Bi_4Ti_3O_(12)陶瓷的制备及微观结构

以过量的Bi2O3和TiO2为组分,采用固相烧结法制备Bi4Ti3O12陶瓷。借助XRD和SEM分析相成分和微观结构。结果表明:经750℃/2h预烧后,合成粉体由Bi4Ti3O12、少量的Bi12TiO20和Ti5O9以及Bi2O3组成。成型烧结后,Bi12TiO20和Ti5O9的衍射峰消失,出现了Bi2Ti2O7的衍射峰。1000℃烧结后,Bi2Ti2O7的衍射峰消失,产物基本为Bi4Ti3O12相。SEM分析表明,温度低时,气孔较多,晶粒较细;温度升高后,晶粒长大,气孔减少;到1000℃时,气孔显著减少,晶粒尺寸约为2～5μm。     

低温烧结CuO-V_2O_5-Bi_2O_3掺杂Zn_3Nb_2O_8陶瓷的微波介电性能

研究了CuO–V2O5–Bi2O3作为烧结助剂对Zn3Nb2O8陶瓷的烧结特性、微观结构、相结构及微波介电性能的影响。CuO–V2O5–Bi2O3复合掺杂可以将Zn3Nb2O8陶瓷的烧结温度从1150℃降到900℃。在900℃烧结4h的Zn3Nb2O8–0.25%(质量分数,下同)CuO–1.5%V2O5–1.5%Bi2O3陶瓷的密度达到了理论密度的98.1%,相对介电常数为18.8,品质因数与谐振频率之积为39442GHz。该体系的介电性能和陶瓷的致密度与烧结助剂的含量及烧结温度密切相关,陶瓷的致密度和相对介电常数随CuO–V2O5–Bi2O3烧结助剂含量的增加而增加,同样陶瓷的致密度和相对介电常数也随烧结温度的升高而提高。     

溶胶-凝胶法制备巨介电常数材料CaCu3Ti4O12

通过溶胶-凝胶法制备CaCu3Ti4O12干凝胶,再经700～900℃,6～10h预烧和950～1 100℃,16～20h烧结,成功制备了CaCu3Ti4O12粉体和CaCu3Ti4O12巨介电常数陶瓷材料.用X射线衍射、扫描电镜分别确定了样品的结晶性能和形貌.用阻抗分析仪在10～106Hz范围内测试了陶瓷样品的介电性能.结果表明:粉体的结晶性能与煅烧温度有关,陶瓷介电性能与其晶粒大小有关.相对于传统固相反应合成法制备的粉体和陶瓷,粉体的预烧和陶瓷的烧结温度都有明显降低,烧成温度至少降低100℃.在800℃预烧的CaCu3Ti4O12粉体并在1 100℃温度下烧结制备的陶瓷,其介电常数可达194753.     

添加剂对MgTiO3陶瓷性能的影响

研究了H3BO3,CaO-SiO2-B2O3玻璃料及V2O5的添加对MgTiO3陶瓷的烧结和介电性能的影响,并对影响机理作了初步探讨。结果表明:合适的添加剂能够使MgTiO3陶瓷在1240～1300℃之间烧结;添加质量分数为3%的H3BO3,V2O5或1%的CaO-SiO2-B2O3玻璃料的MgTiO3陶瓷的介电常数分别为20.8,17.5和19.8,在5～20MHz下,介电损耗低,多为10-4数量级;在10kHz下,介电常数的温度系数在-66×10-6/℃左右,是一种性能良好的微波介质材料。     

添加剂对钛酸镁陶瓷性能影响的研究进展

综述了添加剂对钛酸镁陶瓷性能影响的研究现状,烧结及介电性能等方面的进展。研究结果中可以看出,Bi2O3-V2O5、Co2O3、ZnO等氧化物及氧化物玻璃料的添加可以不同程度地大幅降低陶瓷的烧结温度。在Mg2TiO4中掺杂不同添加剂可适当改变其介电常数,满足其介电常数材料的应用需要;在MgTiO3中掺入不同添加剂可不同程度改变其介电常数,得到具有较高Q*f值且τf≈0的钛酸镁基陶瓷材料。从当前研究现状可以看出,掺杂改性是获得所需性能材料的强有力手段,也是今后对钛酸镁基陶瓷性能优化的主要研究方向之一。     

