Phase behavior of complex superprotonic solid acids

Superprotonic phase transitions and thermal behaviors of three complex solid acid systems are presented, namely Rb3H(SO4)2-RbHSO4 system, Rb3H(SeO4)2-Cs3H(SeO4)2 solid solution system, and Cs6(H2SO4)3(H1.5PO4)4. These material systems present a rich set of phase transition characteristics that set them apart from other, simpler solid acids. A.C. impedance spectroscopy, high-temperature X-ray powder diffraction, and thermal analysis, as well as other characterization techniques, were employed to investigate the phase behavior of these systems.

Rb3H(SO4)2 is an atypical member of the M3H(XO4)2 class of compounds (M = alkali metal or NH4+ and X = S or Se) in that a transition to a high-conductivity state involves disproportionation into two phases rather than a simple polymorphic transition [1]. In the present work, investigations of the Rb3H(SO4)2-RbHSO4 system have revealed the disproportionation products to be Rb2SO4 and the previously unknown compound Rb5H3(SO4)4. The new compound becomes stable at a temperature between 25 and 140 °C and is isostructural to a recently reported trigonal phase with space group P3̅m of Cs5H3(SO4)4 [2]. At 185 °C the compound undergoes an apparently polymorphic transformation with a heat of transition of 23.8 kJ/mol and a slight additional increase in conductivity.

The compounds Rb3H(SeO4)2 and Cs3H(SeO4)2, though not isomorphous at ambient temperatures, are quintessential examples of superprotonic materials. Both adopt monoclinic structures at ambient temperatures and ultimately transform to a trigonal (R3̅m) superprotonic structure at slightly elevated temperatures, 178 and 183 °C, respectively. The compounds are completely miscible above the superprotonic transition and show extensive solubility below it. Beyond a careful determination of the phase boundaries, we find a remarkable 40-fold increase in the superprotonic conductivity in intermediate compositions rich in Rb as compared to either end-member.

The compound Cs6(H2SO4)3(H1.5PO4)4 is unusual amongst solid acid compounds in that it has a complex cubic structure at ambient temperature and apparently transforms to a simpler cubic structure of the CsCl-type (isostructural with CsH2PO4) at its transition temperature of 100-120 °C [3]. Here it is found that, depending on the level of humidification, the superprotonic transition of this material is superimposed with a decomposition reaction, which involves both exsolution of (liquid) acid and loss of H2O. This reaction can be suppressed by application of sufficiently high humidity, in which case Cs6(H2SO4)3(H1.5PO4)4 undergoes a true superprotonic transition. It is proposed that, under conditions of low humidity, the decomposition/dehydration reaction transforms the compound to Cs6(H2-0.5xSO4)3(H1.5PO4)4-x, also of the CsCl structure type at the temperatures of interest, but with a smaller unit cell. With increasing temperature, the decomposition/dehydration proceeds to greater and greater extent and unit cell of the solid phase decreases. This is identified to be the source of the apparent negative thermal expansion behavior.

References

[1] L.A. Cowan, R.M. Morcos, N. Hatada, A. Navrotsky, S.M. Haile, Solid State Ionics 179 (2008) (9-10) 305.

[2] M. Sakashita, H. Fujihisa, K.I. Suzuki, S. Hayashi, K. Honda, Solid State Ionics 178 (2007) (21-22) 1262.

[3] C.R.I. Chisholm, Superprotonic Phase Transitions in Solid Acids: Parameters affecting the presence and stability of superprotonic transitions in the MHnXO4 family of compounds (X=S, Se, P, As; M=Li, Na, K, NH4, Rb, Cs), Materials Science, California Institute of Technology, Pasadena, California (2003).

激光二极管抽运的国产Yb:YAG陶瓷激光器

研究了国产Yb:YAG陶瓷的激光输出特性。激光器采用激光二极管(LD)纵向同轴抽运Yb:YAG陶瓷样品,样品的掺杂原子数分数为1%,一端面镀940 nm和1030 nm双增透膜,另一端面镀1030 nm增透膜,激光器在1031 nm处获得了近红外激光输出。实验中分别测试了Yb:YAG陶瓷在不同输出透射率(T=4%,8%,10%)条件下的激光输出特性。整个实验过程中,激光器维持基横模运转。当输出透射率为10%,吸收的抽运功率为9 W时,激光器获得最大的激光输出功率为1.63 W,相应的斜率效率为23.2%。

Wave interactions in periodic structures and periodic dielectric waveguides

This work is concerned with a general analysis of wave interactions in periodic structures and particularly periodic thin film dielectric waveguides.

