ZnSe单晶的气相生长及光学性质

用改进的化学气相输运技术(CVT),以Zn(NH4)3Cl5为新的气相输运剂,直接从单质Zn和Se一步在封密管中生长了ZnSe单晶,升华温度1001～1020℃,管内温差<4℃。经过两周生长,得到8mm×7mm×0.8mm的绿色ZnSe晶体。XRD表明晶体表面为(111)面;受气固界面形貌影响,双晶衍射半高峰宽为50s;PL谱由DPA和SA两个发光峰组成;并研究了晶体片的吸收光谱、荧光光谱、反射光谱和红外透过等光学性质。     

ZnSe晶体的气相法制备和性能研究

采用化学气相输运法,以单质Zn和Se为原料生长ZnSe晶体。比较了加碘(Zn-Se-I2)和未加碘(Zn-Se)两种情况下产物的特征,借助XRD和SEM检测仪器对所生长的ZnSe晶体的结构、形貌和成分进行了分析。结果表明,加入碘后生长的ZnSe晶体为橙黄色,具有较好的结晶性能,晶格常数为5.668nm,Zn与Se的化学成分比为1∶1,没有其它杂质峰;未加碘的产物为多孔状陶瓷,说明加碘可以明显提高ZnSe的结晶性能,解决了一致升华范围较窄的限制条件,避免了ZnSe生长动力学的限制,因此可以获得理想化学计量比的ZnSe晶体。     

ZnSe单晶CVT法生长与系统优化

采用热力学数值计算的方法, 分析了ZnSe-I₂、H₂、HCl和NH₄Cl化学气相输运系统的特性. 对比计算结果表明, ZnSe-NH₄Cl系统具有压力高、输运反应焓变适中的特点. NH₃分解产生的H₂起着调节输运组分H₂Se分压的作用. 以ZnSe-I₂输运系统中实际输运组分分压值为参考, 确定了ZnSe-NH₄Cl系统中单晶生长工艺参数范围: 温度在1000℃左右, NH₄Cl的浓度范围在0.5~1.0mg/mL之内. 采用该工艺生长了尺寸约为8mm×6mm×4mm的ZnSe单晶, 生长态(111)面摇摆曲线半峰宽为60.48’’, 蚀坑密度(EPD)为(4.5~5.0)×10⁴/cm².     

Ni 基高温合金中 MC 碳化物生长的理论形貌

本文应用 PBC 理论证实了 MC 碳化物从 Ni 基高温合金熔体中生长的理想形貌是以{111}面为外表面的八面体.认为 MC 的一种生长基元为由金属原子和周围六个碳原子组成的八面体配位体,在近平衡条件下MC 碳化物的晶体生长机制是该配位体沿晶体的{111}面层状生长.     

ZnSe多晶料的合成方法及其工艺研究

简述了单晶生长用ZnSe多晶料的制备方法.分别以颗粒状和粉末状的高纯单质Zn和Se为原料,采用元素直接合成法合成了ZnSe多晶料,分析了直接合成的困难所在.理论分析和实验研究均表明:前期H2-O2焰下高温灼烧(～1500℃)使Zn和Se充分反应,是合成工艺的关键;延长后期恒温时间(不少于2周),使扩散反应进行完全,有利于获得更接近化学计量比的ZnSe多晶料.     

半导体纳米材料Zn(en)3 Se,ZnSe及其光学性能研究

以有机溶剂热技术制备片状Zn（en）3Se（en为乙二胺）纳米材料,DTG、IR、XRD分析结果表明该化合物中乙二胺与中心离子Zn^2＋通过配位键相结合;以制得的纳米Zn（en）3Se为母体,在氮气氛中煅烧至980℃,热分解制得棒状纳米ZnSe;以TEM、ED初步研究了两者的形貌、结构;以提拉法分别将Zn（en）3Se、ZnSe纳米材料涂布在ITO导电玻璃上,制得纳米颗粒／ITO复合膜,并研究其光学特性。结果表明,Zn（en）3Se属立方晶系,呈片状结构;ZnSe属六方纤锌矿型,棒直径在40nm左右;可能的生长机理是乙二胺作为模板分子,首先嵌入到ZnSe无机结构框架中,接着受热分解逃逸出无机框架形成一维纳米棒。PL分析表明Zn（en）3Se的荧光红移至448nm处。     

