Selective single pulse femtosecond laser removal of alumina (Al2O3) from a bilayered Al2O3/TiAlN/steel coating

We studied surface modification of a double layer protective coating on steel induced by single fs laser pulse irradiation in ambient air. The outer alumina (Al₂O₃) layer, which protects against aggressive environments, was 1.7 μm thick and the titanium aluminum nitride (TiAlN) layer in contact with the steel surface had a thickness of 1.9 μm. The pulses (λ = 775 nm, τ = 200 fs) were generated by a Ti:sapphire laser source. The pulse energy was varied from 0.32 μJ to 50 μJ, corresponding to an incident laser fluence of 0.11 J cm^− 2 to 16.47 J cm^− 2. The surface damage threshold was found to be 0.20 J cm^− 2 and the alumina layer removal was initiated at 0.56 J cm^− 2. This selective ablation of alumina was possible in a wide range of fluences, up to the maximum applied, without ablating the TiAlN layer beneath.     

HOPG上ALD沉积Al2O3介电薄膜的生长行为研究

本文采用原子层沉积(ALD)的方法,选择三甲基铝(TMA)和H₂O₂作为反应前驱体,在高定向热解石墨(HOPG)基体上沉积Al₂O₃。系统研究了反应温度和生长周次对Al₂O₃生长行为的影响。研究表明：受HOPG表面饱和成键的影响,Al₂O₃在衬底表面处形核困难,在生长初期主要表现为台阶处择优生长,其形态为线状结构。当沉积100周次Al₂O₃时,其中在沉积温度为50 °C、150 °C和200 °C时呈现为纳米线状结构,而在100 °C时呈现为非连续薄膜。随着生长周次的增加,不同温度下沉积态Al₂O₃都趋于形成连续薄膜,表明其生长行为发生了由三维岛状生长模式向二维平面生长模式的转变。分析认为,生长模式的转变是由纳米线状结构横向生长造成的;横向生长速率主要受生长温度影响。拉曼结果表明：沉积后的石墨烯层结构未受影响,可保留其原有的优越性能。     

Oxidation behavior of Ti3AlC2 at 1000-1400 °C in air

The isothermal oxidation behavior of bulk Ti₃AlC₂ has been investigated at 1000-1400 °C in air for exposure times up to 20 h by means of TGA, XRD, SEM and EDS. It has been demonstrated that Ti₃AlC₂ has excellent oxidation resistance. The oxidation of Ti₃AlC₂ generally followed a parabolic rate law with parabolic rate constants, k_p that increased from 4.1×10⁻¹¹ to 1.7×10⁻⁸ kg² m⁻⁴ s⁻¹ as the temperature increased from 1000 to 1400 °C. The scales formed at temperatures below 1300 °C were dense, adherent, resistant to cyclic oxidation and layered. The inner layer of these scales formed at temperatures below 1300 °C was continuous α-Al₂O₃. The outer layer changed from rutile TiO₂ at temperatures below 1200 °C to a mixture of Al₂TiO₅ and TiO₂ at 1300 °C. In the samples oxidized at 1400 °C, the scale consisted of a mixture of Al₂TiO₅ and, predominantly, α-Al₂O₃, while the adhesion of the scales to the substrates was less than that at the lower temperatures. Effect of carbon monoxide at scale/substrate was involved in the formation of the continuous Al₂O₃ layers.     

