TiAl合金表面Si-Co-Y扩散渗层的高温抗氧化性能

采用扩散共渗方法在TiAl合金表面制备了Si-Co-Y渗层,分析了渗层的组织结构、形成机理及其在950 ℃时的抗氧化性能。所制备的Si-Co-Y渗层组织致密,呈多层结构：主要由TiSi₂表层,TiSi₂+Ti₅Si₄+Ti₅Si₃混合组成的外层,Ti₅Si₃中间层和TiAl₂内层组成；渗层生长过程由Si的向内扩散控制,且遵循先沉积Si后沉积Co的有序过程。氧化实验结果表明,Si-Co-Y渗层具有良好的高温抗氧化性能,在950 ℃氧化100 h后表面形成了由SiO₂, TiO₂和Al₂O₃组成的保护性氧化膜；该氧化膜的生长遵循抛物线规律,氧化增重的抛物线速率常数约为6.3×10_-2 ^mg₂^/cm₄ ^h_1/2^,较基体合金低约一个数量级。     

磁致涡流效应对化成铝箔Al2O3-TiO2复合膜结构及性能的影响

以TiCl₄为前驱体溶液,通过磁场辅助电沉积法在腐蚀箔表面形成具有高介电常数的Al₂O₃-TiO₂复合氧化膜。系统研究了磁致涡流效应（MHD效应,Magnetohydrodynamics）对电解液中离子扩散行为及Al₂O₃-TiO₂复合氧化膜结构与性能的影响规律。采用XRD能谱、扫描电镜SEM以及EDS能谱等手段对氧化膜晶相、表面/截面形貌以及Ti元素分布进行表征。结果表明,随着磁感应强度B的增强,电解液中Ti⁴⁺向箔面及蚀孔内的扩散速率增大,复合膜层中锐钛矿型TiO₂含量提高,且其在箔面及蚀孔内部分布均一性提升。另外,氧化膜阳极升压曲线、Tafel极化曲线及交流阻抗曲线的分析结果表明,MHD效应提高了复合氧化膜介电常数,减少了阳极氧化阶段的形成电量,对应的化成箔比电容增大至58.29 μF/cm²,较之无MHD制备的Al₂O₃-TiO₂化成箔,其形成电量减少了24.6%,比电容增加了10.1%。     

在Q235钢表面原位生长的氧化铁膜对其在含Cl-溶液中腐蚀行为的影响Ⅰ-原位生长的γ-FeOOH膜的防护性能

    利用动电位极化曲线和交流阻抗谱等电化学测量技术,研究了Q235钢表面原位生长的γ- FeOOH膜在0.25 mol/L Na₂SO₄+10^-4mol/L NaCl、0.25 mol/L Na₂SO₄+10-3mol/L NaCl、0.25 mol/L Na₂SO₄+10^-2 mol/L NaCl水溶液中的电化学行为及在不同浓度的Cl^-水溶液中γ-FeOOH膜对Q235钢的保护作用.结果表明,Cl^-含量较低时,γ-FeOOH膜的存在明显地促进了Q235钢的阴极反应,该膜对基材无保护作用;随Cl-浓度的增加,阴极电流密度大幅减小,当Cl^-浓度达到10^-2 mol/L时,γ-FeOOH 膜能在一定程度上抑制基材的腐蚀,此时γ-FeOOH膜表现出对基材有保护作用.     

Co对铸态TiAl-Nb合金组织和高温氧化性能的影响

采用非自耗电弧熔炼方法经多次重熔制备了Ti45Al-6Nb-xCo合金(x=0, 0.5, 1, 2和4 at.%),研究了不同Co含量合金的组织结构和高温抗氧化性能。结果表明,增加合金中的Co含量能够细化α₂+γ片层组织,促进合金中形成γ和B₂相,并抑制α₂相形成;合金中Co含量超过2 at.%会导致富Co相析出和组织粗化。1000℃空气中的恒温氧化结果表明,适量的Co合金化能够显著改善TiAl-Nb合金的高温抗氧化性能;Ti45Al-6Nb-1Co合金的氧化的抛物线速率常数约为1.36×10^_-2mg^₂/cm^₄h,较Ti45Al-Nb合金低约1个数量级;但Co含量超过2 at.%后,随Co含量增加,合金的氧化速率呈增加趋势。     