甲烷浓度对CVD金刚石薄膜晶体学生长过程的影响

采用X射线衍射技术、电子背散射衍射技术和扫描电镜分别观察了不同甲烷浓度条件下沉积的CVD自支撑金刚石薄膜的宏观织构、微区晶界分布和表面形貌.研究了金刚石晶体{100}面和{111}面生长的晶体学过程.研究表明,{100}面通过吸附活性基团CH^2- 2,而{111}面通过交替吸附活性基团CH^-3和CH^-3后脱氢堆积碳原子.低甲烷浓度时,{111}面表面能低于{100}面,使{111}面生长略快于{100}面.甲烷浓度升高,动力学作用增强使{100}面生长明显快于{111}面,使金刚石薄膜产生{100}纤维织构;同时显露的{100}面平行于薄膜表面,竞争生长使位于晶体侧面的{111}面由于相互覆盖而减小,形成了不同于单晶体自由生长的薄膜表面形貌组织.     

钙钛矿结构的有机-无机杂化功能材料:(p-CphAH)2PbCl4

利用溶液降温的方法从盐酸溶液中生长出一种新的有机-无机层状钙钛矿结构的单晶(p-CphAH)2PbC14(p-CphAH为对氯苯铵离子).借助于元素分析值、核磁谱、X射线衍射方法、紫外及荧光光谱,系统研究化合物的结构和光学性能.标题化合物晶体为浅黄色长棱柱体,单斜晶系,C2/m空间群;a=2.2149(5)nm,b=0.7737(3)nm,c=1.7083(5)nm,β=104.784(5)°,V=2.8310(2)nm3.     

用热壁外延法在CaAs(100)上生长ZnSe薄膜

用封闭和开口两种热壁外延法在GaAs(100)衬底上生长ZnSe薄膜。着重讨论了这两种方法对所生长薄膜质量的影响。α台阶仪的测量、X-射线衍射结果和Raman光谱的分析等一致表明,当实验偏离严格热壁外延技术时,所长薄膜的质量明显下降。在源温Tso=700℃、壁温Tw=550℃、衬底温度Tsu=320℃时,用封闭(严格)的热壁外延法成功地长出质量较佳的ZnSe(100)单晶薄膜。XPS测量分析表明此单晶薄膜中Zn和Se的成分比为1:1。     

一种基于D-π-A型芴衍生物的合成、核磁共振谱及光谱性能研究

合成了一种具有D-π-A结构特征的新型芴衍生物:2-(2,4-二氟苯基)-7-(4-甲氧基苯基)-9,9-二辛基芴(1)。通过元素分析、红外光谱(IR)以及全面的一维核磁共振氢谱(1 H NMR)、碳谱(13 C{1 H}NMR)、氟谱(19F{1 H}NMR)对其结构进行了全面表征。通过优化反应物的投料顺序,得到较为合理的合成方法。详细分析了核磁共振谱谱线特征。利用紫外-可见吸收和荧光光谱研究了化合物的发光性能。结果表明,在CH2Cl2溶液中,化合物1在300~330nm波段有吸收峰,归属于π-π*跃迁;其光学带隙Eg为3.39eV,发射峰值位于383nm,并且具有强烈的深蓝色荧光发射(激发波长为310nm),在CH2Cl2溶液中量子效率达到0.70。此外,化合物1的吸收和发射光谱具有溶剂极性依耐性。     

Real gas choked flow conditions at low reduced-temperatures

Real gas choked mass flux is calculated for a frictionless stream expanding isentropically until it reaches the speed of sound and without phase changes. The other parameters associated with the choked state are the pressure, density, temperature ratios, and the speed of sound. Departure of the choked mass flux from the ideal gas model is discussed first in absolute terms and then in relative terms, using the Principle of Corresponding States, for gases with boiling points in the low temperature range. Reduced-stagnation pressures are examined up to values of 30 for hydrogen, neon, nitrogen, argon, methane, krypton, xenon, and R-14 and up to 100 for ⁴He. The corresponding reduced-stagnation temperatures go down to 1.4 and in some cases down to 1.2 for nitrogen and argon. Also discussed are the limiting values of stagnation parameters for which no phase change occurs in the choked state. Compared to the ideal gas, the mass flux may almost double and the critical pressure ratio may decrease by an order of magnitude. The relevance of results is discussed qualitatively and quantitatively for Joule-Thomson cryocooling.     

