Ti掺杂VO2(M)粉体制备及性能研究

M相二氧化钒(VO₂(M))是一种在68℃左右具有特殊相变特性的智能隔热窗材料,然而VO₂(M)的相变稳定性还较差、对太阳光的调制能力还不够高,严重限制其在智能隔热窗中的工业化应用。本文主要以五氧化二钒为钒源,草酸为还原剂,尿素为沉淀剂,硫酸钛为掺杂剂,水热还原法制备粉体M相钛(Ti)掺杂VO₂,简称Ti-VO₂(M)粉体。通过X射线衍射仪(XRD)、场发射扫描电子显微镜(SEM)、紫外-可见-近红外分光光度计(UV-Vis-NIR)、差示扫描量热仪(DSC)和X射线能谱仪(EDS)分析所合成粉体的元素/物相组成和结构、结晶形态、太阳光反射率/透过率和相变温度的变化情况,优化Ti^₄₊掺杂量。研究发现,Ti^₄₊掺杂量控制在3%时,制备的Ti-VO₂(M)粉体的综合性能最优,为进一步应用智能隔热有机玻璃提供重要的数据与技术支撑。     

纳米柱状多孔WO3- x /TiO2 薄膜的电致变色性能

采用反应磁控溅射在掠射角度α=0°和α=80°的条件下制备氧化钨（WO_3-x）薄膜,然后在其表面沉积二氧化钛（TiO₂）。利用X射线衍射仪（XRD）、场发射扫描电镜（FE-SEM）和X射线光电子能谱仪（XPS）对WO_3-x/TiO₂薄膜的晶体结构、表面/断面形貌以及表面化学成分进行表征。在三电极体系1 mol/L LiClO₄/PC溶液中,采用电化学工作站和紫外-可见分光光度计测试了WO_3-x/TiO₂薄膜的电致变色性能。XRD结果表明,WO_3-x/TiO₂薄膜为非晶态结构,与掠射角度无关。当掠射角度为80°时,获得了纳米柱状多孔薄膜。从 W 4f和Ti 2p的XPS谱图确认氧化钨为亚化学计量比的WO_3-x,而氧化钛为满足化学计量比的TiO₂。与致密薄膜相比,纳米柱状多孔薄膜需要较低的驱动电压且具有较快的响应速度。纳米柱状多孔薄膜的电荷容量为83.78 mC,是致密薄膜电荷容量30.83 mC的2倍以上。在±1.2 V驱动电压下,注入和脱出离子扩散速率分别为D_in=5.69×10^-10 cm²/s和D_de= 5.08×10^-10 cm²/s。与纯WO₃薄膜相比,WO_3-x/TiO₂薄膜的电致变色循环稳定性更好。纳米柱状多孔薄膜在可见光范围内具有较大的光调制幅度,因此其光密度变化（ΔOD）大于致密薄膜。     

喷丸处理对45钢表面Al+注入层抗高温氧化性的影响

为改善45钢的抗高温氧化性能，在其表面制备单一Al⁺注入层和喷丸+Al⁺注入层。检测表征改性层的表面粗糙度、显微硬度、微观形貌、以及铝元素含量，并进行600℃、200 h下的抗高温氧化性能试验。研究结果表明：喷丸处理45钢表面呈现出凹坑、丘陵状、具有近似等轴状纳米晶结构，Al⁺注入使纳米晶进一步细化。喷丸处理使45钢的表面粗糙度Ra从0.42 μm增至1.15 μm，显微硬度、注入铝元素含量及氧化增重分别从单一Al⁺注入层的257 HV_0.05增至喷丸+Al⁺注入层的最高505 HV_0.05，从3.7%增至4.2%和从14.8 mg·cm^-2降至8.3 mg·cm^-2。即喷丸处理有效增强了45钢表面Al⁺注入层的抗高温氧化性能。     