原子层沉积Al2O3 保护层氢终端金刚石MISFETs的电学特性

研究了Zr-Si-N氢终端金刚石（H-diamond）绝缘栅场效应晶体管（MISFET）在有无Al₂O₃保护层情况下的电学特性。分别采用原子层沉积法（ALD）和射频溅射法（RF）制备了Al₂O₃保护层和Zr-Si-N栅介质层。MISFETs的转移特性曲线表明,其栅阈值电压在有无Al₂O₃保护的情况下从-2.5 V变化到3 V,表明器件从常关型转换为常开型。输出和转移特性曲线揭示了氧化铝的存在保护了氢终端,使其免受磁控溅射过程的损伤。     

Bulk WC-Al2O3 composites prepared by spark plasma sintering

WC and WC-Al₂O₃ materials without metallic binder addition were densified by spark plasma sintering in the range of 1800-1900 °C. The densification behavior, phase constitution, microstructure and mechanical properties of pure WC and WC-Al₂O₃ composite were investigated. The addition of Al₂O₃ facilitates sintering and increases the fracture toughness of the composites to a certain extent. An interesting phenomenon is found that a proper content of Al₂O₃ additive helps to limit the formation of W₂C phase in sintered WC materials. The pure WC specimen possesses a hardness (HV₁₀) of 25.71 GPa, fracture toughness of 4.54 MPa·m^1/2, and transverse fracture strength of 862 MPa, while those of WC-6.8 vol.% Al₂O₃ composites are 24.48 GPa, 6.01 MPa·m^1/2, and 1245 MPa respectively. The higher fracture toughness and transverse fracture strength of WC-6.8 vol.% Al₂O₃ are thought to result from the reduction of W₂C phase, the crack-bridging by Al₂O₃ particles and the local change in fracture mode from intergranular to transgranular.     

Cyclic oxidation behavior and thermal barrier effect of YSZ-(Al2O3/YAG) double-layer TBCs prepared by the composite sol-gel method

Novel YSZ (6 wt.% yttria partially stabilized zirconia)-(Al₂O₃/YAG) (alumina-yttrium aluminum garnet, Y₃Al₅O₁₂) double-layer ceramic coatings were fabricated using the composite sol-gel and pressure filtration microwave sintering (PFMS) technologies. The thin Al₂O₃/YAG layer had good adherence with substrate and thick YSZ top layer, which presented the structure of micro-sized YAG particles embedded in nano-sized α-Al₂O₃ film. Cyclic oxidation tests at 1000 °C indicated that they possessed superior properties to resist oxidation of alloy and improve the spallation resistance. The thermal insulation capability tests at 1000 °C and 1100 °C indicate that the 250 μm coating had better thermal barrier effect than that of the 150 μm coating at different cooling gas rates. These beneficial effects should be mainly attributed to that, the oxidation rate of thermal grown oxides (TGO) scale is decreased by the “sealing effect” of α-Al₂O₃, the “reactive element effect”, and the reduced thermal stresses by means of nano/micro composite structure. This double-layer coating can be considered as a promising TBC.     

Effect of applied current on the electrodeposited Ni-Al2O3 composite coatings

Nano-sized Al₂O₃ ceramic particles (50 nm) were co-deposited with nickel using electrodeposition technique to develop composite coatings. The coatings were produced in an aqueous nickel bath at different current densities and the research investigated the effect of applied current on microstructure and thickness of the coatings. The variation in some mechanical properties such as hardness, wear resistance, and the adhesive strength of the composite coatings is influenced by the applied current and this was also studied. The morphology of the coatings was characterized by scanning electron microscopy and energy dispersive X-ray spectroscopy. The hardness, wear resistance, and bond strength of the coatings were evaluated by Vickers micro-hardness test, pin-on-disc test, and tensile test, respectively. Results showed that the Al₂O₃ particles were uniformly distributed in the coatings, and the coatings deposited at a current density of 0.01 A/cm² was most favorable in achieving a maximum current efficiency which causes the co-deposition of a maximum amount of Al₂O₃ particles (4.3 wt.%) in the coatings. The increase in Al₂O₃ particles in the coatings increased the mechanical properties of the Ni-Al₂O₃ composite coatings by grain refining and dispersion strengthening mechanisms.     

