Effect of vacuum heat treatment on tensile strength and fracture performance of cold-sprayed Cu-4Cr-2Nb coatings

The previous study [1] indicated that dense thick Cu-4Cr-2Nb coatings could be formed by cold spraying, and the post-spray heat treatment could significantly influence the microstructure and microhardness of the as-sprayed Cu-4Cr-2Nb coatings. In this study, the tensile strength and fracture performance of the Cu-4Cr-2Nb coatings after annealing were investigated. The vacuum heat treatment was conducted under 10⁻² Pa at 850 °C for 4 h. Results showed that the heat treatment had a great contribution to the healing-up of the incompleteness of the interfaces between the deposited particles. In addition, the coating microhardness decreased from 156.8 ± 4.6 Hv_0.2 for the as-sprayed coatings to 101.7 ± 4.5 Hv_0.2 for the annealed ones. The mean tensile strength of the annealed coatings was approximately 294.1 ± 36.1 MPa compared to that of 45.0 ± 10.5 MPa for the as-sprayed ones, which results from the partially metallurgically bonded zones between the deposited particles inducing by the heat treatment process.     

Vapor Pressure Assisted Void Growth and Cracking of Polymeric Films and Interfaces

Pores and cavities form at filler particle-polymer matrix interfaces, at polymer film-silicon substrate interfaces as well as in molding compounds of IC packages. Moisture diffuses to these voids. During reflow soldering, surface mount plastic encapsulated devices are exposed to temperatures between 210 to 260°C. At these temperatures, the condensed moisture vaporizes. The rapidly expanding water vapor can create internal pressures within the voids that reach 3–6 MPa. These levels are comparable to the yield strengths of epoxy molding compounds and epoxy adhesives, whose glass transition temperatures T _g range between 150 to 300°C. Under the combined action of thermal stress and high vapor pressure (relative to the yield strength at T _g), both pre-existing and newly nucleated voids grow rapidly and coalesce. In extreme situations, vapor pressure alone could drive voids to grow and coalesce unstably causing film rupture, film-substrate interface delamination and cracking of the plastic package.Vapor pressure effects on void growth have been incorporated into Gurson's porous material model and a cohesive law. Crack growth resistance-curve calculations using these models show that high vapor pressure combined with high porosity bring about severe reduction in the fracture toughness. In some cases, high vapor pressure accelerates void growth and coalescence resulting in brittle-like interface delamination. Vapor pressure also contributes a strong tensile mode component to an otherwise shear dominated interface loading. An example of vapor pressure related IC package failure, known as popcorn cracking, is discussed.     

Effect of oxygen segregation on the surface structure of single-crystalline niobium films on sapphire

Single-crystalline Nb films are grown on (1120) oriented sapphire substrates by electron-beam evaporation in ultra-high vacuum. The films are studied in-situ by RHEED and Auger analysis. At a substrate temperature T _S=750° C the RHEED pattern shows a smooth growth of bcc-Nb in the [110] direction. In addition to the fundamental streaks, we observe superlattice streaks of fractional order in several azimuthal directions. The reciprocal lattice of the surface is determined. The basic vectors of the superlattice in real space are given by b ₁=2a ₁, b ₂=–a ₁+3a ₂ where a ₁ and a ₂ are the basic vectors of the Nb (110) surface. Auger analysis shows that the surface of these films is contaminated with oxygen. Therefore, the superstructure is attributed to a modified surface structure due to segregated oxygen, possibly having diffused from the sapphire to the film surface. The superstructure dissappears during further evaporation of Nb at T _S<450° C with a concomitant decrease of the oxygen signal. Nb films on sapphire with a clean, oxygen-free surface can only be prepared at lower temperatures in an island-growth mode.     

Enhanced ionic conductivity at the interface between sapphire and solid lithium iodide

We have studied the enhanced ionic conductivity of thin films of LiI evaporated onto a planar sapphire surface carrying interdigital Au-electrodes. The interface conductivity parallel to the surface was measured in situ for increasing film thickness, up to 3,000 Å. The specific conductivity of LiI in the first 300 Å — adjacent to the sapphire — was found to exceed the bulk conductivity of LiI by nearly one order of magnitude. From our observations we conclude that the specific conductivity of LiI decreases exponentially with distance from the sapphire surface reaching the bulk LiI-value only at a distance of 3,000 Å. The conductivity of a 350 Å thick film varies with temperature (25°CT120°C) in accordance with an activation energy of 0.40±0.04 eV. This is in good agreement with the activation energy of bulk LiI in the extrinsic region.     

