Study on Lattice Parameter Variance and Eutectic Reaction during Crystal Growth of Nd,Cr∶GSGG by Czochralksi Method

During the crystal growth of Nd,Cr∶GSGG by Czochralski method,in some cases eutectic reaction occurred in the nether region of the crystal,and the boule was divided into two obvious different parts,which is upper Nd,Cr∶GSGG crystal and the nether coexisting Nd,Cr∶GSGG and GdScO_(3).By X-ray powder diffraction,the structure change of NdCr∶GSGG crystal ofΦ27 mm×120 mm with eutectic along its grown direction<111>was studied.By the least square method and extrapolation function f=sinθ-sinθ^(1-t)(t is an adjustable parameter),the lattice parameters of Nd,Cr∶GSGG and additional GdScO_(3)phase were computed.The results indicate that the lattice parameters of Nd,Cr∶GSGG increase along its growth direction,which changes from a=(1.25650±0.00007)nm of the top to(1.25798±0.00010)nm of the bottom.In the process of Nd,Cr∶GSGG growth,Gd^(3+)in Nd,Cr∶GSGG is partly replaced by Nd^(3+)with larger ionic radii,and the volatilization of Ga component results in its composition variance,which cause the lattice parameters increase along growth direction.In the eutectic section,there are the Nd,Cr∶GSGG and the second phase orthorhombic GdScO_(3).The lattice parameters of GdScO_(3)are a=0.5443±0.0007,b=0.5699±0.0005 and c=(0.7865±0.0009)nm,and that of Nd,Cr∶GSGG is(1.25798±0.00010)nm.In the final growth stage,excessive volatilization of Ga composition during the crystal growth causes the growth melt deflect of the Nd,Cr∶GSGG solid solution range seriously,and results in the eutectic reaction,and the outgrowth of Nd,Cr∶GSGG and GdScO_(3).So it is necessary to decrease the effect of gallium volatilization during the growth in order to avoid eutectic growth and obtain a high-quality Nd,Cr∶GSGG.

可调谐激光晶体Cr:GSGG的光谱分析及晶场参数计算

用提拉法成功生长出了优质的Cr3^＋：Gd，Sc2Ga2O12晶体，测定了室温下的吸收光谱和不同温度下的荧光光谱，计算了晶场参数，发现荧光峰值及晶场参数与以前文献报道的均不相同。吸收光谱中，在458．5nm和642．5nm出现了较强的宽带吸收峰，分别对应于Cr3^＋的^4A2→^4T1和^4A2→^4T2孔的吸收跃迁，在678nm处又叠加了一个非常弱的吸收峰，对应于^4A2→^4T1的吸收跃迁。测试了晶体从7K到室温的荧光光谱和荧光寿命，在650～850nm范围内出现了宽带荧光，对应于Cr^3＋的^4T2→^4A2的发射跃迁。随着温度的升高，荧光峰向长波方向移动，荧光峰半高宽增大，室温下其荧光峰值在732nm，半高宽约为80nm。低温（7K）下的荧光谱中，在694nm处观察到了尖而锐的R线（零声子线），对应于Cr^3＋的^2E→^4A2的发射跃迁。由于温度猝灭效应，随着温度升高，晶体的荧光寿命降低，室温下荧光寿命约为114μs。计算了晶场强度参数Dq／B=2．49,^4T2零声子能级与^2E能级的间距AE为204cm^-1，这些参数表明Cr^3＋处在较弱的晶场中，有利于^4T2→^4A2的宽带跃迁，Cr：GSGG晶体是较为理想的可调谐激光工作物质。

Effects of Cr content on microstructure and mechanical properties of single crystal superalloy

Two experimental single crystal superalloys with 2% Cr and 4% Cr (mass fraction) were cast in a directionally solidified furnace, while other alloying element contents were kept unchanged. The effects of Cr content on the microstructure, phase stability, tensile properties at 1100 °C and stress rupture properties at 1070 °C and 160 MPa of the single crystal superalloy were investigated. The results show that the size ofγ′ phase particles become small and uniform, and the cubic shape turns a little regular with the increase of Cr content. Theγ′ directional coarsening and rafting were observed in the 2% Cr and 4% Cr alloys after long term aging (LTA) at 1100 °C. The rafting rate ofγ′ phase increased with increasing Cr content. Needle-shaped topologically close packed (TCP) phases precipitated and grew along fixed direction in both alloys. The precipitating rate and volume fraction of TCP phases significantly increased with the increase of Cr content. The tensile property of the alloy increased and the stress rupture properties of the alloy decreased with the increase of Cr content at high temperature. The increase of Cr content increased the partition ratio of TCP forming elements, Re, W, and Mo, and the saturation degrees of these elements inγ phases increased. Therefore, the high temperature phase stability of the alloy decreased with the increase of Cr content.