粉末包埋渗铝与气氛渗铝对P92钢650℃饱和蒸汽氧化行为的影响

表面渗铝技术可以在不改变基体材料力学性能的基础上显著提高基体的抗高温蒸汽氧化性能。 利用低温粉末包埋和气氛渗铝两种方法在 P92 钢表面制备了铝化物涂层,并结合氧化增重法、扫描电镜观察及 XRD 分析,研究了两种工艺下铝化物涂层的 650 ℃饱和蒸汽氧化行为。 结果表明:P92 钢抗氧化能力不足,生成了由外层疏松层瘤状富铁氧化物与表面氧化膜下方内氧化物 FeCr₂O₄ 组成的双层结构氧化膜,外层富铁氧化膜在氧化 300 h 后发生剥落;低温包埋渗铝所得涂层为 β-FeAl 层,氧化 500 h 后试样表面形成极薄的保护性 α-Al₂O₃ 氧化膜(<0. 2 μm);气氛渗铝涂层为单层 Fe₃Al 结构,氧化 500 h 后试样外表面形成了 Fe₃O₄₊Fe₂O₃ 氧化膜,厚度为 1. 3 μm,靠近涂层表面生成单层连续 Al₂O₃ 氧化膜。 采用低温包埋和气氛渗铝均可提升 P92 钢的抗蒸汽氧化能力。     

30CrMnSiA钢表面镉镀层化学转化膜的电化学特性

目的 通过研究镉镀层绿色化学转化膜的电化学性能,获得镉镀层最佳绿色化学钝化工艺。方法 采用无氰镀镉工艺,在30CrMnSiA钢表面电镀镉。采用植酸和钼酸钠在镉镀层表面进行绿色钝化处理,构建复合化学转化膜。通过研究钼酸钠浓度、处理时间和植酸浓度对绿色钝化处理镀镉层在质量分数为3.5%的NaCl溶液中电化学性能的影响,获得最佳的镀镉层绿色钝化工艺。结果 在处理时间为10 min、植酸的质量分数为1.0%的条件下,当钼酸钠的质量分数增至3%时,开路电压先从−0.741 9 V增至−0.739 7 V后,再降至−0.761 1 V,电荷转移电阻Rct从2.34 kΩ.cm²增至8.79 kΩ.cm²,腐蚀抑制率从72.9%增至92.8%,自腐蚀电流密度Jcorr从81.47 μA/cm²降至最低值(6.887 2 μA/cm²)。当钼酸钠和植酸的质量分数分别为2.0%和1.0%时,随着处理时间的延长,开路电压从−0.755 9 V增至−0.729 5 V,Rct先增至6.68 kΩ.cm²,然后降至5.28 kΩ.cm²,自腐蚀电流密度从16.26 μA/cm²降至4.527 μA/cm²。当钼酸钠的质量分数为2.0%、处理时间为10 min时,随着植酸浓度的增加,试样的开路电压从−0.739 3 V降至−0.756 1 V,Rct先增至6.68 kΩ.cm²,然后降低,自腐蚀电流密度Jcorr呈现先降至最小值后再增大的趋势。结论 与镉镀层相比,经化学转化膜处理后试样表现为高的开路电压、大的电荷转移电阻和低的自腐蚀电流。得到了耐蚀性好且成本较低的镉镀层表面绿色钝化工艺,钼酸钠和植酸的质量分数分别为2.0%和1.0%,处理时间为10 min。     

机械能助渗锌铝渗层的防腐耐磨性能分析

高温高湿高盐雾苛刻环境中螺栓件的腐蚀问题备受广大学者关注。 结合紧固件装配需求,采用机械能助渗技术在 450 ℃温度下制备 Zn-Al 功能渗层。 通过扫描电子显微镜( SEM)、能谱分析(EDS)、显微硬度计、X 射线衍射仪 (XRD)等对锌铝渗层的厚度、物相、硬度和形貌进行表征,采用电化学工作站和摩擦磨损试验机对锌铝渗层的防腐耐磨性能进行研究。 结果表明:机械能助渗制备的锌铝渗层有利于提高基体的防腐耐磨性能。 当锌粉的质量分数为 35%、 铝粉为 15%,保温时间为 4. 5 h,渗炉转速为 7 r/ min 时,涂层呈现出最佳的防腐耐磨性能。 此渗层主要由 Al₂O₃ 、Γ1 相(Fe₁₁Zn₄₀ )和 δ1 相( FeZn_{6. 67}、 FeZn_{8. 87}、 FeZn_{10. 98})组成,其厚度为 91. 12 μm,表面硬度为 413. 2 HV_{0. 05},腐蚀电位为 -0. 9286 V,腐蚀电流密度为 2. 2493 A·cm^-2,低频区阻抗模值为 2284 Ω·cm²,平均摩擦因数为 0. 3887,磨痕宽度为 734. 66 μm,磨痕深度为 21. 7 μm,磨损体积为 16. 75×10^-3mm³。     

