Nd∶NaBi(WO_4)_2晶体生长

采用Czochralski法生长出尺寸为 8mm× 2 0mm的掺钕的钨酸铋钠 [分子式 :Nd∶NaBi(WO4) 2 ,简称 :Nd∶NBW ]激光晶体 ,研究了生长工艺参数对Nd∶NBW晶体结构完整性的影响 ,确定了最佳的生长工艺参数 :轴向温度梯度为 0 .7～ 1℃ /mm ,生长速率 0 .2～ 0 .5mm/h ,晶体转速 1～ 4r/min。并利用了X射线衍射确定了Nd∶NBW晶体属于四方晶系 ,I41 /a空间群 ,其晶格常数为a =0 .5 2 75nm ,c=1.14 93nm。通过TG -DTA分析了Nd∶NBW晶体的相关物理、化学性质 ,确定了其熔点为 936.2℃ ,并与纯的钨酸铋钠晶体 (分子式 :NaBi(WO4) 2 ,简称 :NBW)进行了对比性研究     

Nd:NaBi(WO4)2晶体生长

采用Czochralski法生长出尺寸为φ8mm×20 mm的掺钕的钨酸铋钠[分子式:Nd:NaBi(WO4)2,简称:Nd:NBW]激光晶体,研究了生长工艺参数对Nd∶NBW晶体结构完整性的影响,确定了最佳的生长工艺参数:轴向温度梯度为0.7～1 ℃/mm,生长速率0.2～0.5 mm/h,晶体转速1～4 r/min.并利用了X射线衍射确定了Nd∶NBW晶体属于四方晶系,I41/a空间群,其晶格常数为a=0.527 5 nm, c=1.149 3 nm.通过TG-DTA分析了Nd∶NBW晶体的相关物理、化学性质,确定了其熔点为936.2 ℃,并与纯的钨酸铋钠晶体(分子式:NaBi(WO4)2,简称:NBW)进行了对比性研究.     

Yb:NGW激光晶体生长及光谱性能

采用提拉法生长了φ30mm×70mm的掺镱钨酸钆钠[Yb:NaGd(WO4)2,Yb:NGW]晶体,并对晶体进行了退火处理。讨论了Yb:NGW晶体的生长工艺。确定了最佳生长工艺参数为:提拉速率为1～2mm/h,转速为15～18r/min,冷却速率为10℃/h,轴向温度梯度为液面上0.7～1℃/mm。通过热重–差热分析(thermogravimetry–differential thermal analysis,TG–DTA),X射线衍射(X-raydiffraction,XRD)对退火的晶体进行表征。测试了晶体的红外光谱和Raman光谱,并对出现的峰值进行了振动归属。测量了晶体的吸收光谱和荧光光谱。由TG–DTA曲线得到晶体熔点为1252.02℃。XRD分析表明:晶体属于四方晶系、白钨矿结构、I41/a空间群,计算的晶胞参数a=0.53603nm,c=1.11628nm。吸收光谱显示:晶体在968nm处吸收峰最强,半峰宽为57nm,适合激光二极管泵浦。     

掺钕钨酸钆钠晶体生长、结构及光谱特性

采用提拉法生长了尺寸为φ(30～35)mm×80mm的掺钕钨酸钆钠[Nd:NaGd(WO4)2,Nd:NGW]晶体。生长Nd:NGW晶体的最佳工艺参数为:晶体的提拉速率为1～2mm/h,晶体转速为15～18r/min,冷却速率为10℃/h,液面上轴向温度梯度为0.7～1℃/mm。通过热重-差热分析(thermogravimetry-differential thermal analysis,TG-DTA),X射线衍射(X-ray diffraction,XRD)对晶体进行表征。测试了晶体的红外及Raman光谱,分析了晶体的振动模式,并将晶体振动光谱进行归属。由TG-DTA曲线得到晶体熔点为1251.7℃。XRD分析表明:晶体属于四方晶系、白钨矿结构、I41/a空间群,晶胞参数a=0.53213nm,c=1.13070nm。吸收光谱表明:Nd:NGW晶体在805nm附近有较强、较宽的吸收峰,吸收截面积为3.581×10-20cm2,适合于激光二极管泵浦。     