As-cast microstructures and behavior at high temperature of chromium-rich cobalt-based alloys containing hafnium carbides

Hafnium is often used to improve the high temperature oxidation resistance of superalloys but not to form carbides for strengthen them against creep. In this work hafnium was added in cobalt-based alloys for verifying that HfC can be obtained in cobalt-based alloys and for characterizing their behavior at a very temperature. Three Co–25Cr–0.25 and 0.50C alloys containing 3.7 and 7.4 Hf to promote HfC carbides, and four Co–25Cr– 0 to 1C alloys for comparison (all contents in wt.%), were cast and exposed at 1200 °C for 50 h in synthetic air. The HfC carbides formed instead chromium carbides during solidification, in eutectic with matrix and as dispersed compact particles. During the stage at 1200 °C the HfC carbides did not significantly evolve, even near the oxidation front despite oxidation early become very fast and generalized. At the same time the chromium carbides present in the Co–Cr–C alloys totally disappeared in the same conditions. Such HfC-alloys potentially bring efficient and sustainable mechanical strengthening at high temperature, but their hot oxidation resistance must be significantly improved.     

Degradation behaviour of sputtered Co–Al coatings on superalloy

Degradation behaviour of sputtered Co–Al coatings on Superni-718 substrate has been investigated. Cyclic high temperature oxidation tests were conducted on uncoated and coated samples at peak temperatures of 900 °C for up to 100 thermal cycles between the peak and room temperatures. The results showed that a dense scale formed on the coated samples during thermal cycling at the peak temperature of 900 °C. The external scale exhibited good spallation resistance during cyclic oxidation testing at both temperatures. The improvement in oxide scale spallation resistance is believed to be related to the fine-grained structure of the coating. Nanostructured Co–Al coatings on Superni-718 substrate were deposited by DC/RF magnetron sputtering. FE-SEM/EDS, AFM, and XRD were used to characterize the morphology and formation of different phases in the coatings, respectively. The Co–Al coating on superalloy substrate showed better performance of cyclic high temperature oxidation resistance due to its possession of β-CoAl phase as Al reservoir and the formation of Al₂O₃ and spinel phases such as CoCr₂O₄ and CoAl₂O₄ in scale. The oxidation results confirmed an improved oxidation resistance of the Co–Al coating on superalloy as compare to bare substrate in air at 900 °C temperature up to 100 cycles.     

Capacitance based mass metering for cryogenic fluids

This paper describes a method for measuring the mass of cryogenic fluids in on-board rocket propellant tanks or ground storage tanks. Linear approximations to the Clausius-Mossotti relationship serve as the foundation for a capacitance based mass sensor, regardless of fluid density stratification or tank shape. Sensor design considerations are presented along with the experimental results for a capacitance based mass gage tested in liquid nitrogen. This test data is shown to be consistent with theory resulting in a demonstrated mass measurement accuracy of ±0.75% and a deviation from linearity of less than ±0.30% of full scale mass. Theoretical accuracies are also shown to be ±0.73% for hydrogen and ±1.39% for oxygen for a select range of pressures and temperatures.     

Equipment using a “static-analytic” method for solubility measurements in potentially hazardous binary mixtures under cryogenic temperatures

A new apparatus designed to study, at cryogenic temperatures, thermodynamic equilibria of potentially explosive binary systems such as hydrocarbon-oxygen mixtures is described herein. This equipment has an equilibrium cell which was especially designed to minimize hazards while allowing accurate phase equilibrium measurements. Reliability of results, obtained with this equipment has been verified by working on the nitrogen-propane system, for which data are already available in literature, over a large range of compositions and at various temperatures. Four isothermal curves describing liquid phase compositions at 109.98, 113.77, 119.75 and 125.63 K have been determined. Our experimental data are represented within 2% in compositions and in pressures through the Peng-Robinson equation of state implying Mathias-Copeman alpha function and Huron-Vidal mixing rule. Comparisons to literature allow pointing out: good agreement is observed with Kremer and Knapp data (1983) while the three sets of Poon and Lu data (1974) presenting systematic positive deviation are consequently judged as suspicious.     