复合喷丸强化对A-100钢旋转弯曲疲劳寿命的影响

对未喷丸、一次喷丸和复合喷丸的A-100钢试样进行了表面形貌、表面粗糙度、残余应力场及旋转弯曲疲劳寿命的测试,研究表面形貌、表面粗糙度、残余应力场和旋转弯曲疲劳寿命的关系,揭示A-100钢复合喷丸强化机理。结果表明：与一次喷丸相比,在表面形貌方面,复合喷丸可获得更为平整的表面形貌和更低的表面粗糙度值,复合喷丸后,Rz值较一次喷丸降低24%~47%;在残余应力方面,复合喷丸的最大残余压应力值、最大残余应力值深度和最大残余应力场深度基本无变化,而近表层（0~100 μm）的残余压应力值增大。表面形貌的改善及残余压应力场是复合喷丸强化效果的两个主要成因。在一次喷丸的基础上,复合喷丸可进一步提高A-100钢的疲劳寿命,且可以在较低的喷丸强度下获得更优的强化效果。在σ_max=1000 MPa,R=-1条件下,其旋转弯曲疲劳寿命较未喷丸试样可提高50倍以上,较一次喷丸试样可提高5倍以上。     

γ-TiAl合金表面Al2O3/Al复合涂层的抗高温熔盐腐蚀性能研究

采用磁控溅射技术于γ-TiAl合金表面制备Al₂O₃/Al复合涂层。在850 °C下、 100 wt.% Na₂SO₄熔盐中观测Al₂O₃/Al复合涂层的高温腐蚀行为。结果表明,Al₂O₃/Al复合涂层具备由Al₂O₃表层、富Al中间层以及互扩散层组成的梯度结构,因而有效地提高了基体γ-TiAl合金的抗高温腐蚀性能。在腐蚀实验后,涂层试样表面相结构为Al₂O₃,TiO₂和TiAl₃。致密的Al₂O₃/Al复合涂层有效地抑制了O_2-,S_-和Na₊对基体γ-TiAl合金的侵蚀。并且,Al₂O₃/Al复合涂层的梯度结构亦使其表现出了优异的抗开裂和抗剥落性能。     

CoCrNiAlY涂层制备工艺对组织形态及高温氧化行为的影响

为了研究CoCrNiAlY涂层微观组织结构对高温氧化行为和剥落行为的影响规律,采用激光熔覆技术和等离子喷涂工艺在718高温合金表面制备CoCrNiAlY涂层,观察其微观组织形态。利用XRD和SEM对1150 ℃高温氧化试验样品进行氧化层物相分析和形貌观察。结果表明,激光熔覆制备的CoCrNiAlY涂层中形成了胞状亚结构的等轴晶凝固组织,相对于等离子喷涂制备的CoCrNiAlY涂层结构更致密,具有更优异的抗高温氧化性能。在高温氧化过程中,等离子喷涂CoCrNiAlY涂层生成了以Cr₂O₃结构为主的复合氧化膜。激光熔覆CoCrNiAlY涂层生成Al₂O₃结构的单一氧化膜,而且熔覆层中原位形成的Y₂O₃钉扎作用能有效提高氧化膜的抗剥落性。文中系统分析讨论了两种不同工艺制备的组织形态对高温氧化膜形成机制的影响,激光熔覆涂层在高温下主要是以界面扩散方式形成致密的Al₂O₃膜,等离子喷涂涂层在高温下以界面反应的方式快速形成Cr₂O₃复合氧化膜。     

Photoluminescence properties and energy-transfer of thermal-stable Ce, Mn-codoped barium strontium lithium silicate red phosphors

A series of thermal-stable Ce³⁺, Mn²⁺-codoped barium strontium lithium silicate (BSLS) phosphors was synthesized by a high-temperature solid-state reaction. The XRD patterns of this phosphor seem to be a new phase that has not been reported before. BSLS:Ce³⁺, Mn²⁺ showed two emission bands under 365 nm excitation: one observed at 421 nm was attributed to Ce³⁺ emission, and the other found in red region was assigned to Mn²⁺ emission through Ce³⁺-Mn²⁺ efficient energy transfer. The Mn²⁺ emission shifted red along with the replacement of barium by strontium, which was due to the change of crystal field. A composition-optimized phosphor, BSLS:0.10Ce³⁺, 0.05Mn²⁺ (Ba = 65), exhibited strong and broad red-emitting and supreme thermal stability. The results suggest that this phosphor is suitable as a red component for NUV LED or high pressure Hg vapor (HPMV) lamp.     

