激光辅助热喷涂NiCoCrAlYTa/ZrO2/BaF2·CaF2涂层的组织及性能∗

高温耐磨涂层是航空发动机关键摩擦副可靠使用的重要保障,鉴于其服役环境日益严苛复杂,进一步提高涂层的高温耐磨性能是十分必要的。利用激光辅助热喷涂技术制备 NiCoCrAlYTa / ZrO₂ / BaF₂·CaF₂ 高温耐磨涂层,利用 SEM、EDS 分析高温耐磨涂层的横截面微观组织及化学成分,研究 ZrO₂ / BaF₂·CaF₂质量分数、激光功率及扫描速度对耐磨涂层微观组织、力学性能及高温耐磨性能的影响。结果表明：激光辅助处理可以诱导耐磨涂层表面形成具有树枝状结构的 ZrO₂陶瓷层; 当激光功率为 80 W,扫描速度为 8 mm / s,喷涂粉末为 75 wt.% NiCoCrAlYTa+25 wt.% ZrO₂ / BaF₂·CaF₂时,制备涂层的微观组织、综合力学性能及高温耐磨性能达到最好;在此工艺参数下,涂层顶部的 ZrO₂ 陶瓷层最为致密均匀,其平均纳米硬度为 13.6 GPa,平均弹性模量为 182.5 GPa,800 ℃时的磨损率为 2.7×10^?5 mm³ ·N^?1 ·m^?1 。将高温耐磨涂层的组分设计与激光辅助热喷涂工艺相结合,可为提高涂层综合性能的提供解决途径。     

微织构排布方式对水润滑轴承启停过程摩擦学性能的影响

梯度排布微织构在提升水润滑轴承摩擦学性能方面具有显著效果,然而梯度排布微织构在水润滑轴承中的应用仍缺乏系统性研究。为了探究梯度排布微织构对水润滑轴承启停过程摩擦学性能的影响,基于 Greenwood-Tripp 微凸体接触模型、 Archard 磨损模型求解轴瓦表面的磨损量。通过 CFT-I 材料表面性能综合测试仪对 CNC 雕刻机加工的织构化表面进行水润滑条件下的摩擦学试验研究。针对光滑、单一圆形织构、圆形与三角形以轴向交错平行（¹₁2 ）和周向交错平行分布（1212）方式梯度排布的表面,测量各个表面的磨损量和摩擦因数。通过立体显微镜、扫描电子显微镜对摩擦磨损试验前后的表面形貌和摩擦因数进行分析。数值模拟和试验结果显示,与光滑表面和单一织构化表面相比,梯度排布微织构化表面磨损量和摩擦因数显著降低;圆形与三角形以¹₁2 方式的梯度排布微织构化表面摩擦学性能最佳,接触表面磨损量最小、表面摩擦因数最低。 梯度排布微织构在流体润滑过程中相互影响,可以起到提高轴承表面举升力,减少表面接触,降低表面磨损和摩擦因数的作用。研究不同形状、排布方式下梯度排布微织构化表面的磨损量和摩擦因数的变化规律,可为舰船装备水润滑轴承研制阶段主动设计提供理论基础。     