The electromagnetic wave propagation in an asymmetric dielectric waveguide with a periodically perturbed surface is analyzed in terms of a Floquet mode solution. First order approximate analytical expressions for the space harmonics are obtained. The solution is used to analyze various applications: (1) phase matched second harmonic generation in periodically perturbed optical waveguides; (2) grating couplers and thin film filters; (3) Bragg reflection devices; (4) the calculation of the traveling wave interaction impedance for solid state and vacuum tube optical traveling wave amplifiers which utilize periodic dielectric waveguides. Some of these applications are of interest in the field of integrated optics.

A special emphasis is put on the analysis of traveling wave interaction between electrons and electromagnetic waves in various operation regimes. Interactions with a finite temperature electron beam at the collision-dominated, collisionless, and quantum regimes are analyzed in detail assuming a one-dimensional model and longitudinal coupling.

The analysis is used to examine the possibility of solid state traveling wave devices (amplifiers, modulators), and some monolithic structures of these devices are suggested, designed to operate at the submillimeter-far infrared frequency regime. The estimates of attainable traveling wave interaction gain are quite low (on the order of a few inverse centimeters). However, the possibility of attaining net gain with different materials, structures and operation condition is not ruled out.

The developed model is used to discuss the possibility and the theoretical limitations of high frequency (optical) operation of vacuum electron beam tube; and the relation to other electron-electromagnetic wave interaction effects (Smith-Purcell and Cerenkov radiation and the free electron laser) are pointed out. Finally, the case where the periodic structure is the natural crystal lattice is briefly discussed. The longitudinal component of optical space harmonics in the crystal is calculated and found to be of the order of magnitude of the macroscopic wave, and some comments are made on the possibility of coherent bremsstrahlung and distributed feedback lasers in single crystals.

调Q及连续掺Yb光纤激光器中的自锁模研究

在用半导体激光器抽运的单包层掺Yb调Q光纤激光器中观察到了清晰稳定的自锁模脉冲序列。脉冲包络形状为调Q脉冲。每个锁模脉冲的幅值由其在调Q脉冲中的相应位置决定。经过分析，认为自相位调制是调Q光纤激光器中产生锁模的主要原因。自相位调制的存在使得光脉冲的频谱被展宽，当这种展宽和腔的模式间隔相差不多时，腔内的模式便能相互作用，直到它们之间产生一个固定的相位关系。也即形成锁模。在此基础上。去掉声光晶体，并用两个光栅作为腔镜，实现了全光纤法布里-珀罗(F-P)腔锁模光纤激光器。改变腔结构，分别采用光栅和光纤反射圈作为

Cr^4＋：YAG被动调QNd：YAG陶瓷激光器的研究

介绍了近几年迅速发展的一种新型激光介质——透明Nd：YAG多晶陶瓷的发展状况，对比分析了多晶陶瓷与单晶的光谱特性、激光特性和连续实验研究情况。并对钛宝石激光器调谐至808nm，端面抽运Nd：YAG陶瓷被动调Q全固态激光器的脉冲运转进行了较为详细的理论分析和实验研究。采用初始透射率为90％的Cr^4＋：YAG可饱和吸收晶体，被动调Q的阈值功率为119mW，当端面抽运功率为465mW时，获得波长为1064nm，脉宽为16ns，重复频率为18．18kHz，单脉冲能量为3．4μJ，平均输出功率为61mW的稳定调Q

部分抽运的板条激光器的热效应分析

基于热传导方程和高斯-赛德尔数值计算方法，对部分抽运板条激光器的温度分布、热应力和热致折射率变化等热效应进行了详细分析，并与单侧抽运及双侧抽运方式进行了比较。结果表明，设计合理的部分抽运板条激光器，可以获得较高的抽运效率，其热效应相比于均匀抽运的情况并没有显著劣化，不论是采用锯齿形传播方式还是直线传播方式的激光器都可以获得较好的光束质量，当一束高斯激光直线经过板条晶体中部时，光束质量因子为1．4，若采用锯齿形传播方式，则光束质量因子可提高到1．1。

部分端面抽运的Nd：YVO4板条固体激光器

利用自制高功率激光二极管（LD）列阵堆和波导整形抽运耦合系统，将抽运光耦合至Nd：YVO4板条晶体，平平腔运转得到了1.064μm的偏振激光输出。在最大抽运功率为84W时，透过率为10％的输出腔镜得到了31W的激光功率输出，光一光效率37％，斜效率45％，板条晶体两个方向的输出光束质量差别较大。为了进一步提高光束质量，使用柱面镜混合腔结构，在最大抽运功率为86W时，得到了19．3W的1064nm激光输出，测得的非稳腔和稳腔两个方向的M^2因子分别为1.4和1．7。