激光热喷涂Co30Cr8W1.6C3Ni1.4Si涂层在PAO+2.5%MoDTC油中摩擦学特性

为了提高TC4合金的耐磨性能,采用激光热喷涂技术在其表面制备了Co₃₀Cr₈W_1.6C₃Ni_1.4Si涂层。通过扫描电子显微镜（SEM）和X射线衍射（XRD）分析了涂层的形貌和物相,并通过摩擦磨损实验研究了涂层在PAO+2.5% MoDTC（质量分数）油中的磨损行为。结果表明,激光热喷涂的Co₃₀Cr₈W_1.6C₃Ni_1.4Si涂层主要由Ti、WC_1-x、CoO、Co₂Ti₄O和CoAl相组成,在涂层界面形成冶金结合。在激光功率为1000、1200和1400 W时所制备的涂层平均摩擦因数分别为0.151、0.120和0.171,其对应的磨损率分别为1.17×10^-6、1.33×10^-6和2.80×10^-6 mm³?N^-1?m^-1,磨损机理为磨粒磨损,其枝晶尺寸对降磨起主要作用。     

石墨烯量子点/纳米Al2O3协同生长润滑转移膜机制∗

为改善环氧树脂(EP)的摩擦学性能,将氮掺杂的石墨烯量子点(N-GQDs)和 Al2O3 纳米颗粒(Nano-Al₂O₃ )杂化物添加到环氧树脂中制备 EP 纳米复合材料。 利用 MRH-1A 摩擦试验机考察纳米复合材料在 PAO 油润滑条件下的摩擦磨损性能, 结合磨损表面的形貌及摩擦化学分析,研究界面转移膜的形成机理和润滑效应。 试验结果表明,3N-GQDs-1Nano-Al₂O₃ / EP 纳米复合材料获得了最好的摩擦学性能,其最低摩擦因数和磨损率分别为 0. 08 和 7. 4×10^-5 mm³ / Nm。 同时对偶金属表面上能够观察到一层均匀的转移膜,其中 C、N、O 元素主要分布于沟壑,而 N、Al 元素则集中于高台区域。 机理分析表明,N-GQDs 和 Nano-Al₂O₃ 有效促进了转移膜的生成,从而避免了摩擦界面的直接接触。     

Cr3C2-NiCr/TiSiN-CrAlN复合涂层制备及高温摩擦学行为研究

目的 基于表面耐高温薄膜和高承载金属陶瓷涂层性能优势协同的设计思想,制备Cr3C2-NiCr/ TiSiN-CrAlN复合涂层,提高硬质薄膜机械性能和不同温度下的摩擦学性能。方法 采用超音速火焰喷涂(HVOF)和电弧离子镀(AIP)技术制备Cr3C2-NiCr/TiSiN-CrAlN复合涂层,通过扫描电子显微镜、X射线衍射仪、纳米压入仪、划痕仪和高温摩擦磨损试验机等对复合涂层的微观结构、机械性能和不同温度下的摩擦磨损行为进行系统研究。结果 Cr3C2-NiCr/TiSiN-CrAlN复合涂层微观结构致密,界面结合良好,其顶层耐高温薄膜由CrAlN结合层和TiSiN-CrAlN交替多层构成,总厚度约6.7 μm,低于不锈钢表面直接沉积TiSiN-CrAlN薄膜的厚度(约9.6 μm)。Cr3C2-NiCr支撑层微观结构和形貌影响其表面沉积TiSiN-CrAlN薄膜的结晶性。Cr3C2-NiCr/TiSiN-CrAlN复合涂层具有优异的机械性能,其纳米硬度和弹性模量分别高达(37.3±2.6)GPa和(506.1±10.6)GPa,结合力相比不锈钢表面TiSiN-CrAlN多层膜显著提高。得益于Cr3C2-NiCr支撑层的引入,复合涂层在不同温度下的摩擦因数和磨损率均比单一薄膜的低,其摩擦因数在900 ℃下可稳定保持在0.44左右,磨损率约为3.13×10^?5 mm³/(N.m),表现出良好的高温摩擦学性能。此外,磨损机制分析表明,500 ℃以下主要为磨粒磨损和黏着磨损,摩擦因数较大、不稳定,但磨损率基本不变;700 ℃时由于Cr3C2-NiCr层的支撑作用而无明显的疲劳磨损,氧化磨损发生;900 ℃时氧化磨损主导,摩擦界面生成主要成分为TiO2、Cr2O3的摩擦反应膜。结论 采用HVOF和PVD相结合的方法在不锈钢表面制备的Cr3C2-NiCr/TiSiN-CrAlN复合涂层具有良好的机械性能和优异的高温摩擦学性能,可进一步改善耐高温薄膜的综合性能,具有良好的应用前景。     