Nanocrystallization and photoluminescence of Ce/Dy/Eu-doped fluorosilicate glass ceramics

Ce³⁺-Eu²⁺-Dy³⁺-Eu³⁺-doped fluorosilicate glass ceramics containing orthorhombic CaCeOF₃ nanocrystals were prepared by annealing the precursor glass above 640 °C, along with the reduction of Eu³⁺ → Eu²⁺. Under near ultraviolet excitation, the emission bands of Eu²⁺ or Dy³⁺ were enhanced by several ten or hundred times, owing to energy transfers from Ce³⁺ to Eu²⁺ or Dy³⁺. The glass and glass ceramics emitted warm white light deriving from the blue, yellow and red emission from Eu²⁺, Dy³⁺ and Eu³⁺. Tuning the annealing temperature, the Eu²⁺/Eu³⁺ ratio and the warm white Commission Internationale de I’Eclairage (CIE) coordinates can be adjusted. Thus, the present materials can be applied on warm white high power light-emitting-diodes for indoor illumination application.     

Upconversion luminescence of Yb/Tb/Er-doped fluorosilicate glass ceramics containing SrF2 nanocrystals

Yb³⁺/Tb³⁺/Er³⁺-doped transparent alkaline earth fluorosilicate glass ceramics containing SrF₂ nanocrystals were prepared and their microstructures and spectroscopic properties were investigated. The formation of SrF₂ nanocrystals enriched with Yb³⁺/Tb³⁺/Er³⁺ in the glass ceramics was confirmed by XRD, HRTEM and SAED. The glass ceramics exhibited intense upconversion luminescence behaviors, owing to efficient energy transfers from Yb³⁺ to Er³⁺ and Tb³⁺ and low phonon assistant non-radiative transition probabilities of excited Er³⁺ and Tb³⁺. The upconversion could be enhanced significantly by increasing the annealing temperature and the luminescence color could be adjusted by varying the Yb³⁺/Tb³⁺/Er³⁺ ratio. Upconversion of Er³⁺ could be described as sequential energy transfer from single Yb³⁺ to single Er³⁺, while upconversion of Tb³⁺ described as cooperative energy transfer from double Yb³⁺ to single Tb³⁺.     

Substrate Effect on the High-Temperature Oxidation Behavior of a Pt-Modified Aluminide Coating. Part I: Influence of the Initial Chemical Composition of the Coating Surface

The effect of substrate composition on the oxidation behavior of the industrial NiPtAl coating RT22 ^TM was investigated by studying the isothermal and cyclic-oxidation behavior of this coating deposited on three different Ni-base superalloys (CMSX-4 ^TM , SCB ^TM and IN792 ^TM ). Isothermal tests were performed at 900, 1050 and 1150°C for 100 h. Cyclic oxidation was studied at 900°C with a holding time of 300 h for up to 52 cycles (i.e, 15,600 h at 900°C). Thermogravimetric analysis (TGA), X-ray diffraction (XRD), microstructural and analytical investigations using scanning-electron microscopy (SEM) and transmission-electron microscopy (TEM), both equipped with energy-dispersive X-ray spectroscopy (EDS) were performed to characterize the oxidation behavior of the systems studied. An effect of the superalloy substrate was observed and related to the initial chemical composition of the coating surface which depends on the superalloy and the associated heat treatments. The effect of the substrate’s alloying elements is discussed. Particularly the influence of Ti and Ta that formed rutile-type oxides inducing oxide-scale cracking and spallation. The excellent resistance to cyclic oxidation of the coating systems studied at 900°C was also demonstrated from very long duration tests of 15,600 h.     

Cl-浓度对含盐污水中 10#碳钢腐蚀行为的影响

针对兰州石化某常减压装置换热器管束(主要材质为10#碳钢)在使用过程中发生腐蚀的问题,通过浸泡试验和电化学测试,研究了壳程介质中的Cl-浓度对10#碳钢在含盐污水中腐蚀行为的影响。结果表明:弱碱性溶液中的OH-与Cl-竞争吸附,使得Cl-浓度的变化对碳钢的腐蚀速率基本没有影响,其腐蚀速率在0.145～0.185 mm/a之间。     

Impact of Ce ion on microstructure and luminescence character of Ho/Yb co-doped ZrO2 nanocrystal

By solid-state synthesis method, Ho³⁺/Yb³⁺ co-doped CeO₂-ZrO₂ nano-powders have been prepared. The concentration of Ce⁴⁺ ions has greater effect to the oxygen lattice structure. When the concentration of Ce⁴⁺ ions is 30 mol%, the oxygen lattice is a tetrahedral space group and the luminescence intensity of the sample is strongest. The results show that the lattice structure can be changed by inducting the Ce⁴⁺ ions into Ho³⁺/Yb³⁺ co-doped ZrO₂. And the emission character can be improved.     