Synthesis and electrochemical performance of Li(Ni0.8Co0.15Al0.05)0.8(Ni0.5Mn0.5)0.2O2 with core-shell structure as cathode material for Li-ion batteries

The core-shell structure cathode material Li(Ni_0.8Co_0.15Al_0.05)_0.8(Ni_0.5Mn_0.5)_0.2O₂ (LNCANMO) was synthesized via a co-precipitation method. Its applicability as a cathode material for lithium ion batteries was investigated. The core-shell particle consists of LiNi_0.8Co_0.15Al_0.05O₂ (LNCAO) as the core and a LiNi_0.5Mn_0.5O₂ as the shell. The thickness of the LiNi_0.5Mn_0.5O₂ layer is approximately 1.25 μm, as estimated by field emission scanning electron microscopy (FE-SEM). The cycling behavior between 2.8 and 4.3 V at a current rate of 18 mA g⁻¹ shows a reversible capacity of about 195 mAh g⁻¹ with little capacity loss after 50 cycles. High-rate capability testing shows that even at a rate of 5 C, a stable capacity of approximately 127 mAh g⁻¹ is retained. In contrast, the capacity of LNCAO rapidly decreases in cyclic and high rate tests. The observed higher current rate capability and cycle stability of LNCANMO can be attributed to the lower impedance including charge transfer resistance and surface film resistance. Differential scanning calorimetry (DSC) indicates that LNCANMO had a much improved oxygen evolution onset temperature of approximately 251 °C, and a much lower level of exothermic-heat release compared to LNCAO. The improved thermal stability of the LNCANMO can be ascribed to the thermally stable outer shell of LiNi_0.5Mn_0.5O₂, which suppresses oxygen release from the host lattice and not directly come into contact with the electrolyte solution. In particular, LNCANMO is shown to exhibit improved electrochemical performance and is a safe material for use as an electrode for lithium ion batteries.     

Oxidation behaviour of Ti-46.7Al-1.9W-0.5Si in air and Ar-20%O2 between 750 and 950 °C

The oxidation behaviour of an intermetallic alloy, Ti-46.7Al-1.9W-0.5Si, was studied in air and Ar-20%O₂ atmospheres at 750, 850 and 950 °C. Oxidation of the alloy followed a parabolic rate law at low temperature (750 °C) in both environments. The alloy oxidised parabolically in air and at a slower rate in Ar-20%O₂ at 850 °C. Following a parabolic oxidation for a relatively short exposure period (72 h) at 950 °C, the oxidation rate was reduced after prolonged exposure (up to 240 h) in air. The alloy oxidised in a slower manner in the Ar-20%O₂ atmosphere at 950 °C. Higher oxidation rates were observed in air than in Ar-20%O₂ at all three experimental temperatures. Multi-layered scales developed in both environments. The scale formed in air consisted of TiO₂/Al₂O₃/TiO₂/TiN/TiAl₂ layers, ranging from the surface to the substrate—whilst the scale developed in the Ar-20%O₂ atmosphere comprised of the sequence TiO₂/Al₂O₃/TiO₂/Al₂O₃/Ti₃Al/substrate. The two layers of Al₂O₃ in Ar-20%O₂ were more effective in providing protection of the substrate against high temperature corrosion than the single layer of Al₂O₃ formed in air.     

Role of Al2O3 layer in oxidation resistance of Cu-Al dilute alloys pre-annealed in H2 atmospheres

Copper was alloyed with small amounts of Al (0.2, 0.5, 1.0 and 2.0 mass%) to improve the oxidation resistance. Copper (6 N) and the Cu-Al alloys were oxidized at 773-1173 K in 0.1 MPa oxygen atmosphere after hydrogen annealing at 873 K. Continuous very thin Al₂O₃ layers were formed on the surface of all Cu-Al dilute alloys during the hydrogen annealing. Oxidation resistance of Cu-Al alloys was improved especially for Cu-2.0Al at 773-973 K, while it decreases on increasing the oxidation temperature. Cu-Al alloys followed the parabolic rate law at 1173 K, but most of other cases do not at and below 1073 K. Oxidation resistance for Cu-Al alloys was found relevant to the maintenance of the thin Al₂O₃ layer at the Cu₂O/Cu-Al alloy interface.     

