) crystalline structure, (ii) higher H, (iii) lower (− 1.5 GPa) macrostress σ and (iv) higher ratio H³ / E*²≈0.14 GPa. On the contrary, the Zr–Cu–O films with high (24 to 44 at.%) Cu content exhibit (i) X-ray amorphous structure, (ii) lower H≈11 GPa and lower ratio H³ / E*²≈0.075 GPa. A special attention was devoted to the investigation of cracking of Zr–Cu–O films under high (0.5 and 1 N) loads of the diamond indenter. The relations between the film cracking and properties of the film and the substrate were used to assess the toughness of the Zr–Cu–O film. It was found that the film toughness increase with increasing H³ / E*² ratio. It was shown that the addition of Cu to ZrO₂ film can improve its toughness.     

双脉冲电源参数对电铸金刚石-镍复合膜品质的影响

采用电铸法制备了金刚石-镍复合膜,研究了平均电流密度、正向脉冲频率、正向脉冲占空比、反向脉冲占空比等双脉冲电源参数对镀层厚度的均匀性、沉积速率、硬度、表面形貌的影响.结果表明:随着平均电流密度的增加,沉积速率增大并趋于稳定,复合膜硬度先增大后减小,厚度的均匀性变差;随着正向脉冲频率的增加,沉积速率和硬度都增大,厚度的均...     

Optical Constant and Electrical Resistivity of Annealed Sn_3Sb_2S_6 Thin Films

In this study,we report the annealing effects on the physical properties of Sn_3Sb_2S_6 thin films.Sn_3Sb_2S_6 thin films were prepared onto non-heated glass substrates via thermal evaporation technique.The as-deposited films were annealed in air for 1 h in the temperature range from 100 to 300 °C.X-ray diffraction results show that the crystallinity of the thin films increased after annealing.The microstructure parameters crystallite size,dislocation density,lattice strain and stacking fault probability were calculated.The optical properties were obtained from the analysis of the experimental recorded transmittance and reflectance spectral data over the wavelength range 300–1800 nm.High absorption coefficient(10~5cm~(-1)) reached to the visible and near-IR spectral range.A decrease in optical band gap from 1.92 to 1.71 e V by increasing the air annealing temperature was observed.Oscillator energy E_o and dispersion energy E_d of the films after annealing were estimated according to the model of Wemple–Di Domenico single oscillator.Spitzer–Fan model was applied to determine the electron free carrier susceptibility and the ratio of carrier concentration to the effective mass.The layers annealed at temperatures 150 ℃ undergo abrupt changes in their electrical properties and exhibit a resistive hysteresis behavior.These properties confer to the material interest perspectives for its application in diverse advanced technologies such as photovoltaic applications and optical storage.