Luminescence properties of Eu and Eu doped calcium-deficient hydroxyapatite prepared in air

Eu-doped calcium-deficient hydroxyapatite Ca_8.95Eu_0.05HPO₄(PO₄)₅OH (designated CDHA:Eu) was prepared via the coprecipitation method and calcined in air. Phase purity, crystal structure and morphology of the CDHA:Eu were characterized using X-ray diffraction spectrometer and scanning electron microscopy. The photoluminescence excitation and emission spectra of Eu²⁺ and Eu³⁺ ions were measured using luminescence spectrometer. The emission spectra showed a broad emission band centered at 450 nm corresponded to the typical 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ions, and sharp peaks corresponded to the ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3, 4) transitions of Eu³⁺ ions. This research was focused on the site-distribution of Eu³⁺ ions. The Eu³⁺ in different sites had different spectroscopic features and the charge compensation mechanisms were also discussed.     

Upconversion luminescence properties of Tm-Yb co-doped titania-zirconia composites nanocrystals

Tm³⁺-Yb³⁺ co-doped titania-zirconia composites were synthesized by co-precipitation method with aqueous ammonia as precipitator. Time evolution of upconverted emission of thulium in ZT_0.4-Tm_0.01Yb_0.04 (40%ZrO₂-60%TiO₂-1%Tm³⁺-4%Yb³⁺) demonstrated ZT_0.4 to be a promising matrix in the field of upconversion luminescence. Raman spectrum shows low phonon energy (800 cm⁻¹) of ZT_0.4 ensuring a fluent phonon transition process. The luminescent properties were investigated by photoluminescence spectra. Strong blue and red upconversion emissions could be observed which were attributed to ¹G₄-³H₆, ³F₂-³H₆, ¹G₄-³F₄ transitions, respectively.     

Photoluminescent properties of LiSrxBa1−xPO4:RE (RE = Sm, Eu) f-f transition phosphors

Rare-earth ions (Sm³⁺ or Eu³⁺) doped LiSr_xBa_1−xPO₄ (x = 0, 0.2, 0.4, 0.6, 0.8, 1.0) f-f transition phosphor powders were prepared by a high temperature solid-state reaction. The resulted phosphors were characterized by X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy. The results of XRD indicate that the phase structure of the sample changes from LiBaPO₄ to LiSrPO₄ when x changes from 0 to 1.0. The excitation spectra indicate that only direct excitation of rare earth ions (Sm³⁺ or Eu³⁺) can be observed. The doped rare earth ions show their characteristic emission in LiSr_xBa_1−xPO₄, i.e., Eu³⁺⁵D₀-⁷F_J (J = 0, 1, 2, 3, 4), Sm³⁺⁴G_5/2 → ⁶H_J (J = 5/2, 7/2, 9/2, 11/2), respectively. The dependence of the emission intensities of the LiSr_xBa_1−xPO₄:Sm³⁺ and LiSr_xBa_1−xPO₄:Eu³⁺ phosphors on the x value and Ln³⁺ (Ln³⁺ = Sm³⁺, Eu³⁺) concentration is also investigated.     

Investigation on temperature dependence of photoluminescence in Sr1.7Eu0.3MxCeO4.15+x/2 (M = Li, Na, K, x = 0, 0.3) red phosphors

The temperature-dependent luminescence of Sr_1.7Eu_0.3M_xCeO_4.15+x/2 (M = Li⁺, Na⁺, K⁺, x = 0, 0.3) samples was investigated and discussed in the temperature range from 303 to 573 K. It is found that the thermal quenching temperature of samples decreases with Li⁺-/Na⁺-doping but increases with the incorporation of K⁺. We suggest that these observations are resulted from two factors. One is that the incorporation of Li⁺/Na⁺/K⁺ ions reduces the strength of potential field at the O²⁻ sites, and then results in a red-shift of the Eu-O charge transfer band. The other is that Δr expands with Li⁺-/Na⁺-doping but shrinks with K⁺-doping. We consider that it is a feasible way to adjust the temperature-dependent luminescence properties of materials by introducing appropriate impurities.