Effect of substrate temperature on the surface and interface oxidation of NiTi thin films

NiTi shape memory alloy thin films are deposited on pure Cu substrate at substrate ambient temperatures of 300 °C and 450 °C. The surface and interface oxidation of NiTi thin films are characterized by X-ray photoelectron spectroscopy (XPS). After a subsequent annealing treatment the crystallization behavior of the films deposited on substrate at different temperatures is studied by X-ray diffraction (XRD). The effects of substrate temperature on the surface and interface oxidation of NiTi thin films are investigated. In the film surface this is an oxide layer composed of TiO₂. The Ni atom has not been detected on surface. In the film/substrate interface there is an oxide layer with a mixture Ti₂O₃ and NiO in the films deposited at substrate temperatures 300 °C and 450 °C. In the films deposited at ambient temperature, the interface layer contains Ti suboxides (TiO) and metallic Ni.     

Photoreflectance characterization of CdTe thin films grown by Molecular Beam Epitaxy on GaAs(100)

CdTe films have been grown on top of GaAs(100) by means of Molecular Beam Epitaxy (MBE) at 300 °C substrate temperature. Different procedures for the CdTe growth and for the preparation of the GaAs substrates resulted in diverse crystalline qualities of the CdTe films. We present the results obtained from PhotoReflectance (PR) measurements of these films employing HeNe and Ar-ion lasers as modulating excitation. For Ar excitation, the ratio of CdTe to GaAs signal strength for the E ₀ transition is enhanced, allowing a differentiation of the contributions from film and substrate. Both the PR line shape and intensity are correlated to the structural quality of the CdTe films. One of the samples presented a below-band-gap transition of the GaAs substrate around 30±5 meV from E ₀ which is attributed to donor states produced by Te atoms diffused in the interface; this result demonstrates the high sensitivity of the photoreflectance technique to the structural properties of interfaces.     

超导Nb-Ge溅射膜的俄歇电子能谱及电子能谱化学分析

利用表面分析仪器俄歇电子能谱(AES)仪和电子能谱化学分析(ESCA)仪对超导Nb-Ge溅射膜进行表面和深度剖面分析,以探讨在溅射沉积成膜过程中A15结构Nb₃Ge能够稳定生长的机制,以及影响其转变温度T_c的因素。分析结果表明,超导Nb-Ge膜中含有O,C和Al等杂质,其中O的含量对T_c有重要影响。表面上未发现有聚集的Ge。Nb/Ge密度比由表面层的3.1向内部逐渐降至2.26。X射线光电子能谱(XPS)的分析表明:Nb,Ge,C和O的谱峰沿深度均有不同程度的化学位移和峰形变化,这明这些元素的化学态在膜内是复杂的。但其中Nb的变化最小,可能对高T_cA15Nb₃Ge相的生长起稳定作用。 关键词：     

Strengthening sapphire at elevated temperatures by SiO2 films

SiO₂ films have been prepared on sapphire by radio frequency magnetron reactive sputtering in order to increase the optical and mechanical properties of infrared windows and domes of sapphire at elevated temperatures. Infrared transmission and flexural strength of uncoated and coated sapphires have been investigated at different temperatures. SiO₂ films were shown to have apparent antireflective effect on sapphire substrate at room temperature. With increasing temperature, the coated sapphires have larger average transmission than the uncoated ones. The temperature was proven to only weakly affect the absorption coefficient and antireflection capability of the deposited films. It is also indicated that the flexural strengths of the c-axis sapphire samples coated with SiO₂ films are increased by 1.2 and 1.5 times than those of uncoated at 600 and 800 °C, respectively.     

Anatase TiO2 films based CO gas sensor: Film thickness, substrate and temperature effects

Electrical response of anatase TiO₂ films is discussed for different concentrations of CO gas (20-100 ppm) in a nitrogen gas ambient. We investigated temperature (100-300 °C) and film thickness (100-1000 nm) effects for films deposited on glass, sapphire (0 0 0 1) and, Si(1 0 0) substrates. In general, there is a drop in resistance of the device when exposed to CO gas. Films deposited on sapphire showed a larger decrease in the resistance at 300 °C compared to those deposited on glass and silicon substrates. However, films grown on glass and silicon substrates showed a larger decrease in the resistance values for temperature around 200 °C when CO (ppm) values are greater than 40. The change in resistance of the films varies as square root of the CO gas concentration at 200 °C for films deposited on all the three substrates. In general, the decrease in resistance for thicker films is large compared to thinner ones, indicating participation of the bulk in the detection of CO gas. In the presence of O₂, film loses its sensitivity to CO gas when the concentration level of O₂ approaches 1800 ppm.     