高功率脉冲磁控溅射技术制备纳米级ZrO2薄膜的高耐腐蚀性

高质量的金属氧化物薄膜在航天航空、海洋船舶等极端环境下的关键部件有着广泛的应用需求,但传统制备技术易导致薄膜疏松多孔,产生空隙裂纹等缺陷,高功率脉冲磁控溅射技术(HiPIMS)已被证明是一种有效制备无空洞和无弧滴致密薄膜的有效方法。通过 HiPIMS 技术在不锈钢表面制备超薄致密 ZrO₂ 薄膜,重点研究不同 O₂流量下耐腐蚀性能的调控规律。 通过扫描电子显微镜(SEM)、光电子能谱仪(XPS)、X 射线衍射仪(XRD)、原子力显微镜(AFM)、纳米压痕仪(Nano Test P3)、电化学设备(CS300)等对 ZrO₂薄膜的表面形貌、物相结构、力学性能、耐腐蚀性能等方面进行研究。研究结果显示, 在 O₂流量为 40 mL/ min 时,ZrO₂ 薄膜的纳米硬度 H 最高为 26.38 GPa,弹性模量 E 为 290.9 GPa;同时,在电化学腐蚀试验中,其自腐蚀电流密度 I_corr达到 45.802 pA / cm² ,与 304L 不锈钢相比降低了 4 个数量级;电化学阻抗谱(EIS)显示,随 O₂流量的增加,容抗弧半径、低频区阻抗值和相角均随之不断增大,进一步表明 O₂ 流量为 40 min / mL 制备薄膜的耐腐蚀性能最优。通过 HiPIMS 技术能够制备出高质量的 ZrO₂ 薄膜,其高耐腐蚀性对基体起到了强效的防护作用,对防腐薄膜的研究和应用具有一定参考价值。     

298 K下离子液体BMIMPF6 中电沉积制备镧金属薄膜

以无水硝酸镧、1-丁基-3-甲基咪唑六氟磷酸（BMIMPF₆）和助溶剂丙酮为电解液,在室温（298 K）下电沉积制得镧金属薄膜。电解液BMIMPF₆的电化学窗口为-2.5~1.5 V vs. Pt,La³⁺还原为La²⁺发生于-1.7 V vs. Pt,La²⁺还原为La⁰发生于-2.1 V vs. Pt。BMIMPF₆的低吸湿性有利于在空气气氛下电沉积镧。使用扫描电子显微镜和光学显微镜观察到所制备的薄膜织构致密,经能量色散谱和X射线光电子能谱对沉积薄膜进行了表征,确定了薄膜中含有大量镧元素。通过探究电压扫描速率和硝酸镧浓度对La³⁺的电化学行为的影响,证明La³⁺的还原反应是一个受物质扩散控制的不可逆过程,La³⁺在BMIMPF₆中的扩散系数为1.47×10^-9 cm²·s^-1。本研究为获得金属镧薄膜和镧氧化物薄膜提供了一种简便的方法,并且有望用于电沉积制备其它镧系元素薄膜。     

聚四氟乙烯表面PDA/TiO2复合薄膜的构建及其细胞响应性

聚四氟乙烯（PTFE）具有良好的生物稳定性,是一种被广泛应用的生物材料。利用聚多巴胺（PDA）化学及原位共沉积法,在PTFE基板表面沉积制备复合薄膜,以改善其表面的亲水性和细胞响应特性。研究结果显示,由PDA和TiO₂构成的薄膜可以有效地沉积与PTFE基板表面。薄膜均匀且与基板结合牢固,剪切强度可达23.5 MPa。薄膜中的TiO₂含量可以通过沉积液中的TiO₂水溶胶加入量调节。具有薄膜的PTFE表面成纤维细胞和成骨细胞响应性较之PTFE基板显著改进,1 d的细胞粘附试验和3 d的细胞增殖试验均显示涂层表面细胞数量显著高于无涂层的PTFE。这种在PTFE表面构建二氧化钛涂层的方法简单易行,在PTFE植入体表面修饰方面具有较好的应用前景。     

多孔ZrO2-8 wt% Y2O3涂层的制备及性能

航空发动机的效率与转动叶片和机匣之间的间隙密切相关。为了控制转子和静子之间的间隙,需要在机匣表面制备可磨耗的封严涂层。在发动机的高温端,ZrO₂-8wt% Y₂O₃涂层是经常采用的封严涂层基体。涂层中的孔隙可以增加涂层的可磨耗性。本文利用聚苯酯(PHB)增加等离子喷涂的ZrO₂-8 wt% Y₂O₃涂层的孔隙率。为了避免聚苯酯在等离子喷涂过程中的烧损,利用溶胶-凝胶法在聚苯酯颗粒表面沉积一层TiO₂层。文中将讨论采用此方法制成的涂层的形态、孔隙率、硬度和可磨耗性。结果表明,在喷涂粉末中混合包覆型的聚苯酯后,涂层的孔隙率将会得到提升,涂层硬度将会下降。磨耗试验的结果表明涂层的磨耗深度随着涂层孔隙率的增加而增加。     