Yb:NaY(WO4)2激光晶体的光谱性能

采用提拉法生长出了Yb：NaY(WO4)2晶体,给出了晶体生长的最佳工艺参数：拉速0．5～4mm／h,转速30～40r／min,冷却速率18℃／h。由TG-DTA分析得到晶体的熔点为1209℃。测试了该晶体的Raman光谱、吸收光谱和荧光光谱,计算了吸收光谱和荧光光谱中的有关参数。结果表明：该晶体发射波长为1010nm,在848,968nm附近有较强、较宽的吸收峰,适合于LD泵浦。     

提拉法生长钨酸钆镉晶体

用提拉法生长了四方晶系白钨矿结构的钨酸钆镉[CdGd2(WO4)4,CGW]晶体.通过X射线衍射分析计算出晶胞参数a=b=0.5204 nm,c=1.1360 nm.为改进CGW晶体的生长工艺,采取了一些避免生长过程中出现组分过冷现象的工艺措施,提出了晶体生长的最佳工艺参数:拉速为0.84 mm/h,转速为40 r/min,熔体中界面处的温度梯度为46～47 ℃/cm,冷却速率为32 ℃/h.测试了晶体的紫外-可见光谱和Raman光谱,测量得到晶体在紫外波段的截止波长为326 nm,并讨论了晶体的紫外吸收边起源和Raman光谱中各峰的振动归属.     

Yb∶NaY(WO_4)_2激光晶体的光谱性能

采用提拉法生长出了Yb∶NaY(WO4 ) 2 晶体 ,给出了晶体生长的最佳工艺参数 :拉速 0 .5～ 4mm/h ,转速 3 0～ 40r/min ,冷却速率 18℃ /h。由TGDTA分析得到晶体的熔点为 12 0 9℃。测试了该晶体的Raman光谱、吸收光谱和荧光光谱 ,计算了吸收光谱和荧光光谱中的有关参数。结果表明 :该晶体发射波长为 10 10nm ,在 848,968nm附近有较强、较宽的吸收峰 ,适合于LD泵浦     

NaBi(WO4)2晶体生长与光谱性能

采用提拉法生长出钨酸铋钠晶体[分子式NaBi(WO4)2, 简称NBW].生长过程中, 对影响晶体开裂的原因进行了详细的分析, 设计了合理的工艺参数 液面上下10mm内的温度梯度为0.8 ℃/mm, 径向温度梯度小于0.3 ℃/mm.拉速为2～4 mm/h, 转速为10～15 r/min, 降温速率为25 ℃/h, 生长出尺寸为45 mm×35 mm的高质量的钨酸铋钠晶体.X射线衍射分析结果表明, NBW晶体属于四方晶系,空间群为I41/a.光透射测试结果表明了NBW晶体的抗辐照损伤能力强;发射光谱分析发现它的发射峰值位于可见光绿光波段.     

铒镱共掺钨酸钆钾激光晶体生长、结构及光谱特性

采用顶部籽晶提拉法生长出铒镱共掺钨酸钆钾[Er3 :Yb3 :KGd(WO4)2,Er:Yb:KGW]激光晶体.这种晶体的最佳生长工艺参数为:转速为10～15 r/min,提拉速率为1～2mm/d,降温速率为0.05～0.1℃/h,生长周期为10～15d.X射线衍射分析表明,所生长的晶体为β-Er:Yb:KGW.经热重-差热分析确定:晶体的熔点为1 079℃,相转变温度为1 024℃.测量晶体的红外及Raman光谱,并对峰值及相应的原子基团振动进行了归属.晶体样品的吸收光谱显示:在380,523,935 nm和981 nm处存在较强的吸收峰,主峰981 nm处的吸收截面积为3.35×10-20 cm2.分别在488 nm和980 nm波长光激发下,均可以产生较强的1.53 μm对人眼安全的激光,表明Yb3 对Er3 具有敏化作用,既提高了对泵浦光的吸收效率,又降低了激光振荡阈值.     