Thermal Stability of Amorphous Hydride Mg_(50)Ni_(50)H_(54) and Mg_(30)Ni_(70)H_(45)

The thermal stability of amorphous ternary hydrides Mg_(50)Ni_(50)H_(54) and Mg_(30)Ni_(70)H_(45) and their corre-sponding amorphous binary alloys Mg_(50)Ni_(50) and Mg_(30)Ni_(70) were studied with X-ray diffraction(XRD) and differential scanning calorimetry(DSC). Samples of the amorphous alloys were preparedby mechanical alloying and the amorphous hydrides were obtained by charging the alloys with gas-eous hydrogen at 3.0 MPa and 423 K. It was found that the amorphous hydrides released most oftheir hydrogen before the crystallization of the essentially hydrogen depleted amorphous alloy. Thecrystallization temperature of amorphous Mg_(50)Ni_(50)H_(54) elevated and that of amorphousMg_(30)Ni_(70)H_(45) did not change in relation to the original binary amorphous alloy. This is very excep-tional for amorphous hydrides. The reason for the effects of hydrogen absorption/desorption on thecrystallization of amorphous alloys was discussed.     

长余辉材料Sr_4Al_(14)O_(25)∶Eu~(2+),Nd~(3+)的溶胶凝胶法制备及性能研究

首次研究了以Nd~(3+)离子为辅助激活剂,对Eu~(2+)掺杂的发光材料Sr_4Al_(14)O_(25):Eu~(2+)余辉性能的影响.用溶胶凝胶法合成了Eu~(2+), Nd~(3+)共掺杂的Sr_4Al_(14)O_(25):Eu~(2+),Nd~(3+)发光粉末,并用扫描电镜、X射线衍射计、荧光分光光度计、余辉亮度测试仪、热释光剂量计等手段对粉末样品进行了表征.结果表明,在1350℃得到了单一的Sr_4Al_(14)O_(25)相,粉末颗粒平均粒度在1μm左右.Eu~(2+), Nd~(3+)共掺杂的Sr_4Al_(14)O_(25):Eu~(2+),Nd~(3+)发光粉末有402和485nm两个发射峰,与Eu~(2+)单掺杂的Sr_4Al_(14)O_(25):Eu~(2+)相比,发射峰位置没有变化,但适量的掺杂可以大大提高余辉时间和余辉亮度,余辉时间可达18h以上.最后通过对热释光谱的分析解释了双掺杂发光粉余辉性能增强的原因,适宜深度的陷阱可以有效存储光能,增强余辉的时间和强度.     

Gas gap thermal switches using neon or hydrogen and sorption pump

The very low pressure obtained thanks to adsorption phenomenon at low temperature can be used to build cryogenic heat switches, which offer the possibility to make or break thermal contact between two parts of a cryogenic system. The ON (conducting) and OFF (insulating) states of the switch are obtained by varying the gas pressure between two copper blocks separated by a gap of 100 μm. This pressure is controlled by acting upon the temperature of a small sorption pump (activated charcoal) connected to the gap space. For a “high” sorption pump temperature, the gas previously adsorbed in the sorption pump is released to the gap between the two blocks, allowing a good thermal conduction through the gas (ON state). On the opposite, cooling the sorption pump allows a very good vacuum between the copper blocks, which efficiently break the thermal contact (OFF state). Experimental thermal characteristics (Conductance in the ON and OFF state, ON-OFF switching temperature) of such a “Gas Gap Heat Switch” are described using hydrogen or neon as exchange gas and are compared with theoretical calculations.     

Development of No-Vent™ liquid hydrogen storage system for space applications

A number of technological advances required to store and maintain normal-boiling-point and densified cryogenic liquids, including liquid hydrogen, under zero boil-off conditions in-space, for long periods of time, have been developed. These technologies include (1) thermally optimized compact cryogen storage systems that reduce environmental heat leak to the lowest-temperature cryogen, which minimizes cryocooler size and input power, and (2) actively-cooled shields that surround the storage systems and intercept heat leak. The processes and tools used to develop these technologies are discussed. A zero boil-off liquid hydrogen storage system technology demonstrator for validating the actively-cooled shield technology is presented.     

链结构对偏氟乙烯铁电共聚物介电性质的影响

用改进的介电松弛谱仪(精度 2‰)测定了 VDF(52)/TrFE(48)和VDF(47.5)/TrFE(47.5)/HeFP(5)在-120—140℃,10~(-2)-10~4Hz 范围的复数介电常数。介电松弛研究结果显示5mol%的 HeFP 导致三元共聚物 T_c 下降(30℃),非晶松弛强度减弱,T_g 降低(3℃),并引起局域松弛活化能升高(10.1kJ/mol),松弛时间增长。