Al2O3-nanodiamond composite coatings with high durability and hydrophobicity prepared by aerosol deposition

We attempted the room-temperature fabrication of Al₂O₃-based nanodiamond (ND) composite coating films on glass substrates by an aerosol deposition (AD) process to improve the anti-scratch and anti-smudge properties of the films. Submicron Al₂O₃ powder capable of fabricating transparent hard coating films was used as a base material for the starting powders, and ND treated by 1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFOTES) was added to the Al₂O₃ to increase the hydrophobicity and anti-wear properties. The ND powder treated by PFOTES was mixed with the Al₂O₃ powder by ball milling to ratios of 0.01 wt.%, 0.03 wt.%, and 0.05 wt.% ND. The water contact angle (CA) of the Al₂O₃-ND composite coating films was increased as the ND ratio increased, and the maximum water CA among all the films was 110°. In contrast to the water CA, the Al₂O₃-ND composite coating films showed low transmittance values of below 50% at a wavelength of 550 nm due to the strong agglomeration of ND. To prevent the agglomeration of ND, the starting powders were mixed by attrition milling. As a result, Al₂O₃-ND composite coating films were produced that showed high transmittance values of close to 80%, even though the starting powder included 1.0 wt.% ND. In addition, the Al₂O₃-ND composite coating films had a high water CA of 109° and superior anti-wear properties compared to those of glass substrates.     

Effects of Al and Al4C3 contents on combustion synthesis of Cr2AlC from Cr2O3-Al-Al4C3 powder compacts

Preparation of the ternary carbide Cr₂AlC was conducted by combustion synthesis in the mode of self-propagating high-temperature synthesis (SHS) from the Cr₂O₃-Al-Al₄C₃ powder compact. Effects of the contents of Al and Al₄C₃ on the product composition and combustion behavior were studied by formulating the reactant mixture with a stoichiometric proportion of Cr₂O₃:Al:Al₄C₃ = 3:5x:y, where x and y varied from 1.0 to 1.5. When compared to those of the powder compact with Cr₂O₃:Al:Al₄C₃ = 3:5:1 (i.e., x = y = 1.0), the combustion temperature and reaction front velocity increased with content of Al, but decreased with that of Al₄C₃. Besides Cr₂AlC and Al₂O₃, the final products always contained a secondary phase Cr₇C₃ that was substantially reduced by adopting additional Al and Al₄C₃ in the reactant compacts. For the sample with Cr₂O₃:Al:Al₄C₃ = 3:7.5:1 (x = 1.5), solid state combustion reached a peak temperature of 1245 °C and yielded Cr₂AlC with a trivial amount of Cr₇C₃. Although Cr₇C₃ was lessened by introducing extra Al₄C₃, the increase of Al₄C₃ from y = 1.1 to 1.5 produced almost no further reduction of Cr₇C₃ in the final product. This is partly attributed to the low combustion temperature in the range of 1065-1095 °C for the samples with additional Al₄C₃, and in part, due to the role of Al₄C₃ which might react with Cr to form Cr₇C₃, Cr₂Al, and Cr₂AlC.     

Structural and dielectric properties of Bi2Zn2/3Nb4/3O7 thin films prepared by pulsed laser deposition at low temperature for embedded capacitor applications