NaM(WO4)2(M:Bi3+,Y3+,Gd3+)晶体生长与结构

采用提拉法生长出了钨酸铋钠[NaBi(WO4)2,NBW]、钨酸钇钠[NaY(WO4)2,NYW]和钨酸钆钠[NaGd(WO4)2,NGW]晶体.通过热重-差热分析(tbermogravimetry-differential thermal analysis,TG-DTA),X射线衍射(X-ray diffraction,XRD)分析对晶体进行表征.由TG-DTA曲线得到NBW,NYW和NGW晶体的熔点分别为937.7,1210.0℃和1 252.8℃.XRD分析表明:3种晶体都属于四方晶系、白钨矿结构、I41/a空间群.计算了3种晶体的晶胞参数,NBW晶体的晶胞参数要大于NYW和NGW晶体的.测试了晶体的红外光谱及Raman光谱,分析了晶体的振动模式,并将晶体振动光谱进行归属.通过比较认为三者结构基本相同.     

Generating Line Spectra from Experimental Responses. III. Interconversion between Relaxation and Retardation Behavior

Abstract

An algorithm is described which allows relaxation line spectra to be interconverted into retardation line spectra, and vice versa. The first line spectrum is generated from a given experimental response such as the relaxation modulus, the storage modulus, or the loss modulus, or from a response such as the creep compliance, storage compliance, or loss compliance. The interconversion algorithm is here applied to the standard linear solid and liquid models, and to a 32-line spectrum simulating the behavior of an entangled polymer.     

吡贝地尔的波谱学分析与结构确证

通过波谱学分析对吡贝地尔的化学结构进行确证。测定了吡贝地尔的高分辨质谱(HRMS)、核磁共振波谱(包括1 HNMR、13 CNMR、DEPT-135和HSQC)、质谱(MS)、紫外光谱(UV)、红外光谱(IR)等,并且对样品进行了差热分析(DSC)和热重分析(TGA)。对该化合物所有的1 HNMR和13 CNMR谱信号进行了归属,讨论了红外和紫外特征吸收峰所对应官能团的振动形式。对吡贝地尔的质量控制具有重要的参考价值。     

Bi0.6Ca0.4Mn0.2Fe0.8O3的介电性能研究

用溶胶-凝胶法制备了Bi0.6Ca0.4Mn0.2Fe0.8O3样品,通过检测样品的X衍射、介电谱和阻抗谱,对其微观结构和介电性能进行了研究.研究表明:随着频率的增加,样品的介电常数逐渐减小,而随着温度的增加,样品的介电常数逐渐加大.同时发现,通过在Bi0.6Ca0.4MnO3的Mn位进行Fe掺杂,明显的改善了Bi0....     

Novel scheelite-type [Ca0.55(Nd1-xBix)0.3]MoO4 (0.2 ≤ x ≤ 0.95) microwave dielectric ceramics with low sintering temperature

Novel scheelite-type [Ca_0.55(Nd_1-xBi_x)_0.3]MoO₄ (0.2 ≤ x ≤ 0.95) ceramics were prepared using the solid-state reaction method. According to the X-ray diffraction data, a solid solution was formed in 0.2 ≤ x ≤ 0.95 and all the samples belong to pure scheelite phase with the tetragonal structure. As revealed by Raman spectroscopy, the number of vibrational modes decreased with the increase in x value, which further indicated that Bi³⁺ ions occupied A-site of scheelite structure. As the x value increased, the sintering temperature decreased from 740°C to 660°C; the permittivity increased from 12.6 to 20.3; the Qf value first decreased slightly and gradually remained stable. Based on the infrared reflectivity spectrum analysis, the calculated permittivity derived from the fitted data shared the same trend with the measured value. The [Ca_0.55(Nd_0.05Bi_0.95)_0.3]MoO₄ ceramic sintered at 660 °C attained a near-zero value temperature coefficient ~τ_f (−7.1 ppm/°C) and showed excellent microwave dielectric properties with a ɛ_r ~ 20.3 and a Qf ~ 33 860 GHz, making this system a promising candidate in the ultralow temperature cofired ceramic (ULTCC) technology.     