钛酸铋陶瓷靶材的热压烧结

纯相、高致密度、结晶良好的陶瓷靶材是物理气相沉积薄膜的前提.采用热压烧结方法制备钛酸铋(Bi4Ti3O12)陶瓷靶材,重点研究了制备工艺对靶材的物相、微观结构和致密度的影响.以Bi2O3和TiO2微粉为原料,采用固相反应法,在800℃合成出纯相的Bi4Ti3O12粉体;加入过量3wt%的Bi2O3,可以有效防止烧结过程中因Bi挥发所产生的杂相,得到纯相的Bi4Ti3O12陶瓷;采用热压烧结方法,进一步实现了Bi4Ti3O12粉体的致密烧结,确定了适宜的制备条件为850℃,30MPa,2b,在该条件下制备的Bi4Ti3O12陶瓷致密度达到99%,晶粒呈片层状,大小约2-4μm,可满足靶材制备薄膜的需求.     

SrTiO3基高压陶瓷电容器材料的改性研究

研究了Bi2O3·3TiO2和MgTiO3的加入量对SrTiO3基高压陶瓷电容器材料性能的影响,并用扫描电子显微镜（SEM）对样品进行形貌观察。实验结果表明：加入适量的Bi2O3·3TiO2能提高材料的介电常数和降低介质损耗,适量MgTiO3的加入改善了材料的温度特性,且其晶粒尺寸均匀。     

添加剂对0.95MgTiO3-0.05CaTiO3陶瓷性能的影响

采用同相反应法分别制备了V2O5,Co2O3和ZnO氧化物掺杂的0.95MgTiO3-0.05CaTiO3(95MCT)介质陶瓷.研究了V2O5,Co2O3和ZnO氧化物掺杂对95MCT陶瓷烧结特性和介电性能的影响.结果表明:V2O5.Co2O3和ZnO氧化物掺杂的95MCT陶瓷的主晶相为MgTiO3和CaTiO3两相结构,无中间相MgTi2O5出现.V2O5,Co2O3和ZnO氧化物掺杂可以有效地降低95MCT陶瓷的烧结温度,提高致密化程度,降低介电损耗,调节温度系数.ZnO掺杂的95MCT陶瓷性能最好:烧结温度降低至1 250℃,介电常数为21.7,烧结密度可达3.8g、cm3(理论密度的98.4%),介电损耗降低至10-5,温度系数为0.12×10-5/℃.     

铋层状化合物Sr0.3Ba0.7Bi4-xLaxTi4O15陶瓷材料的介电性能

采用固相烧结工艺制备了铋层状化合物Sr0．3Ba0.7Bi4-xLaxTi4O15铁电陶瓷。X射线衍射证实：La含量很大的范围内(x=0～1)均形成了层状钙钛矿结构固熔体。Sr0.3Ba0.7Bi3.25La0.75Ti4O15粉料在低温下难以烧结,随着烧结温度的提高,Sr0．3Ba0.7Bi4-xLaxTi4O15陶瓷密度增加的同时,产生焦绿石相,但La的加入在一定程度上抑制焦绿石相的形成．Sr0．3Ba0.7Bi4-xLaxTi4O15陶瓷的介电常数峰在10kHz时较宽,在100Hz时,介电常数峰被随温度升高而逐渐增大的介电常数所“屏蔽”,材料损耗角正切随温度升高而增大,在低频下增加得更快。     

Li2Zn3(1-x)Ca3xTi4O12微波陶瓷介电性能研究

本文以Li2CO3,ZnO,CaCO3,TiO2为原料,采用固相反应法制备了Li2Zn3(1-x)Ca3xTi4O12(x=0,0.05,0.1,0.15)陶瓷,并研究了CaTiO3固溶量对其显微结构和微波介电性能的影响.结果表明:Li2Zn3Ti4O12晶相中固溶CaTiO3相,晶胞参数会增大;少量CaTiO3相固溶于Li2Zn3Ti4O12陶瓷后,提高了Li2Zn3Ti4012陶瓷的烧结温度及其介电常数,但降低了其品质因素,可增大其温频系数.在1100℃/2 h烧结条件下,Li2Zn2.7Ca0.3Ti4O12陶瓷微波介电性能达到:εr=24,Q×f=50000 GHz,Tf=-25×10-6/℃.     