Bi₂Zn_2/3Nb_4/3O₇ thin films were deposited on Pt/TiO₂/SiO₂/Si(1 0 0) substrates at a room temperature under the oxygen pressure of 1-10 Pa by pulsed laser deposition. Bi₂Zn_2/3Nb_4/3O₇ thin films were then post-annealed below 200 °C in a rapid thermal process furnace in air for 20 min. The dielectric and leakage current properties of Bi₂Zn_2/3Nb_4/3O₇ thin films are strongly influenced by the oxygen pressure during deposition and the post-annealing temperature. Bi₂Zn_2/3Nb_4/3O₇ thin films deposited under 1 Pa oxygen pressure and then post-annealed at a temperature of 150 °C show uniform surface morphologies. Dielectric constant and loss tangent are 57 and 0.005 at 10 kHz, respectively. The high resolution TEM image and the electron diffraction pattern show that nano crystallites exist in the amorphous thin film, which may be the origin of high dielectric constant in the Bi₂Zn_2/3Nb_4/3O₇ thin films deposited at low temperatures. Moreover, Bi₂Zn_2/3Nb_4/3O₇ thin film exhibits the excellent leakage current characteristics with a high breakdown strength and the leakage current density is approximately 1 × 10⁻⁷ A/cm² at an applied bias field of 300 kV/cm. Bi₂Zn_2/3Nb_4/3O₇ thin films are potential materials for embedded capacitor applications.     

Synthesis and characterization of Al2O3-Ce0.5Zr0.5O2 powders prepared by chemical coprecipitation method

Al₂O₃-Ce_0.5Zr_0.5O₂ catalytic powders were synthesized by the coprecipitation (ACZ-C) and mechanical mixing (ACZ-M) methods, respectively. As-synthesized powders were characterized by XRD, Raman spectroscopy, surface area and thermogravimetric analyses. It was found that the mixing extent of Al³⁺ ions affected the phase development, texture and oxygen storage capacity (OSC) of the Ce_0.5Zr_0.5O₂ powder. Single phase of ACZ-C could be maintained without phase separation and inhibit α-Al₂O₃ formation up to 1200 °C. The specific surface area value of ACZ-C (81.5 m²/g) was larger than that of ACZ-M (62.1 m²/g) and Ce_0.5Zr_0.5O₂ (17.1 m²/g) powders, which were calcined at 1000 °C. In comparison with ACZ-C and Al₂O₃, which were calcined at high temperature (900–1200 °C), it was found that the degradation rate of specific surface area of ACZ-C was lower than that of Al₂O₃. ACZ-C sample showed a higher thermal stability to resist phase separation and crystallite growth, which enhanced the oxygen storage capacity property for Ce_0.5Zr_0.5O₂ powders.     

The corrosion behavior of plasma sprayed Fe2Al5 coating in molten Zn

Aluminum coating was plasma sprayed on Fe-0.14-0.22 wt.% C steel substrate, and heat diffusion treatment at 923 °C for 4 h was preformed to the aluminum coating to form Fe₂Al₅ inter-metallic compound coating. The corrosion mechanism of the Fe₂Al₅ coating in molten zinc was investigated. SEM and EDS analysis results show that the corrosion process of the Fe₂Al₅ layer in molten zinc is as follows: Fe₂Al₅ → Fe₂Al₅Zn_x (η) → η + L(liquid phase) → L + η + δ(FeZn₇) → L + δ → L. The η phase and the eutectic structure (η + δ) prevent the diffusion of zinc atoms efficiently. Therefore the Fe₂Al₅ coating delays the reaction between the substrate and molten zinc, promoting the corrosion resistance of the substrate.     

Preparation, structure and photoluminescence of nanoscaled-Nd: Lu3Al5O12

Nd:Lu₃Al₅O₁₂ (Nd:LuAG) nano-crystalline was synthesized by co-precipitation method. Its phase transformation, structure, absorption and photoluminescence properties were studied. The Nd:LuAG polycrystalline phase is formed above 900 °C and its particle sizes are in the range of 18-36 nm. The structure of Nd:LuAG was refined by Rietveld method. The lattice parameters and the distortion of Lu³⁺-O²⁻ polyhedron in Nd:LuAG are larger than that of in pure LuAG. Because the distortion of Lu³⁺-O²⁻ polyhedron is larger than that of Y³⁺-O²⁻ polyhedron in YAG and the distance of Lu³⁺-O²⁻ is smaller than that of Y³⁺-O²⁻ in YAG, Nd³⁺ in LuAG experiences a stronger crystal field effect, which is proved by the crystal field strength and the chemical environment parameter. The absorption spectrum shows that Nd:LuAG has a broad absorption band at 808 nm with FWHM above 6 nm, which is favorable for improving laser efficiency. The fluorescence lifetime from ⁴F_3/2 → ⁴I_11/2 transition is 320 μs and longer than that of Nd:YAG. The longer lifetime is propitious to energy storage. The emission cross section at 1064 nm is 2.89 × 10⁻¹⁹ cm², taking into account the Boltzmann distribution of the excited state. The emission cross section in Nd:LuAG is also larger than that of Nd:YAG, which is useful for laser operation. All results indicate that Nd:LuAG is a promising crystal material to apply in high energy lasers.     