Phase composition,Raman spectra,infrared spectra and dielectric properties of Li2MgTi1-x(Mg1/3Nb2/3)xO4 ceramics at microwave frequency

The Li₂MgTi_1-x(Mg_1/3Nb_2/3)_xO₄ (0?≤x?≤?0.5) ceramics were prepared by the conventional solid-state method. The relationship among phase composition, substitution amount and microwave dielectric properties of the ceramics was symmetrically investigated. All the samples possess the rock salt structure with the space group of Fm-3m. As the x value increases from 0 to 0.5, the dielectric constant linearly decreases from 16.75 to 15.56, which can be explained by the variation of Raman spectra and infrared spectra. The Q·f value shows an upward tendency in the range of 0?≤x?≤?0.3, but it then decreases when x?>?0.3. In addition, the temperature coefficient of resonant frequency (τ_f) is shifted toward zero with the increasing (Mg_1/3Nb_2/3)⁴⁺ addition. By comparison, the Li₂MgTi_0.7(Mg_1/3Nb_2/3)_0.3O₄ ceramics sintered at 1400?°C can achieve an excellent combination of microwave dielectric properties: ε_r=?16.19, Q·f =?160,000?GHz and τ_f =??3.14?ppm/°C.     

A/B-site cosubstituted Ba4Pr28/3Ti18O54 microwave dielectric ceramics with temperature stable and high Q in a wide range

High permittivity Ba₄(Pr_1-xSm_x)_28/3Ti_18-yAl_4y/3O₅₄(0.4≤x ≤ 0.7, 0≤y ≤ 1.5) ceramics were synthesized using a standard solid-state method. The effects of Sm³⁺ substitution into the A-site and Sm³⁺/Al³⁺ cosubstitution into the A/B-sites on the microstructure, crystal structure, Raman spectra, infrared reflectivity (IR) spectra and dielectric characteristics were investigated in a Ba₄Pr_28/3Ti₁₈O₅₄ solid solution. In the ceramic samples of Ba₄(Pr_1-xSm_x)_28/3Ti₁₈O₅₄(0.4≤x ≤ 0.7), Sm³⁺ partial substitution for Pr³⁺ could improve the quality factor (Qf) value and reduce the TCF value. Nevertheless, the quality factor (Qf~10,000GHz) needed further improvement and the TCF values (+12.3~+35.4 ppm/°C) were still too large. Therefore, Al³⁺ was introduced for further optimization of the TCF values and Qf values of the Ba₄(Pr_1-xSm_x)_28/3Ti₁₈O₅₄ ceramics. Sm/Al cosubstitution led to a good combination of high ε_r (ε_r ≥ 70), high Qf (Qf ≥ 12,000 GHz), and near-zero TCF (−10 < TCF < +10 ppm/°C) in a wide range (0.4≤x ≤ 0.7). Infrared reflectivity (IR) spectra indicated that A-TiO₆ vibration modes gave the primary contribution rather than Ti–O bending and stretching modes. The decrease in the degree of B-site cations order could be confirmed by Raman spectra. XPS results demonstrated that the improvement of quality factor (Qf) value was strongly related to the suppression of Ti³⁺. Excellent dielectric properties were achieved in Ba₄(Pr_1-xSm_x)_28/3Ti_18-yAl_4y/3O₅₄ microwave ceramics with x = 0.5 and y = 1.25: ε_r = 72.5, Qf = 13,900GHz, TCF = +1.3 ppm/°C.     