TiB2涂层熔盐电沉积制备与表征

炭阴极在铝电解槽中受熔盐和铝液腐蚀而影响寿命,而TiB₂涂层是铝电解槽理想的阴极材料。本文以石墨为基体,在KF-KCl-K₂TiF₆-KBF₄熔盐中以0.4-0.7A.cm_-2^{电流密度、}700-800℃温度电沉积TiB₂涂层,通过XRD衍射仪、SEM-EDS、表面粗糙度测量仪及附着力测试仪对不同电流密度和温度下制备的涂层进行表征。结果表明：在石墨基体上可以得到均匀连贯的TiB₂涂层;增大电流密度、降低电解温度可以细化涂层晶粒,提高涂层致密性;在0.6 A.cm_-²、750℃最优电沉积条件下制得的TiB₂涂层的厚度为229 μm,择优取向为<110>,表面粗糙度为14.85 μm,涂层与石墨基体的结合力为6.39 MPa。     

O2/Ar流量比及退火对氧化锆薄膜结构及摩擦学性能的影响

采用多弧离子镀(MAIP)方法在 Inconel 718 高温合金基体上沉积了氧化锆(ZrO_x )薄膜,并对该薄膜进行了 800 ℃退火处理;研究了 O₂ / Ar 两种气体流量比 R_{O2/ Ar}(0. 25、0. 43、0. 67、1. 00、1. 50)及退火处理对沉积态薄膜的微观结构、力学性能及摩擦学性能的影响。 结果表明:随着 R_{O2/ Ar} 从 0. 25 升高到 1. 50,沉积态薄膜的主要物相组成由不稳定的锆的氧化物(h-ZrO_{0. 35} 、h-ZrO₂ 、h-Zr₃O)逐渐转变为稳定的 m-ZrO₂ ,薄膜截面结构由起初疏松的柱状晶逐渐转变为排列致密的柱状晶,薄膜硬度逐渐升高,O₂ / Ar 比为 1. 50 时最大为 16. 7 GPa。 低 R_{O2/ Ar} 下沉积的薄膜摩擦学性能很差,很快磨穿失效。 当 R_{O2/ Ar} 超过 0. 67 时,薄膜的摩擦寿命显著提高,R_{O2/ Ar} 为 1. 50 时薄膜磨损率最低为 1. 45×10^-6 mm³ / (N·m)。 沉积态薄膜经过退火处理后主要物相转变为 m-ZrO₂ ,薄膜表面变得更加光滑致密,薄膜硬度、弹性模量以及摩擦学性能均较退火前明显改善。     

ZrO2纳米颗粒对Al-12.5%Si合金PEO陶瓷层性能的影响

采用外加ZrO₂纳米颗粒的电解液体系在Al-12.5%Si合金表面制备ZrO₂- Al₂O₃- SiO₂三相PEO陶瓷层。利用SEM和XRD对陶瓷层微观结构和物相进行分析,并对其隔热及热冲击性能进行测试。结果表明：ZrO₂纳米颗粒显著提高了膜层的致密度和结合性,并有效减弱了Si元素对PEO成膜的抑制作用,提高了成膜速率;三相PEO陶瓷层的主要物相为SiO₂及高温稳定相α-Al₂O₃和c-ZrO₂,其独特的微结构和成分致使ZrO₂纳米颗粒改性的陶瓷层具有良好的热防护性能和热冲击性能。     