Mechanochemical synthesis of Al2O3-TiB2 nanocomposite powder from Al-TiO2-H3BO3 mixture

Alumina-titanium diboride nanocomposite (Al₂O₃-TiB₂) was produced using mixtures of titanium dioxide, acid boric and pure aluminum as raw materials via mechanochemical process. The phase transformation and structural characterization during mechanochemical process were utilized by X-ray diffractometry (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and thermogravimetric analyses (TG-DTA) techniques. A thermodynamic appraisal showed that the reaction between TiO₂, B₂O₃ and Al is highly exothermic and should be self-sustaining. XRD analyses exhibited that the Al₂O₃-TiB₂ nanocomposite was formed after 1.5 h milling time. The results indicate that increasing milling time up to 40 h had no significant effect other than refining the crystallite size.     

Low temperature growth of nanocrystalline TiO2 films with Ar/O2 low-field helicon plasma

TiO₂ thin films were deposited on silicon wafer substrates by low-field (1 < B < 5 mT) helicon plasma assisted reactive sputtering in a mixture of pure argon and oxygen. The influence of the positive ion density on the substrate and the post-annealing treatment on the films density, refractive index, chemical composition and crystalline structure was analysed by reflectometry, Rutherford backscattering spectroscopy (RBS) and X-ray diffraction (XRD). Amorphous TiO₂ was obtained for ion density on the substrate below 7 × 10¹⁶ m^− 3. Increasing the ion density over 7 × 10¹⁶ m^− 3 led to the formation of nanocrystalline (~ 15 nm) rutile phase TiO₂. The post-annealing treatment of the films in air at 300 °C induced the complete crystallisation of the amorphous films to nanocrystals of anatase (~ 40 nm) while the rutile films shows no significant change meaning that they were already fully crystallised by the plasma process. All these results show an efficient process by low-field helicon plasma sputtering process to fabricate stoichiometric TiO₂ thin films with amorphous or nanocrystalline rutile structure directly from low temperature plasma processing conditions and nanocrystalline anatase structure with a moderate annealing treatment.     

Piezoelectric and dielectric properties of Dy2O3-doped (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ + x wt% Dy₂O₃ with x = 0-0.3 ceramics were synthesized by conventional solid-state processes. The effects of Dy₂O₃ on the microstructure, the piezoelectric and dielectric properties were investigated. X-ray diffraction pattern confirmed that the coexistence of tetragonal and rhombohedral phases in the (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ composition was not changed by adding 0.05-0.3 wt% Dy₂O₃. SEM images indicate that all the ceramics have pore-free microstructures with high density, and that doping of Dy₂O₃ inhibits the grain growth of the ceramics. The addition of Dy₂O₃ shows the double effects on decreasing the piezoelectric and dielectric properties for 0 < x < 0.15 when Dy³⁺ ions substitute B-site Ti⁴⁺ ions, and increasing the properties for 0.15 < x < 0.3 when Dy³⁺ ions enters into A-site of the perovskite structure. The optimum electric properties of piezoelectric constant d₃₃ = 170 pC/N and the dielectric constant ?_r = 1900 (at a frequency of 1 kHz) are obtained at x = 0.3.