退火对Nd,Cr:GSGG激光晶体吸收光谱的影响

本文应用吸收光谱法,对提拉法生长的Nd,Cr:GSGG晶体在不同气氛下退火后的光谱变化进行了研究。氧化气氛下退火后的吸收光谱中,在1μm处出现了由于晶体中存在Cr4+离子所引起的两个吸收带,被称为1μm吸收损失。还原气氛(CO和H2)下退火后的吸收光谱中,在1μm处的吸收带基本消失,这对于提高激光效率是非常有利的。此外,在642nm处的吸收带强度有一定的减弱。这些数据对于晶体后处理工艺的改进和激光器设计具有重要的参考价值。

灯泵Cr,Nd:GSGG晶体热效应的有限元研究

为了减少LD抽运全固态激光器输出高功率而产生激光晶体热效应的影响。采用ANSYS有限元分析软件分析晶体的热导率随温度的非线性变化,得到了闪光灯泵浦的Cr,Nd:GSGG晶体的内部温度场,热应力场分布。模拟出提高冷却水与晶体的传热系数,降低冷却水的温度,端面修磨后晶体的温度场分布,应力分布以及形变等。仿真结果表明,提高冷却水与晶体的传热系数,降低冷却水的温度可以有效降低晶体棒内的温度,而端面的适当修磨对于热透镜效应的改善起到一定作用。

Influence of Cr addition on microstructure of a 5% Re-containing single crystal nickel-based superalloy

Based on a 5% （mass fraction） Re-containing single crystal nickel-based superalloy with 3% （mass fraction） Cr, the microstructural variation with Cr addition was investigated. The experimental results show that segregation of alloying elements was enhanced in as-cast microstructure with Cr addition; and the volume fraction of eutectic is increased. However, the solidus and liquidus temperatures are remarkably reduced. With the increase of Cr content, the average γ＇ size and volume fraction are decreased in the fully heat treated microstructure. X-ray diffraction results indicate that γ/γ＇ lattice misfit becomes more negative. According to the energy dispersive spectroscopy （EDS） results, Cr is mainly distributed in the γ matrix; and more y-forming elements, such as Re and W, enter the γ matrix, while the γ/γ＇ partition ratio of Cr is inversely decreased.

Nd,Cr∶GSGG激光棒在应用方面的研究

实验通过对Nd,Cr∶GSGG激光棒在不同电压和泵浦脉冲宽度的条件下静态激光的输出能量及效率的分析。显示出Nd,Cr∶GSGG晶体拥有比YAG晶体更好的热力学性质,以及更高的转换效率。证明了它将在大功率激光器领域得到更广泛的应用。

Li(Sc,M)Si_(2)O_(6)∶Cr^(3+)(M=Ga^(3+)/Lu^(3+)/Y^(3+)/Gd^(3+))的近红外发光性能

荧光转换型近红外发光二极管(NIR pc-LED)具有体积小、谱带宽、峰位易调谐等优点,是新一代NIR光源发展的前沿,其关键在于研发可被蓝光有效激发的高效率宽带近红外荧光粉。LiScSi_(2)O_(6)∶Cr^(3+)荧光材料的激发波长为460 nm,发射峰位在845 nm,光谱带宽为156 nm,内量子效率为64.4%。基于该体系,本文通过M离子(M=Ga^(3+),Lu^(3+),Y^(3+),Gd^(3+))取代Sc^(3+)的方式对其性能进行调控。结果表明,引入M离子易生成杂相或发生相变,降低了材料的发光性能。本文从晶体结构出发对其调控过程进行了分析。