Ferroelectric Ceramics in the PbMg1/3Nb2/3O3-PbCd1/3Nb2/3O3 System

Solid solutions (1-x)PbMg_1/3Nb_2/3O₃ + xPbCd_1/3Nb_2/3O₃ with x = 0-0.30 are investigated with purpose to work out a capacitor ceramics with good dielectric properties and low sintering temperature. It is found that the perovskite phase forms at sintering near to 980°C and begins to decompose at higher temperatures. When x grows from 0 to 0.30, the Curie temperature linearly grows from -10°C to +25°C, the dielectric permittivity ε_m in the Curie point T_C decreases from 18000 to 6800 and the phase transition becomes more diffused. The dielectric permittivity at room temperature is rather high and the temperature stability is improved. The system is of interest, because it can serve as a base for working out some ceramic materials for capacitors with low sintering temperature, which needs of no special atmosphere at burning.     

3-溴甲基-3-甲基氧杂环丁烷的合成

以2,2-二溴甲基丙醇（BBMP）为初始原料,通过与碱发生关环反应生成3-溴甲基-3-甲基氧杂环丁烷（BrMMO）。讨论了碱的种类和用量对BBMP关环产率的影响以及反应体系中碱的浓度、反应温度和反应时间对合成BrMMO产率的影响。通过实验确定的最佳工艺条件为：BBMP与NaOH摩尔比为1.0∶1.1,NaOH醇溶液的质量分数为12%,反应温度为78℃,反应时间为4h时,BrMMO产率为65%。最终产品经元素分析、IR和1HNMR检测确定为BrMMO。该试验工艺简单,原料易得,且溶剂便于回收、污染小。     

3-叠氮甲基-3-甲基氧丁环的合成

以三羟甲基乙烷与碳酸二乙酯为原料,经环化反应合成了3-羟甲基-3-甲基氧丁环(HMM O)。在低温下,HMM O与对甲苯磺酰氯反应生成3-磺酸酯甲基-3-甲基氧丁环(M TM O)。M TM O和叠氮化钠发生叠氮化反应形成叠氮单体3-叠氮甲基-3-甲基氧丁环(AMM O)。三步反应收率分别为76%,96%,85%。用核磁、红外、元素分析和DSC表征了化合物的结构与性能。结构鉴定表明为目标化合物AMM O。     

3-溴甲基-3-甲基氧杂环丁烷的合成

以2,2-二溴甲基丙醇(BBMP)为初始原料,通过与碱发生关环反应生成3-溴甲基-3-甲基氧杂环丁烷(BrMMO).讨论了碱的种类和用量对BBMP关环产率的影响以及反应体系中碱的浓度、反应温度和反应时间对合成BrMMO产率的影响.通过实验确定的最佳工艺条件为:BBMP与NaOH摩尔比为1.0∶1.1,NaOH醇溶液的质量分数为12%,反应温度为78℃,反应时间为4 h时,BrMMO产率为65%.最终产品经元素分析、IR和1HNMR检测确定为BrMMO.该试验工艺简单,原料易得,且溶剂便于回收、污染小.     

The Preparation and Crystal Structure of TlMnCl3, TlFeCl3, TlCoCl3 and TlNiCl3

The compounds TlMnCl₃, TlFeCl₃, TlCoCl₃ and TlNiCl₃ were prepared by heating T1C1 with the corresponding transition metal dichloride in an evacuated ampoule. Atomic positions were determined from powder photographs. All four compounds were found to be related to the perovskite type structure. TlMnCl₃ has a cubic structure, space group Pm3m, with a_o = 5.025 Å. The other three compounds are hexagonal, probable space group P6₃mc, with cell dimensions (in Å) a₀ = 6.976 and c₀ = 6.008 for the Fe compound, a₀ = 6.907 and c₀ = 5.981 for the Co compound and a₀ = 6.863 and c₀ = 5.881 for the Ni compound. The three hexagonal compounds are isomorphous. A measureable concentration of basal plane stacking faults was found to occur in TlFeCl₃ and also, to a lesser degree, in TlCoCl_3.     