Electrochemically assisted co-deposition of calcium phosphate/collagen coatings on carbon/carbon composites

Calcium phosphate (CaP)/collagen coatings were prepared on the surface of carbon/carbon (C/C) composites by electrochemically assisted co-deposition technique. The effects of collagen concentration in the electrolyte on morphology, structure and composition of the coatings were systematically investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transformed infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The adhesive strength of the coatings was also evaluated by scratch tests and tensile bond tests. It was demonstrated that the coatings of three-dimensional collagen network structure was formed on the C/C composites from the electrolyte containing collagen. The surface of the collagen network was covered by uniform CaP aggregates. The coatings were actually composites of CaP and collagen. Hydroxyapatite (HA) was a favorable composition in the coatings with the increase of the collagen concentration in the electrolyte. The formed collagen network increased the cohesive and adhesive strength of the coatings. The adhesive strength between the coatings and substrates increased as the collagen concentration in the electrolyte increased. The coatings prepared at the collagen concentration of 500 mg/L in the electrolyte were not scraped off until the applied load reached 32.0 ± 2.2 N and the average tensile adhesive strength of the coatings was 4.83 ± 0.71 MPa. After C/C coated with composite coatings (500 mg/L) being immersed in a 10⁻³ M Ca (OH)₂ solution at 30-33 °C for 96 h, nano-structured HA/collagen coatings similar to the natural human bone were obtained on the C/C.     

Effects of crystalline quality on the ultraviolet emission and electrical properties of the ZnO films deposited by magnetron sputtering

The ZnO films were deposited on c-plane sapphire, Si (0 0 1) and MgAl₂O₄ (1 1 1) substrates in pure Ar ambient at different substrate temperatures ranging from 400 to 750 °C by radio frequency magnetron sputtering. X-ray diffraction, photoluminescence and Hall measurements were used to evaluate the growth temperature and the substrate effects on the properties of ZnO films. The results show that the crystalline quality of the ZnO films improves with increasing the temperature up to 600 °C, the crystallinity of the films is degraded as the growth temperature increasing further, and the ZnO film with the best crystalline quality is obtained on sapphire at 600 °C. The intensity of the photoluminescence and the electrical properties strongly depend on the crystalline quality of the ZnO films. The ZnO films with the better crystallinity have the stronger ultraviolet emission, the higher mobility and the lower residual carrier concentration. The effects of crystallinity on light emission and electrical properties, and the possible origin of the n-type conductivity of the undoped ZnO films are also discussed.     

Microstructure and mechanical properties of continuous Al2O3 fibre reinforced Ni45Al45Cr7.5Ta2.5 alloy (IP75) matrix composites

Single crystalline Al₂O₃ fibres (sapphire), coated with the NiAl alloy IP75 by physical vapour deposition (PVD), were assembled to fabricate composites by means of diffusion bonding. The microstructure and chemistry of both as-coated fibre and as-diffusion bonded composites were investigated by electron microscopy and microanalysis. The interface shear stress for complete debonding was measured by fibre push-out tests at room temperature, and the composite tensile strength was measured at 900°C and 1100°C. An amorphous layer with a thickness of about 400?nm formed between the fibre and the matrix during the PVD process and was maintained during diffusion bonding. A Laves phase precipitated along NiAl grain boundaries in the IP75 matrix. This caused a lower tensile strength of the IP75/Al₂O₃ composite at high temperatures compared to as-cast monolithic IP75 and rendered the composite useless for structural applications.     

Deposition of BN interphase coatings from B-trichloroborazine and its effects on the mechanical properties of SiC/SiC composites

Boron nitride thin films were deposited on silicon carbide fibers by chemical vapor deposition at atmospheric pressure from the single source precursor B-trichloroborazine (Cl₃B₃N₃H₃, TCB). The film growth and structure, as a function of deposition temperature, hydrogen gas flow rate, and deposition time, were discussed. The deposition rate reaches a maximum at 1000 °C, then decreases with the increasing of temperature, and the apparent activation energy of the reaction is 127 kJ/mol. Above 1000 °C, gas-phase nucleation determines the deposition process. The deposited BN films were characterized by Raman spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effect of BN interphase on the mechanical properties of the unidirectional SiC fiber-reinforced SiC matrix (SiC/SiC) composites was also investigated. The results show that the flexural strength of SiC/SiC composites with and without coating is 276 MPa and 70 MPa, respectively, which indicates that BN interphase coating deposited from B-trichloroborazine precursor can effectively adjust the fiber/matrix interface, thus causing a dramatic increase in the mechanical properties of the composites.     