石墨烯/6H-SiC(0001)表面高质量USb2 薄膜的制备和表征

重费米子体系可以通过维度等调控手段来展现出丰富而有吸引力的量子基态。首次通过分子束外延技术在石墨烯/6H-SiC（0001）衬底成功制备了高质量的USb₂薄膜。结合反射式高能电子衍射、X射线衍射、电输运和X射线光电子能谱测量,证明了所制备的USb₂薄膜是高质量的单晶薄膜。此外,利用扫描隧道显微镜和角分辨光电子能谱对USb₂薄膜的表面形貌、原子结构和能带结构进行了表征。结果显示,生长的USb₂薄膜的表面原子结构、电输运性质和能带结构与块体USb₂单晶相似。最后,高质量USb₂薄膜的成功制备和表征为未来通过生长理想厚度的超薄膜在低维铀基重费米子系统中探索奇妙性能提供了宝贵的实验经验。     

Preparation of ZrO<Subscript>2</Subscript> dielectric layers by subsequent oxidation after Zr film deposition with negative substrate bias voltage

ZrO₂ dielectric layers were prepared by a two-step process, a deposition of pure Zr film with and without a negative substrate bias voltage and a subsequent oxidation of the Zr films. We focused on the effect of the negative substrate bias voltage on the Zr film deposition and the subsequent oxidation of the Zr films. As a result, the Zr film deposited at the substrate bias voltage of −50 V (Vs = −50 V) was found to have a high intensity peak of Zr (100) and a uniform and smooth surface. From the capacitance-voltage and current-voltage measurements of the ZrO₂ films, a high dielectric constant of 21 and the equivalent oxide thickness (EOT) of 2.6 nm were obtained on the oxidation layer of the Zr film deposited at Vs = −50 V. On the other hand, a low dielectric constant of 15 and the EOT of 3.6 nm was obtained on that of the Zr film deposited at Vs = 0 V. The leakage current density of the ZrO₂ film (Vs = −50 V) was 5.69×10⁻⁴ A/cm², and this value was much lower than the 1.21×10⁻⁴ A/cm² for the ZrO₂ film (Vs = 0 V). It was found that the two-step process by subsequent oxidation after film deposition using a negative substrate bias voltage is useful for obtaining high-quality dielectric layers.     

Influence of deposition temperature on mechanical properties of plasma-sprayed hydroxyapatite coating on titanium alloy with ZrO<Subscript>2</Subscript> intermediate layer

Hydroxyapatite coatings were plasma sprayed on the Ti6A14V substrate with and without an intermediate ZrO₂ layer; meanwhile the temperatures of substrates were varied at 90, 140, and 200 °C. The coatings were subjected to the standard adhesion test per ASTM C633-79. The purpose of the investigation was to study the effects of those processing variables on the bonding strength and failure behavior of the system. It is found that the bonding strengths of HA/ZrO₂ and HA coatings generally decrease with increasing substrate temperature, except for the HA/ZrO₂ coating deposited at 200 °C. The rationale of the results is attributed to the residual stress reported in the literature. Introducing ZrO₂ bond coat is found to significantly promote the bonding strength of HA coating. The possible strengthening mechanism is the rougher surface of ZrO₂ bond coat and the higher toughness of ZrO₂, which provide the mechanical strengthening effects. The slightly denser HA in 200 °C deposited HA coating cannot explain the high bonding strength of the HA/ZrO₂ coating, nor the mechanical strengthening effect of ZrO₂ intermediate layer should apply. It is believed that a stronger diffusion bonding is formed at the interface of HA and ZrO₂, which increases the bonding between them chemically. The bonding strengths of HA/ZrO₂ and HA coatings are correlated with the area fraction of adhesive failure of the coatings. The correlation explains the findings in this study.     

