钙钛矿型LaFeO3和SrFeO3的光催化性能

采用柠檬酸法合成钙钛矿型复合氧化物LaFeO3和SrFeO3,并以其为光催化剂对不同水溶性染料进行光催化降解实验.结果表明:SrFeO3的光催化活性明显高于LaFeO3,这与A位离子(La3+,Sr2+)的电子构型的不同有关.     

掺杂对巨磁电阻钙钛矿La1-xAx(MnB)O3 Curie温度的影响

测定了La1-xAx(MnB)O3（A为二价元素）型巨磁电阻钙钛矿化合物在不同组成的Curie温度。钙钛矿锰氧化物La1-xAx(MnB)O3的A位离子掺杂引起的晶格畸变可以用晶格能来表示，晶格能的大小能很好解释A位离子掺杂引起的Curie温度变化；B位离子掺杂引起的晶格畸变可用极化力来表示，极化力的大小很好解释了B位离子掺杂引起的Curie温度变化。钙钛矿锰氧化物的A，B位离子同时掺杂引起晶格畸变，可以用晶格能和极化力的综合判断系数（晶格能／极化力）来表示，它能很好解释A和B位离子同时改变引起的Curie温度变化，理论与实验结果一致。     

钙钛矿型薄膜材料氧敏性能的研究

以硝酸盐为原料 ,柠檬酸为络合剂 ,采用无机盐溶胶—凝胶法 (ISG)合成了钙钛矿型稀土复合氧化物LaBO3 (B为Ni、Fe、Cr)陶瓷薄膜 ,并研究了它们的氧敏性能。电阻—温度曲线表明 ,LaFeO3 和LaCrO3 陶瓷薄膜为半导体特性 ,而LaNiO3 陶瓷薄膜具有类金属特性 ,并且LaBO3 薄膜材料的氧敏性能主要由B位离子的d电子特性所决定 ,即B位离子越活泼 ,则其氧敏性能越好     

甲烷氧化制合成气LaFeO3催化剂的制备条件考察

采用溶胶-凝胶法制备了钙钛矿型复合氧化物LaFeO3,考察了合成过程中LaFeO3凝胶形成温度、催化材料焙烧温度、焙烧时间、络合剂种类、镧源种类以及氨基乙酸与硝酸根离子比对催化剂结构及性能的影响.结果发现催化剂最佳制备条件为:凝胶形成温度75 ～85℃;焙烧温度在900℃;焙烧时间10 h;氨基乙酸作络合剂;La2O3作为镧源;氨基乙酸与硝酸根离子比4∶3.     

超声辐照制备SrFeO3降解苯酚光催化性能研究

采用超声辐照柠檬酸络合法制备了复合氧化物SrFeO3，以苯酚为光催化探针分子，以450W高压汞灯为光源（主波长〉410nm），研究了SrFeO3光催化性能、研究表明，经过超声辐照制备的SrFeO3光催化活性提高一倍以上。XRD、TEM、DRS表征结果表明，超声辐照制备的SrFeO3粒径均匀、分散性好、粒径较小，光吸收红移显著。探讨了超声提高催化性能的机理。     

掺Sb的SrFeO_(3-δ)在CO_2中化学稳定性的提高

在钙钛矿型混合导体氧化物中,SrFeO3-δ显示了很好的透氧率,但是在CO2的存在下它很容易受到腐蚀。在800℃下SrFeO3-δ在CO2中退火100 h后,SrFeO3-δ分解成SrCO3和SrFe12O19。然而,我们通过在Fe的位置掺杂Sb元素成功地提高了SrFeO3-δ的化学稳定性,并且研究了对Sb的掺杂浓度对SrFe1-x Sbx O3-δ(x=0-0.30)的结构及氧透过率的影响。在800℃时,吹扫气体由He切换成CO2后,SrFeO3-δ的透氧量会立即迅速降低,但是对于样品SrFe1-x Sbx O3-δ(x=0.05-0.20)氧渗透速率反而增加。这项工作表明,掺杂Sb实现了SrFeO3-δ更好的CO2耐受力。     

(Ba1-xSrx)(Mg1/3 Ta2/3)O3微波陶瓷介电性能研究

Ba(Mg1/3Ta2/3)O3(简称BMT)陶瓷是A(B′1/3B″2/3)O3(A=Ba,Sr;B′=Zn,Mg;B″=Nb,Ta)型复合钙钛矿化合物中的一种,A位由Sr离子取代Ba离子,形成(Ba1-xSrx)(Mg1/3Ta2/3)O3(简称BSMT)固溶体型化合物,也具有复合钙钛矿结构。Sr含量x≥0．6时发生相转变,形成一种新的低温相,这是由于氧八面体畸变造成的。这种低温相结构与BMT六方晶系结构相比具有较低的对称性。低温相的形成．可显著降低BSMT陶瓷的烧结温度．在150℃即可烧结致密(BMT为160℃)。BSMT的微观结构和介电性能(如介电常数ε和介电常数温度系数aε)的变化也与此相转变有关。     

Al_2O_3-Cr_2O_3砖显微结构对抗渣性能的影响

分别采用静态坩埚抗渣法和回转抗渣法,对w(Cr2O3)=10%的A和B两种Al2O3-Cr2O3砖进行了抗渣性能对比。结果发现:两种砖的化学组成、显气孔率、体积密度和抗热震性相近,B砖强度优于A砖的。但由于与B砖相比,A砖内部气孔尺寸更小,所用电熔白刚玉骨料形貌平滑,较为致密,粒度呈连续式分布,且A砖中Al2O3-Cr2O3固溶体发育较小,相互交错,形成了孔隙较小的空间网状结构,这种显微结构显著降低了熔渣对耐火材料的渗透和破坏,使A砖的抗渣性优于B砖的。因此,制备微气孔化结构的制品是提高Al2O3-Cr2O3材料抗渣性能的有效途径。     

Ba（1-3x/2）Lax（Mg（1/3）Ta（2/3））O3陶瓷的微波介电性能（英文）

采用固相合成法制备了Ba1–3x/2Lax（Mg1/3Ta2/3）O3陶瓷,研究了La掺杂对钽镁酸钡的结构和微波介电性能的影响。结果表明：A位取代能改进其烧结性能。在x≤0.02时,烧结样品为单相的钙钛矿结构,B位离子1：2有序;当x〉0.02时出现第二相Ba0.5TaO3。B位离子有序度随着x的增大先增加后减小,在x=0.04时出现最大值。x≤0.02时介电常数变化较小,而后其值逐渐增大。品质因数与谐振频率的乘积（Q×f）值随着x的增大先增大后减小,在x=0.02时取得最大值;谐振频率温度系数（τf）值随着x增大而增大。     

BaO-Ln2O3-TiO2系高介电常数微波介质陶瓷的研究进展

简要叙述了BaO-Ln2O3-TiO2系微波介质陶瓷的结构研究情况,介绍了近年来该体系不同离子A、B位取代对微波介电性能的影响,最后提出了该材料需要进一步解决的问题和发展前景.     

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