Tunable color emission in LaScO3:Bi3+,Tb3+,Eu3+ phosphor

LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ (x = 0 − 0.04, y = 0 − 0.05, z = 0 − 0.05) phosphors were prepared via high-temperature solid-state reaction. Phase identification and crystal structures of the LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ phosphors were investigated by X-ray diffraction (XRD). Crystal structure of phosphors was analyzed by Rietveld refinement and transmission electron microscopy (TEM). The luminescent performance of these trichromatic phosphors is investigated by diffuse reflection spectra and photoluminescence. The phenomenon of energy transfer from Bi³⁺ and Tb³⁺ to Eu³⁺ in LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ phosphors was investigated. By changing the ratio of x, y, and z, trichromatic can be obtained in the LaScO₃ host, including red, green, and blue emission with peak centered at 613, 544, and 428 nm, respectively. Therefore, two kinds of white light-emitting phosphors were obtained, LaScO₃:0.02Bi³⁺,0.05Tb³⁺,zEu³⁺ and LaScO₃:0.02Bi³⁺,0.03Eu³⁺,yTb³⁺. The energy transfer was characterized by decay times of the LaScO₃:xBi³⁺, yTb³⁺, zEu³⁺ phosphors. Moreover absolute internal QY and CIE chromatic coordinates are shown. The potential optical thermometry application of LaScO₃:Bi³⁺,Eu³⁺ was based on the temperature sensitivity of the fluorescence intensity ratio (FIR). The maximum S_a and S_r are 0.118 K⁻¹ (at 473.15 K) and 0.795% K⁻¹ (at 448.15 K), respectively. Hence, the LaScO₃:Bi³⁺,Eu³⁺ phosphor is a good material for optical temperature sensing.     

2,2,3-三氯-3-苯基-3-(3-甲基苯甲酰基)丙腈的合成研究

以苯甲酰氯、四氯化碳、间甲基苯甲酰氰为原料,合成了标题化合物。重点考察了氰化过程中不同原料配比、反应温度、时间、溶剂和催化剂用量对收率的影响。实验结果表明,其最佳反应条件为:n(1,1,2-三氯-2-苯基乙烯)∶n(3-甲基苯甲酰氰)=1∶1.2,二氯甲烷为反应溶剂,3 mmol催化剂三乙胺,室温反应5 h,总收率达80.6%。     

Thermal analyses of poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)

Thermal analyses of poly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(HB–HV)], and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(HB–HHx)] were made with thermogravimetry and differential scanning calorimetry (DSC). In the thermal degradation of PHB, the onset of weight loss occurred at the temperature (°C) given by T_o = 0.75B + 311, where B represents the heating rate (°C/min). The temperature at which the weight-loss rate was at a maximum was T_p = 0.91B + 320, and the temperature at which degradation was completed was T_f = 1.00B + 325. In the thermal degradation of P(HB–HV) (70:30), T_o = 0.96B + 308, T_p = 0.99B + 320, and T_f = 1.09B + 325. In the thermal degradation of P(HB–HHx) (85:15), T_o = 1.11B + 305, T_p = 1.10B + 319, and T_f = 1.16B + 325. The derivative thermogravimetry curves of PHB, P(HB–HV), and P(HB–HHx) confirmed only one weight-loss step change. The incorporation of 30 mol % 3-hydroxyvalerate (HV) and 15 mol % 3-hydroxyhexanoate (HHx) components into the polyester increased the various thermal temperatures T_o, T_p, and T_f relative to those of PHB by 3–12°C (measured at B = 40°C/min). DSC measurements showed that the incorporation of HV and HHx decreased the melting temperature relative to that of PHB by 70°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 90–98, 2001