Mechanical and corrosion resistance properties of electrodeposited Cu–ZrO2 nanocomposites

Electrodeposited Cu–ZrO₂ nanocomposites were prepared by suspending ZrO₂ nanoparticles in an acid copper electroplating bath at pH ～1. The calculated average crystallite size of electrodeposited pure copper and Cu–ZrO₂ nanocomposites were ～32 and ～30?nm, respectively. The measured crystallite structure was fcc and the texture was (220) for both electrodeposited pure copper and Cu–ZrO₂ nanocomposites. The surface morphology and composition of electrodeposited pure copper and Cu–ZrO₂ nanocomposites were characterised by SEM with EDX analysis. The microhardness and wear resistance of the electrodeposited Cu–ZrO₂ nanocomposite was higher than that of pure copper. The corrosion resistances of electrodeposited Cu–ZrO₂ nanocomposite and pure copper were evaluated by electrochemical Tafel polarisation studies. This revealed that Cu–ZrO₂ nanocomposites have higher corrosion resistance than electrodeposited pure copper in 3.5% NaCl (w/v) solution.     

Electrolytic MgO/ZrO2 duplex-layer coating on AZ91D magnesium alloy for corrosion resistance

By a two-step fabrication process of electrolytic deposition and annealing treatment, an MgO/ZrO₂ duplex-layer coating has been prepared on AZ91D magnesium alloy as a protective film against corrosion. Owing to the chemical bonding formed after the condensation of precursory hydroxides, the adhesion strength, thickness and compactness of MgO coating on the substrate are significantly enhanced by the intermediate ZrO₂ layer which prevents the formation of corrosion product Mg₂(OH)₃Cl·4H₂O. As a result, the MgO/ZrO₂ duplex-layer coated specimen reveals relatively high corrosion resistance and superior stability in 3.5 wt% NaCl solution with respect to the MgO single-layer coated specimen.     

The tribological behavior of spin-assisted layer-by-layer assembled Cu nanoparticles-doped hydrophobic polyelectrolyte multilayers modified with fluoroalkylsilane

Hydrophobic polyelectrolyte multilayers (PEMs) doped with Cu nanoparticles and modified with fluoroalkylsilane were prepared by a series of reaction cycles which consist of cycling the PEMs-coated substrate in Cu²⁺ and NaBH₄ solutions, where the polyelectrolyte multilayers were constructed by alternate pipetting of the solutions of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrene sulfonate) onto a spinning substrate. The as-prepared hydrophobic surfaces were characterized by means of X-ray photoelectron spectroscopy, atomic force microscopy, and contact angle measurement. The micro-friction and macro-tribological behavior of the multilayers were investigated. Results indicate that the micro-tribological behavior of the PEMs obeys the modified Amonton's Law, and the macro-tribological behavior of the Cu nanoparticles-doped hydrophobic PEMs is closely related to the wettability. Namely, the more hydrophobic the surfaces are, the longer the antiwear life is. Furthermore, the hydrophobic surfaces have lower friction coefficient under water lubrication than under dry-sliding. The reason lies in that the hydrophobic PEMs have low surface energy and less energy loss during sliding under water lubrication, leading to a lower friction coefficient.     

Comparative study on corrosion protection properties of electroless Ni‐P‐ZrO2 and Ni‐P coatings on AZ91D magnesium alloy

Electroless Ni‐P‐ZrO₂ and Ni‐P coatings on AZ91D magnesium alloy were prepared, and their corrosion protection properties were compared in this paper. The potentiodynamic curves and electrochemical impedance spectroscopy (EIS) of the coated magnesium alloy in 3.5% NaCl solution showed that the corrosion performance of Ni‐P‐ZrO₂ composite coating was superior to that of Ni‐P coating. The same conclusion was obtained with salt spray and immersion tests. The corrosion morphologies of two kinds of coatings with various immersion time intervals in 3.5% NaCl solution indicated that most corrosion products concentrated on the nodules boundaries of Ni‐P coating and blocked corrosion pit was the main corrosion form. For the Ni‐P‐ZrO₂ coating, tortuous nodules boundaries were not the weak sites of the coating and corrosion initiated from the nickel phosphor alloy around the nanometer powders. Open corrosion pits occurred on the composite coating surface, and the coating was corroded gradually. Thus, the Ni‐P‐ZrO₂ coating exhibited better corrosion protection property to magnesium alloy substrate than Ni‐P coating.     