高功率脉冲氙灯铈钨电极工作过程中表面稀土元素分布和价态演变

_{为阐明高功率脉冲氙灯铈钨电极运行过程中的演变过程及工作机理,采用金相显微镜、扫描电镜(SEM)、X-射线光电子能谱(XPS)等手段研究了运行不同发次的高功率脉冲氙灯阴极表面形貌、铈元素的价态演变及其浓度-深度分布状况,结果表明：铈钨电极工作表面出现大量的龟裂纹,其裂纹程度和深度、烧蚀状况均与运行发次有关,工作次数越多裂纹和烧蚀情况越严重;随着运行发次增加,阴极表面铈元素含量向表面扩散,含量升高,最高达12%,分布更加均匀;通过对Ce³⁺/Ce⁴⁺比例分析发现：运行10083发次的铈钨阴极表面活性处于较佳状态;运行14486发次的铈钨阴极表面活性层明显减小,仅有6.66nm,氙灯性能处于下降状态。}     

GLC/成分梯度CNx多层膜的微观结构和摩擦学性能

类金刚石碳膜通常内应力大、结合力低,而多层膜结构可提高结合力。 采用磁控溅射技术在 Si 基体上沉积不同 CNx 层厚度的 GLC/ 成分梯度 CNx 纳米多层膜。 通过扫描电子显微镜(SEM)、X 射线衍射仪(XRD)、X 射线光电子能谱(XPS)、Raman 光谱仪、球盘式摩擦仪、纳米压痕仪等对多层膜的表面形貌、微观结构、力学以及摩擦性能进行分析。 结果表明:多层膜表面平整光滑,CNx 层厚度为 50 nm 的多层膜有明显的层状结构。 多层膜中存在石墨相而 CNx 以微晶或非晶存在。 薄膜的 sp3 键含量、结合力、硬度等均随 CNx 层厚度的增加先增加后减小。 CNx 层厚度对多层膜的大气环境摩擦因数影响很小,但显著降低其真空环境摩擦因数。 多层膜的硬度为( 15 ~ 17. 6) GPa,大气中的磨损率为 (1. 03~ 2. 33)×10^-16 m³N^-1m^-1 ,真空中为(2. 06~ 3. 34)×10^-16 m³N^-1m^-1 。 CNx 层厚度为 20 nm 的多层膜综合性能最佳。     

煤油流量对NiCrBSi-CrSi2涂层微观结构及高温磨损性能的影响

在12CrMoVG基体上通过超音速火焰喷涂(HVOF)技术,分别采用不同煤油流量制备了NiCrBSi-CrSi₂复合涂层。利用 XRD、SEM、EDS、Raman、维氏显微硬度计、电子拉伸试验机和高温旋转式摩擦磨损试验机分别表征了不同煤油流量下涂层物相、组织结构、力学性能和高温摩擦磨损性能。结果表明: 不同煤油流量涂层的物相组成基本相同,均有γ-Ni、Ni₃B、Cr₂B、CrSi₂和Cr₅Si₃,但随着煤油流量升高,涂层中的CrSi₂和Cr₂B的部分会分别转变为Cr₅Si₃和CrB相。涂层显微硬度和结合强度随着煤油流量的升高均呈现先增后减的趋势,孔隙率和磨损率表现出先减后增的趋势。当煤油流量为30 L/h时,粉末熔融效果最好,涂层的孔隙率最低为0.17 %,显微硬度较高达到569 HV_0.3,结合强度较高为59 MPa,磨损率最低为2.84×10_-14 m₃^/(N.m)。磨痕表面产生的 Cr₂O₃、SiO₂和NiCr₂O₄等氧化物以及较高的涂层硬度使得30 L/h的涂层显示出最优的耐高温摩擦磨损性能。涂层的磨损机制以氧化磨损和黏着磨损为主。     

磁性纳米材料Fe3O4-RGO-NH2对Ag+的吸附性能研究

采用一步溶剂热法成功制备了新型磁性纳米吸附剂Fe3O4-RGO-NH2,用透射电子显微镜(TEM)、X射线衍射(XRD)、振动样品磁力计(VSM)及Zeta电势对其形貌及晶型结构进行了表征,研究了Fe3O4-RGO-NH2纳米吸附剂对水溶液中Ag⁺的吸附性能。结果表明,水溶液pH值对Ag⁺吸附具有很大影响,pH=4.0时吸附效果最佳。Ag⁺最大吸附量随着初始浓度及吸附时间的增加而增加,Ag⁺的吸附符合准二级动力学模型。     

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.     