拱形激光二极管侧抽运Nd∶YAG固体激光器的实验研究

详细阐述了同心抽运、同心冷却的激光二极管紧包侧抽运Nd：YAG激光器的实验研究工作。这种抽运结构使晶体内的增益场与谐振腔基模实现了良好的匹配，易于得到良好的光束质量和大能量输出，基模提取效率高。模拟分析了晶体内的增益场以及横截面内的温度分布，从不同角度探讨了激光二极管的温度特性对器件工作的影响。研究了晶体的热致退偏效应对器件调Q工作的影响．并且初步探讨了不同腔长、不同腔型下器件的工作情况，这些实验结果对进一步优化使用这种抽运结构有指导意义。所设计的激光器在工作频率6Hz时．得到了斜效率为44．3％的多模调

部分端面抽运板条激光器腔镜倾斜问题研究

部分端面抽运的板条激光器是一种新型固体激光器．配合混合腔可以实现在大功率下保持高光束质量的激光振荡输出。谐振腔的腔镜倾斜是影响激光器输出特性的重要因素，快速傅里叶方法是一种快捷有效的计算方法，利用此方法模拟了腔镜倾斜对近场相位分布和远场光强分布的影响，并分析了光束质量的变化。理论分析表明，腔镜的小角度倾斜对近场相位影响较大，但对远场光强空间分布影响不大；随着倾斜角度不断增大，远场发散角和光束腰宽度也增大，光束质量虽然存在恶化的趋势，但光束质量因子肝值仍然较小，离轴非稳腔仍能保持高光束质量的输出。

基于正交频率变换的高功率蓝绿全固态激光器

对多横模全固态激光器使用正交频率变换进行了分析,计算了频率转换效率与激光发散角的关系。使用双KTP晶体正交倍频的方法,对Nd∶YAG激光器输出的含有高阶横模的激光进行倍频实验研究。在1064 nm Nd∶YAG激光基波功率密度为121 MW/cm2时,其谐波转换效率达到75.5%。研究表明,对于光束质量较差的基波激光,采用正交频率变换的方式,适当选择晶体参数,同样可以获得较高效率的二次谐波输出。

高重复率窄脉宽Nd∶YVO_4板条激光器

部分端面抽运的混合腔板条激光器是一种新型的全固态激光器,采用这种结构,实现了高重复率调Q运转。在脉冲抽运情况下,1kHz运转时,得到脉宽4.6ns,单脉冲能量4.5mJ的激光输出。在连续抽运调Q输出情况下,5kHz高重复率运转时,获得了脉宽6ns,单脉冲能量3.1mJ的脉冲序列输出,平均功率超过15W;当重复率高达25kHz时,得到脉宽9.5ns,单脉冲能量1.2mJ的激光输出,平均功率达30W。实验结果表明,输出水平还有很大的提升空间。

采用国产双包层光纤的声光调Q激光器

实验报道采用我国自行设计的大模场掺镱双包层光纤，利用简单声光调Q装置，成功实现调Q运转；在1－50kHz调制频率下获得了百纳秒的调Q脉冲，其输出光束质量因子大约为2。当重复频率为1kHz时，获得了脉冲宽度为132ns，能量0.93mJ。同时实验中观察到的调Q脉冲常出现一点锁模现象，针对这一现象进行了讨论。

两微米瓦级掺铥短光纤激光器

以短的高掺杂浓度的掺铥硅基光纤为增益介质，采用790 nm波长的激光二极管(LD)为抽运源，得到了波长为2 μm的高功率激光输出。当光纤长度为7 cm时，激光器的阈值泵浦功率为135 mW，最大输出功率为1.09 W，斜率效率为9.6%(相对于耦合进光纤的抽运功率)。该激光器的输出稳定性在5%以内。此外，我们还观察分析了工作温度和其他腔结构参量对该激光器工作性能的影响。

千瓦级双包层光纤激光器冷却方案设计理论和实验研究

尽管双包层光纤激光器的散热性能好于传统的固体激光器的散热性能,光纤激光器中的热沉积仍然是限制提高其输出功率的重要因素.以双端抽运的400W双包层光纤激光器为实例,定量分析了光纤内的热沉积分布.根据所建立的散热模型,为了确保千瓦级双包层光纤激光器安全稳定的运行,抽运端附近的对流换热系数应大于2.8×10-2W·cm-2K-1.据此设计出高功率双包层光纤激光器抽运端冷却装置并成功应用在激光系统中,获得了千瓦级的激光输出.

110-W fiber laser with homemade double-clad fiber

A high-power ytterbium-doped fiber laser (YDFL) with homemade double-clad fiber (DCF) is introduced in this letter. The geometric parameter and laser characteristics of the fiber have been studied. With one-end-pumping scheme, pumped by a high-power laser diode with launching power of 280 W, a maximum continuous wave (CW) output of 110 W is obtained with an optical-to-optical efficiency of 40%.