功能化MIL-101(Cr)修饰QCM气相传感器的组装与甲酸识别

挥发性有机化合物(VOCs)是一类主要的大气污染物,对人体健康和环境均可造成危害,因此发展可快速、灵敏检测VOCs的技术具有重要意义.本文分别以乙二胺(ED)和乙醇胺(EA)修饰MIL-101(Cr),制得了MIL-101(Cr)-ED和MIL-101(Cr)-EA,采用滴涂法制备了3种负载MIL-101(Cr)材料的石英晶体微天平(QCM)气相传感器,研究了其对甲醇、乙醇、异丙醇、丙酮、环己烷、二乙胺、甲酸、甲醛、氨气和乙酸的传感性能.实验结果表明,与负载MIL-101(Cr)的传感器相比,负载MIL-101(Cr)-ED和MIL-101(Cr)-EA的QCM传感器对甲酸的吸附性能显著提高,在甲酸浓度为350 mg/L时,传感器的振荡频率分别下降至-375.6和-232.1 Hz.在甲酸浓度为5~350 mg/L时,负载MIL-101(Cr)-ED的QCM传感器对甲酸响应的灵敏度为0.95 Hz·L·mg^(-1),检测限为0.95mg/L,表现出线性良好、灵敏度高、检测限低和重复性好的特点.这表明此类QCM气相传感器在VOCs实时检测方面具有良好的应用前景.

Microstructural Characterization of the Shear Bands in Fe-Cr-Ni Single Crystal by EBSD

An investigation has been made into the microstructural characterization of the shear bands generated under high-strain rate （≈10^4 s^-1） deformation in Fe-15%Cr-15%Ni single crystal by EBSD-SEM （electron backscatter diffraction-scanning electron microscopy）, TEM （transmission electron in microscopy） and HREM （high- resolution electron microscopy）. The results reveal that the propagation of the shear band exhibits an asymmetrical behavior arising from inhomogenous distribution in plasticity in the bands because of different resistance to the collapse in different crystallographic directions; The γ-ε-α′phase transformations may take place inside and outside the bands, and these martensitic phases currently nucleate at intersections either between the twins and deformation bands or between the twins and ε-sheet. Investigation by EBSD shows that recrystallization can occur in the bands with a grain size of an average of 0.2μm in diameter. These nano-grains are proposed to attribute to the results of either dynamic or static recrystallization, which can be described by the rotational recrystallization mechanism. Calculation and analysis indicate that the strain rate inside the shear band can reach 2.50×10^6 s^-1, which is higher, by two or three orders of magnitude, than that exerted dynamically on the specimen tested.

Synthesis and Crystal Structure of a Cr(Ⅲ) Dimer[Cr_2(8-hqn)_2Cl_4(H_2O)_2]·2(CH_3)_2CO (8-hqn=8-Hydroxyoxyquinolate)

The title complex [Cr2（8-hqn）2Cl4（H2O）2]·2（CH3）2CO （8-hqn = 8-hydroxyoxyquinolate） has been synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in the triclinic system, space group P^-1 with a = 8.719（1）, b = 9.226（1）, c = 9.717（1） A^°, α = 71.916（2）, β= 78.072（2）, γ = 76.014（2）°, V= 713.72（15） A^°^3, Z= 1, Dc= 1.597g/cm^3, F（000） = 350 and μ（MoKa） = 1.177 mm^-1, the final R = 0.0490 and wR = 0.1055 for 1616 observed reflections with I 〉 2σ（I）. It is a dimer constructed by two monomeric units [Cr（8-hqn）Cl2（H2O）] bridged by phenoxide-like oxygen atom from 8-hydroxyoxyquinolate, where the two six-coordinated Cr（Ⅲ）atoms exhibit an octahedral coordination geometry.

Investigation of the high-temperature Cr：LiSrAlF6 crystal by Raman spectroscopy

In this paper, Cr-doped LiSrAlF6 crystals are investigated using high-temperature Raman spectroscopy and the single-crystal Raman spectra of Cr：LiSrAlF6 are analysed by factor group theory and comparison with other fluorides. The results indicate that Cr：LiSrAlF6 is stable below its melting point; Raman peaks located at 561,322 and 250 cm-1 are assigned to the Alg modes of AlF6, SrF6 and LiF6 octachdra, respectively; with temperature increasing, Raman peaks associated with AlF6 octahedra shift towards low frequencies, while LiF6 and SrF6 octahedra are temperature- insensitive; around the crystal melting point, three new Raman peaks occur, which are associated with the AlF6 octahedral chain structure. Finally, the microstruetural evolution of Cr：LiSrAlF6 from room temperature to its melting point is discussed based on its Raman spectra.