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⁺.     

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.     

Tunable red-green-blue multicolor luminescence in Yb/Tm/Ho:Gd3Ga5O12 nano-crystals

The Yb³⁺/Tm³⁺/Ho³⁺: Gd₃Ga₅O₁₂ nano-crystals have been successfully prepared via a citric acid complex procedure. The luminescence spectra were measured and the up-conversion processes were discussed. By means of adjusting the doping concentrations of Yb³⁺/Tm³⁺/Ho³⁺, the red-green-blue up-conversion luminescence changed obviously. Results indicated that the ratio of red-green-blue up-conversion emissions enhanced heavily with the increasing concentrations of Tm³⁺ doped in the Yb³⁺/Tm³⁺/Ho³⁺:Gd₃Ga₅O₁₂ nano-crystals, which was rooted in the three-photon resonant cross relaxation processes(¹G₄ (Tm) + ⁵I₇ (Ho) → ³H₅ (Tm) + ⁵S₂ (Ho)). The tunable red-green-blue luminescence could be used in the fields of display, illumination, and photonics such as the white light generation.     

Structural characterization of layered LiNi0.85−xMnxCo0.15O2 with x = 0, 0.1, 0.2 and 0.4 oxide electrodes for Li batteries

We report the synthesis of LiNi_0.85−xCo_0.15Mn_xO₂ positive electrode materials from Ni_0.85−xCo_0.15Mn_x(OH)₂ and Li₂CO₃. XRD and XPS are used to study the effect of Mn-doping on the microstructures and oxidation states of the LiNi_0.85−xCo_0.15Mn_xO₂ materials. The analysis shows that Mn-doping promotes the formation of a single phase. With increasing substitution of Mn ions for Ni ions, the lattice parameter a decreases, while the lattice parameters c and c/a increase. XPS revealed that the oxidation states of Ni, Co and Mn in LiNi_0.85−xCo_0.15Mn_xO₂ compounds (where x = 0.1, 0.2 and 0.4) were +2/+3, +3 and +4. The substitution of Mn ions for Ni ions induces a decrease in the average oxidation state of Ni. Because the substitution of Mn for Ni ions is complex, the extent of the changes between the lattice parameter and L_M-O differ. The occupation of Ni in Li sites is affected by the ordering of Mn⁴⁺ with Ni²⁺ and Mn⁴⁺ with Li⁺.     

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.     

Luminescence properties of SrIn2O4:Eu incorporated with Gd or Sm ions

The photoluminescence (PL) properties of SrIn₂O₄:Eu³⁺,Gd³⁺ and SrIn₂O₄:Eu³⁺,Sm³⁺ are investigated in this work. When the Gd³⁺ ions are introduced in this compound, the average distance metal-oxygen is increased, and then the vibration of lattice is decreased. It results in that the nonradiation of Eu³⁺ is decreased. Therefore, the emissions of SrIn₂O₄:Eu³⁺ are increased. However, little of energy transfer occurs from Gd³⁺ to Eu³⁺ ions. When the Sm³⁺ ions are introduced into SrIn₂O₄:Eu³⁺, the energy transfers occur from the CTS of O²⁻-Sm³⁺ to Sm³⁺ and Eu³⁺ ions, from the host absorption to Eu³⁺ ions, and from Sm³⁺ to Eu³⁺ ions, but not from the host absorption to Sm³⁺ ions.     

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.     

Synthesis and phosphorescence properties of Mn, La and Ho in MgAl2Si2O8

Mn⁴⁺, La³⁺ and Ho³⁺ doped MgAl₂Si₂O₈-based phosphors were first synthesized by solid state reaction. They were characterized by thermogravimetry (TG), differential thermal analysis (DTA), X-ray powder diffraction (XRD), photoluminescence (PL) and scanning electron microscopy (SEM). The phosphors were obtained at about 1300 °C. They showed broad red and fuchsia-pink emission bands in the range of 610-715 nm and had a different maximum intensity when activated by UV illumination. Such a fuchsia-pink emission can be attributed to the intrinsic d-d transitions of Mn⁴⁺.     

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.