Enhancement of the optical properties of poly vinyl alcohol by doping with silver nanoparticles

Poly vinyl alcohol (PVA) incorporated with different weight percent of Silver nanoparticles (Ag NPs) were prepared. The enhancement factors for each band in the Raman spectra were calculated and the degree of enhancement were found to be increased as the percent of Ag NPs increases up to 0.3%, and thereafter it decreases. Some bands were red shifted while others were blue shifted. The overtones FTIR bands and photoacoustic spectra were recorded and show the same behavior as those bands. The X‐ray diffraction pattern and Raman and photoacoustic spectra showed that PVA has a high degree of crystallinity. The UV–vis spectra of the same samples were red shifted and increase in their intensities up to 0.3% Ag NPs, thereafter the band intensities of the peak corresponding to Ag NPs were diminished. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3608–3614, 2006     

苯甲酸与牛血清白蛋白相互作用的荧光光谱研究

采用荧光光谱、三维荧光光谱、同步荧光光谱研究了苯甲酸与牛血清白蛋白(BSA)分子之间的相互作用机制、特征及苯甲酸对牛血清白蛋白构象的影响。根据不同温度下苯甲酸对牛血清白蛋白的荧光猝灭作用,利用Stem-Volmer和Lineweaver-Burk方程和热力学方程分别处理实验数据,求得它们之间的结合常数K为1.096×103L/mol、结合位点数n为1.12(20℃),ΔH=-31.8 kJ/mol,ΔG=-17.1 kJ/mol,ΔS=-50.2 J.mol-1.K-1。研究发现苯甲酸对BSA内源性荧光的猝灭作用属于静态猝灭,苯甲酸与BSA分子之间的相互作用是一个吉布斯自由能降低的自发过程,两者之间的主要作用力类型为氢键力或范德华力。     

A spectroscopic study of amorphous and crystalline Ti-containing silicas and their surface acidity

Different titanium silicalite (TS-1) samples and TiO₂/SiO₂ aerogels samples have been prepared and characterized structurally by XRD, skeletal FT-IR and FT-Raman spectroscopies and diffuse reflectance UV spectroscopy. The surface acidity of all materials has been investigated by FT-IR spectroscopy of the surface hydroxy groups and of adsorbed acetonitrile. The TS-1 samples are found to be totally free from extra-framework Ti oxide species, while the characteristic features of framework tetrahedrally coordinated Ti cations are well evident. Framework Ti cations substituting for Si into the silicalite MFI structure act as quite strong Lewis acid sites towards acetonitrile. The presence of Ti neither changes significantly the Brønsted acidity of the silicalite silanols, nor results in the formation of new hydroxy groups. TS-1 samples present lower defectivity (smaller amount of clustered hydrolyzed Si–OH OH–Si bonds) than pure silicalite prepared in the same way. Extra-framework TiO₂, instead, is well detectable into aerogel samples, although framework Ti cations are likely also present. The surface of Ti-containing aerogels is covered by large amounts of silanol groups, although these sites do not present enhanced Brønsted acidity. Additionally, Lewis sites are detected whose strength is similar to that observed on TS samples, and is superior to that of the predominant sites on TiO₂. It is suggested that silica tends to cover the TiO₂ core in the case of aerogels. The surface is consequently dominated by silica with Ti sites in substitutional position.     

两种杯[6]芳烃的红外光谱和拉曼光谱研究

研究了两种对－叔丁基杯〔６〕芳烃的红外和拉曼光谱。对－叔丁基杯〔６〕芳烃Ｉ的环状的分子内缔合氢键和部分甲基化的（１，３，５－三甲基）－对－叔丁基杯（６）芳烃Ⅱ的三中心氢键在红外光谱中有明显反映杯（６）芳烃的ｐｉｎｃｈｅｄ ｃｏｎｅ（紧锥型）构象也得到了证明，而两种杯（６）芳烃氢键构象和强度的不同导致了二者的拉曼谱图也存在较大的差异。