电纺丝制备磁性单晶BiFeO_(3)纳米纤维并用于Cr(VI)的可见光催化还原

本工作提出一种将溶胶凝胶与静电纺丝结合的分步快速烧结技术,成功制备了单晶BiFeO_(3)纳米纤维。通过热重差热分析(TG-DTG)、XRD、SEM、TEM、EDS、紫外可见漫反射光谱和氮气吸附脱附曲线等测试对所制备材料的结构和形貌进行表征。同时,考察了BiFeO_(3)纳米纤维在可见光下对水中Cr(VI)的光催化还原性能。结果显示,相比于传统方式制备的纳米颗粒,该材料因更大的比表面积而具有更高的光催化活性。空穴消耗剂酒石酸的加入能够促进该材料对Cr(VI)的光催化还原反应,使还原效率提高87%。总之,本文制备的BiFeO_(3)材料能在可见光下响应,并在常温下具有弱磁性,能通过磁场力回收,在环境净化领域具有广阔的应用前景。

Crystal Growth,Spectroscopic Properties and Energy Levels of Cr^(3+):Li_2Mg_2(MoO_4)_3

This paper reported the crystal growth and spectroscopy characters of Cr^3＋：Li2Mg2（MoO4）3. The refractive index of Cr^3＋：Li2Mg2（MoO4）3 crystal is 1.87 and the hardness is 270 I-IV. This crystal shows broadband absorption property with peak wavelength at about 495 and 699 nm. The absorption crosssection is 14.75 × 10^-20 cm^2 at 495 nm and 9.63 ×10^-20 cm^2 at 699 nm, respectively. The crystal field strength and energy levels of Cr^3＋ ion were calculated based on the spectroscopic data. The Cr^3＋：Li2Mg2（MoO4）3 crystal shows broadband emission extending from 750 to 1300 nm even excited at 10 K. The room temperature emission cross section is 72×10^-20 cm^2 at 926 nm. A discussion of the relation between the spectroscopic properties and crystal field parameters of Cr^3＋：Li2Mg2（MoO4）3 crystal was presented based on the solid state spectroscopytheory.

Diode Pumped High Peak Power Quasi Q-Switched and Passively Q-Switched Nd:YVO₄Lasers at 1064 nm and 532 nm using Cr:YAG and KTP crystals

Diode end-pumped solid-state lasers have the potential to yield high quality laser beams with high efficiency for laser range finding and warning receiver applications as well as day and night military laser designation systems. In this paper we presents theoretical calculations using Advanced Dynamics Professional LASCAD software and experimental studies for a high power pigtailed fiber diode laser module of 8 W operating at 808 nm with a specially designed high efficiency cooling system, end pumped high-efficiency Nd:YVO4 laser of 3 × 3 × 10 mm rod and overall cavity length of 44 mm. To the best of our knowledge a self Q-switching effects was generated in Nd:YVO4 laser by changing the cavity dimensions and the position of the intracavity KTP crystal at certain regime of operation for the first time, in which the cavity length is reduced to be 30 mm and the distance between Nd:YVO4 rod and KTP crystal is only 1mm. Self Q-switched laser pulse at 532 nm with high peak power of 96 W, pulse width of 88 ns at FWHM and repetition rate of 400 kHz was achieved. Experimental studies of a passive Q-switched Nd:YVO4 laser using Cr:YAG crystal with three different transmissions of 30%, 40% and 70% were investigated. Passive Q-switched laser pulse at 1064 nm and narrow line width of less than 1.5 nm with highest peak power of nearly 18 kW, short pulse width of less than 4 ns at FWHM and higher repetition rate of 45 kHz using Cr:YAG with transmission of 30% was achieved for the first time.

大尺寸优质Cr^(3+)∶BeAl_(2)O_(4)晶体生长与性能研究

本文采用感应加热提拉法结合上称重自动控径技术,成功生长出大尺寸、高质量的翠绿宝石(Cr^(3+)∶BeAl_(2)O_(4))晶体。晶坯等径圆柱体尺寸达到ϕ70 mm×140 mm,晶坯质量超过2800 g。通过冷光源照射晶坯,发现晶坯中心区域ϕ10~15 mm存在气泡。采用5 mW绿光激光照射ϕ8 mm×130 mm的翠绿宝石晶体棒,晶体内部无散射颗粒。利用Zygo激光平面干涉仪对晶体棒进行测试,波前畸变为0.3λ@632.8 nm。用电感耦合等离子体原子发射光谱法测定了翠绿宝石晶体的铬离子掺杂浓度,并计算出轴向浓度梯度为0.5×10^(-4)~1.9×10^(-4)cm^(-1)(摩尔分数)。用Perkin Elmer Lambda-950紫外可见近红外分光光度计测试了不同掺杂浓度的翠绿宝石晶体在室温下的吸收光谱,并计算了吸收系数。这些研究结果为翠绿宝石晶体的应用提供了重要的基础数据。