Investigation of SiO2/Si3N4 films prepared on sapphire by r.f. magnetron reactive sputtering

Sapphire is a desired material for infrared-transmitting windows and domes because of its excellent optical and mechanical properties. However, its thermal shock resistance is limited by loss of compressive strength along the c-axis of the crystal with increasing temperature. In this paper, double layer films of SiO₂/Si₃N₄ were prepared on sapphire (α-Al₂O₃) by radio frequency magnetron reactive sputtering in order to increase both transmission and high temperature mechanical performance of infrared windows of sapphire. Composition and structure of each layer of the films were analyzed by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), respectively. Surface morphology and roughness of coated and uncoated sapphire have been measured using a talysurf. Flexural strengths of sapphire sample uncoated and coated with SiO₂/Si₃N₄ have been studied by 3-point bending tests at different temperatures. The results show that SiO₂/Si₃N₄ films can improve the surface morphology and reduce the surface roughness of sapphire substrate. In addition, the designed SiO₂/Si₃N₄ films can increase the transmission of sapphire in mid-wave infrared and strengthen sapphire at high temperatures. Results for 3-point bending tests indicated that the SiO₂/Si₃N₄ films increased the flexural strength of c-axis sapphire by a factor of about 1.4 at 800 °C.     

Facile method to prepare lotus-leaf-like super-hydrophobic poly(vinyl chloride) film

A simple new approach was developed to obtain a super-hydrophobic PVC film from a natural lotus leaf using the nanocasting method. SEM shows that compared with a common smooth PVC film, a lotus-leaf-like surface structure was clearly observed on the super-hydrophobic PVC film. The water contact angle and rolling-off angle on the as-prepared lotus-leaf-like PVC film were 157 ± 1.8° and 3 ± 0.6°, respectively. The samples were kept at temperatures between 5 and 40 °C in the ambient atmosphere for 2 months, and no decrease in water contact angle was observed, nor was contamination observed.     

Defects in nanocrystalline Nb films: Effect of sputtering temperature

Thin niobium (Nb) films (thickness 350-400 nm) were prepared on (1 0 0)Si substrate in a UHV chamber using the cathode beam sputtering. The sputtering temperature T_s was varied from 40 up to 500 °C and the influence of the sputtering temperature on the microstructure of thin Nb films was investigated. Defect studies of the thin Nb films sputtered at various temperatures were performed by slow positron implantation spectroscopy (SPIS) with measurement of the Doppler broadening of the annihilation line. SPIS was combined with transmission electron microscopy (TEM) and X-ray diffraction (XRD). We have found that the films sputtered at T_s = 40 °C exhibit elongated, column-like nanocrystalline grains. No significant increase of grain size with T_s (up to 500 °C) was observed by TEM. The thin Nb films sputtered at T_s = 40 °C contain a high density of defects. It is demonstrated by shortened positron diffusion length and a high value of the S parameter for Nb layer compared to the well-annealed (defect-free) bulk Nb reference sample. A drastic decrease of defect density was found in the films sputtered at T_s ≥ 300 °C. It is reflected by a significant increase of the positron diffusion length and a decrease of the S parameter for the Nb layer. The defect density in the Nb layer is, however, still substantially higher than in the well-annealed reference bulk Nb sample. Moreover, there is a layer at the interface between the Nb film and the substrate with very high density of defects comparable to that in the films sputtered at T_s < 300 °C. All the Nb films studied exhibit a strong (1 1 0) texture. The films sputtered at T_s < 300 °C are characterized by a compressive macroscopic in-plane stress due to lattice mismatch between the film and the substrate. Relaxation of the in-plane stress was observed in the films sputtered at T_s ≥ 300 °C. The width of the XRD profiles of the films sputtered at T_s ≥ 300 °C is significantly smaller compared to the films sputtered at lower temperatures. This is most probably due to a lower defect density which results in reduced microstrains in the films sputtered at higher temperatures.     