Composition, surface structure, and thermal behavior of ZrO2 + TiO2/Ti and ZrO2 + CeOx + TiO2 composites formed by plasma-electrolytic oxidation

Specific surface structures of ZrO₂ + TiO₂ (I) and ZrO₂ +CeO_x + TiO₂ (II) coatings on titanium before and after annealing at 850°C for 24 h in air are studied. Whiskers are found on the surface of type-I coatings before annealing, and perfectly edged crystals composed of TiO₂ and ZrO₂ oxides are found upon annealing. Pores in both coatings have a multilevel structure. In the case of type-I coatings, orifices of pores are covered with titanium. In type-II coatings, pore orifices contain titanium, zirconium, and oxygen. Oxygen deficiency implies that titanium and zirconium are present in pore orifices in metallic state. In type-II coatings, the surface distribution of cerium is heterogeneous. Mechanical treatment of the annealed coatings causes their exfoliation from the substrate metal. In the case of both coatings, the exfoliating surfaces are composed of TiO₂ blocks containing excess oxygen.     

Characterization and properties of the MgF2/ZrO2 composite coatings on magnesium prepared by micro-arc oxidation

Through micro-arc oxidation, the MgF₂/ZrO₂ composite coatings were prepared on magnesium at the different applied voltages (in the range of 400-550 V) in a zirconate electrolytic solution. The morphologies, phase components, microhardness, bond strengths, and corrosion resistances of the composite coatings were investigated. The effect of the applied voltages on the characteristics and properties of the composite coatings and the basic formation mechanism of the coatings were also discussed. The results indicate that the composite coatings are relatively dense and uniform in thickness, and predominantly composed of MgF₂, tetragonal ZrO₂ (t-ZrO₂) and monoclinic ZrO₂ (m-ZrO₂). The composite coatings exhibit a gradient distribution in phase component from the surface to the inner part. It is found that the applied voltage plays an important role in the characteristics and properties of the composite coatings. With the increase of the applied voltage, the thickness and the t-ZrO₂ content of the composite coatings increase, while the m-ZrO₂ content decreases and no significant variation is observed in the MgF₂ content. Moreover, the surface microhardness and bond strength of the coatings increases with the applied voltage increasing. The microhardness values display a gradient distribution in the cross sections of the coatings, and the maximum microhardness value and its corresponding position in the cross sections are related to the applied voltage. In addition, the corrosion resistances of the composite coatings on magnesium surface are obviously superior to the magnesium substrate in the NaCl solutions, and the effect is more remarkable at higher voltage.     

Comparison of structural and optical properties of TeO<Subscript>2</Subscript> nanostructures synthesized using various substrate conditions

Several TeO₂ low-dimensional nanostructures were prepared by thermal evaporation using four substrate conditions: (1) a bare substrate, (2) a scratched substrate, (3) a Au-catalyst-assisted substrate, and (4) a multi-walled carbon nanotube (MWCNT)-assisted substrate. Scanning electron microscopy and transmission electron microscopy analysis reveals that the morphologies of the nanostructures synthesized using these methods gradually changed from nanoparticles to ultra-thin nanowires with single tetragonal-type TeO₂. Photoluminescence (PL) spectra reveal that the PL intensities of the TeO₂ nanomaterials obtained using methods (1) and (2) are slightly increased, whereas the intensities of the TeO₂ nanostructures obtained using methods (3) and (4) differ significantly depending on the initial substrate conditions. The emission peak is also blue-shifted from ~440 nm to ~430 nm for the scratched surface condition due to an excitonic transition. The increase in the blue emission for the MWCNT-assisted condition is attributed to the degree and type of excitons and defects in the TeO₂ nanostructures.