Cr^(3+)掺杂F^(-)修饰BaScO_(2)F钙钛矿结构宽带近红外荧光粉

Cr^(3+)掺杂的近红外荧光材料,因具有高量子效率、可调的宽带发射及在蓝色光谱范围内的强吸收特性而备受关注。通过晶体场工程,可以调节Cr^(3+)掺杂的近红外荧光材料的发射范围,但常规的阳离子取代对发射范围的调节通常限制在近红外Ⅰ区(波长<1000 nm)。在生物医学成像领域,由于生物组织的吸收、散射和自发荧光较低,在近红外Ⅱ区,能够实现更高的穿透深度及无创或微创的深部组织成像。采用高温固相法,以Ba_(2)Sc_(2)O_(5)类钙钛矿型氧化物为基体,合成了一系列基于F^(-)修饰的近红外荧光粉BaSc_(1-x)O_(2)F:xCr^(3+)(x=0.001—0.01)。通过XRD图谱和容差因子计算,证明了合成的样品具有立方钙钛矿结构。另外,通过漫反射光谱(DRS)和X射线光电子能谱(XPS)等表征手段,确认了Cr离子的价态为Cr^(3+)。利用电子顺磁共振(EPR)对Cr^(3+)周围的晶体环境进行检测分析发现,样品在波长700—1400 nm范围内表现出近红外宽带发射,发射中心约在1040 nm处,半峰宽(FWHM)高达250 nm。表明,Cr^(3+)的发射有效覆盖了近红外Ⅱ区。同时,也证明了通过阴离子掺杂调节晶体场强度是可行的。由于PLE光谱和PL光谱在波长700—850 nm范围内存在重叠,随着Cr^(3+)掺杂浓度的增加,发射部分被重吸收,导致发射中心出现明显的红移现象。由于BaSc_(1-x)O_(2)F:xCr^(3+)近红外荧光粉的吸收峰与蓝光LED芯片能够匹配,表明其具有商业化潜力。本研究为生物医学成像领域的近红外Ⅱ区荧光粉转换LED器件提供了优异的宽带近红外光源材料。

Nd:GSGG激光晶体的光谱性能研究

用提拉法成功生长出了Nd3+:Gd3Sc22Ga3O12(Nd:GSGG)晶体,并对其光谱性能进行了研究。测量了晶体在400-2700 nm波段内的吸收光谱。用808 nm波长激发,测量了晶体的荧光光谱和荧光寿命,计算了晶体的发射截面。与Nd:GGG和Nd:YAG的光谱参数进行了比较。

掺杂GSGG激光晶体热导率研究

为研究不同掺杂GSGG激光晶体的导热特性，用瞬态脉冲法测量了273～393K温度范围内自己生长的Cr：GSGG、Nd，Cr：GSGG和Nd-GSGG激光晶体热导率。建立了实验样品温度场模型，推导出晶体热导率随温度升高呈下降变化趋势的结论，这与实验测量结果基本相符，通过对测量结果曲线拟合给出了拟合方程。并从理论上解释了掺入较高浓度的杂质Cr^3＋离子会使得晶体的热导率值有所降低，以及双掺Nd^3＋、Cr^3＋离子和单掺Nd^3＋离子的GSGG晶体热导率值基本相同的原因。

Cr掺杂锐钛矿相TiO_2光学性质的第一性原理研究

本文对Cr掺杂TiO2进行了基于密度泛函理论的第一性原理研究。模拟计算了完整及Cr掺杂TiO2的电子结构,介电函数及吸收光谱的偏振特性。计算结果表明完整的锐钛矿型TiO2晶体在可见光范围内无吸收;掺Cr后晶体的禁带宽度减小到2.25 eV,吸收边红移,并在可见光区域出现了2.51 eV(495 nm)的吸收峰,表明Cr掺杂有利于提高TiO2对太阳光的吸收。计算结果与实验结果基本相符。