Microstructure, bonding strength and thermal shock resistance of ceramic coatings on steels prepared by plasma electrolytic oxidation

Ceramic coatings were successfully prepared on steel by plasma electrolytic oxidation (PEO) in aluminate electrolyte and silicate electrolyte, respectively. The microstructure of the coatings including surface morphology, phase and element composition were studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The bonding strength between the ceramic coating and the substrate was tested using different methods including tensile tests and shearing tests. The thermal shock resistance of the coatings was also evaluated. The results indicated that coatings obtained in both electrolytes were porous and coarse. The average diameters of the pores were below 10 μm. PEO coatings obtained in aluminate electrolyte were composed of Fe₃O₄ and FeAl₂O₄, while those obtained in silicate electrolyte were in a noncrystal state. PEO coatings obtained in aluminate electrolyte showed similar change trend of tensile strength and shearing strength with increasing treating time, namely, a relatively high values with middle time treating and low value with short and long time treating. The best coating was the samples treated with 30 min, whose tensile strength was 20.6 MPa and shearing strength was 16 MPa. The tensile strength and shearing strength of coatings obtained in silicate electrolyte were not strongly influenced by the treating time, the values of which were range in 14 ± 2 MPa and 11 ± 2 MPa, respectively. Coatings obtained in both electrolytes showed the best thermal shock resistance with middle time treating. Coatings obtained in silicate electrolyte show a little better thermal shock resistance than those obtained in aluminate electrolyte.     

Microstructure,creep, and tensile behaviour of a Ti–15Al–33Nb (at.%) beta+orthorhombic alloy

The microstructural evolution, creep and tensile deformation behaviour of a Ti–15Al–33Nb (at.%) alloy was studied. Monolithic sheet material was produced through conventional thermomechanical processing techniques comprising non-isothermal forging and pack rolling. Electron microscopy studies showed that depending on the heat-treatment schedule, this alloy may contain three constituent phases including:?β?(disordered body-centred cubic), α₂ (ordered hexagonal close-packed based on Ti₃Al) and O (ordered orthorhombic based on Ti₂AlNb). Heat treatments at all temperatures above 990°C, followed by water quenching, resulted in fully-β microstructures. Below 990°C, Widmanstätten O-phase or α₂-phase precipitated within the?β?grains. The fine-grained as-processed microstructure, which exhibited 90?vol.% β-phase, exhibited excellent strength (UTS?=?916?MPa) and ductility (?_f>12%). After heat treatment, greater volume fractions of the orthorhombic phase precipitated and resulted in lower ? _f values with UTS values ranging between 836–920?MPa. However, RT elongations of more than 2% were recorded for microstructures containing up to 63?vol.% O-phase. Specimens subjected to 650°C tensile experiments tended to exhibit lower strength values while maintaining higher elongation-to-failure. Tensile creep tests were conducted in the temperature range 650–710°C and stress range 49–275?MPa. The measured creep exponents and activation energies suggested that grain boundary sliding operates at intermediate stress levels and dislocation climb is active at high stresses. Microstructural effects on the tensile properties and creep behaviour are discussed in comparison to a Ti–12Al–38Nb O?+?β alloy.     

Comparison of the properties of Nextel 720/SiC composites at room temperature and 1300°C

Continuous Nextel 720 fibers reinforced SiC composites with PyC interface are fabricated by LPCVI at 1000°C for 200 h using SiCH₃Cl₃ as precursor. The mechanical properties at RT and 1300°C are measured by three-point bending. The microstructures of the interface are characterized by TEM. The results indicate the composites have the metal-like behavior of fracture, whether they are at RT or high temperature. The RT and 1300°C strengths are 310 MPa and 140 MPa, respectively. The RT and 1300°C strains are 0.32% and 0.12%, respectively. The loss of flexural strength and strain of the Nextel 720/SiC composites at high temperature result from stronger residual thermal stress caused by the mismatch of CTE between fibers and matrix. A gap appears between fibers and PyC interface after the 1300°C test, which could be resulted from 7.7% compressive strain of PyC interface caused by the residual thermal stress and 0.1% sintering shrinkage of Nextel 720 fiber.     

Synthesis of epitaxial γAl<Subscript>2</Subscript>O<Subscript>3</Subscript> thin films by thermal oxidation of AlN/sapphire(0001) thin films

The synthesis of epitaxial Al₂O₃ films by oxidizing AlN/sapphire(0001) films was investigated in a synchrotron X-ray scattering experiment. Porous Al₂O₃ nucleates on the surface of the AlN film when annealed above 700 °C in oxygen ambient. As the annealing temperature increases above 900 °C, the entire AlN film is oxidized into an epitaxial Al₂O₃ film that has a cubic spinel structure. With increasing oxidation temperature, more oxygen atoms are incorporated into the oxide structure, resulting in denser oxide films with a larger lattice constant. The crystal domain size increases from 50 Å to 210 Å, suggesting that the initial nucleation of the Al₂O₃ crystalline domains is followed by gradual grain growth. PACS 61.10.Eq; 81.65.Mq; 68.55.Jk; 68.35.Ct