助熔剂法生长CaLa2B10O19晶体

本文通过X射线衍射(XRD)分析、差热分析(DTA)和化学分析研究了CaLa2B10O19(LCB)晶体中的包裹体及在晶体生长过程中包裹体产生的原因.说明了包裹体的主要成份是LaB3O6,高温溶液中B2O3的挥发是造成包裹体产生的主要原因.为消除包裹体的产生,选择了合适的助溶剂,分别以100mol; CaB4O7和50mol; B2O3和150mol; CaB4O7为助溶剂生长出了一定尺寸、光学质量较高的LCB晶体.     

一种具有倍频效应的新型硼酸盐化合物La2SrB10O19

在SrO-La2O3-B2O3体系中合成出一种新的硼酸盐化合物La2SrB10O19.La2SrB10O19的晶体结构与La2CaB10O19相同.La2SrB10O19的粉末倍频效应(SHG)大约是KH2PO4(KDP)的2倍.差热分析结果表明该化合物为非同成分熔融化合物,转熔温度约为983℃,可以用助熔剂法进行晶体生长.反射光谱研究表明La2SrB10O19的紫外吸收边在300nm左右.     

赝二元系LiF-SrAlF5相图

本文通过差热分析(DTA)和X射线粉末衍射(XRD)方法研究了赝二元系LiF-SrAlF5的相平衡关系.该赝二元系在LiF:SrAlF5=1:1处形成一致融熔化合物LiSrAlF6,其熔点为765℃,并分别在LiF-LiFSrAlF6和LiSrAlF6-SrAlF5区域出现两个低共熔点,其共晶温度分别为673℃和705℃,根据体系的相图,采用坩埚下降法生长出氟化物激光晶体Cr3+:LiSrAlF6.     

感应加热碳热还原合成LaB6粉体

以La2O3、B2O3为原料、沥青粉为还原剂,在感应炉中采用碳热还原法快速制备了LaB6粉体.利用XRD、SEM、TEM以及激光粒度分析仪对合成的LaB6粉体进行了表征.结果表明:在感应加热及Ar气气氛下,经1600℃保温30 min后可获得分散性好且晶粒发育良好的LaB6粉体,其d50约为4.58 μm.在感应场下加热可明显缩短反应时间,这主要是由于在高温以及感应场的协同作用下反应体系中的液相快速生成加速了物质的迁移以及B4C过渡相的析出,从而促进了LaB6的形成.     

一个新的过氧钼酸盐(NH4)4(CH6N3)2[Mo7O23(O2)]·3H2O的合成、晶体结构及催化性质

以钼酸铵和盐酸胍为原料,30;双氧水为氧化剂,在室温下采用常规的水溶液法合成了一种新的单过氧七核钼酸盐(NH4)4(CH6 N3)2[Mo7O23(O2)]·3H2O,通过元素分析、X-射线单晶衍射、红外光谱、固体紫外可见光谱对其进行了表征.标题化合物属于单斜晶系,P21/n空间群,a=1.367(14) nm,b=1.085(11) nm,c =2.748(3) nm,β=93.15(2)°,V=4.0685(7) nm3,Z=4,Dc=2.031g· cm-3,R1 =0.0713,wR2 =0.2199(I＞2σ),GOF=1.03.将合成的过氧钼酸盐(NH4)4(CH6N3)2[Mo7 O23 (O2)]·3H2O作为催化剂用于苯甲醇氧化合成苯甲酸的反应,考察了催化剂用量、氧化剂(30;H2O2)的用量、反应温度、反应时间等对苯甲酸产率的影响.最佳催化反应条件是:n(催化剂)∶n(苯甲醇)=0.063∶1,n(H2O2)∶n(苯甲醇)=40∶1,反应温度85℃,反应时间7h,苯甲酸的产率达到82.2;.     

钾明矾基低共熔相变储热材料的制备与研究

以钾明矾(KAl(SO4)2·12H2O)为基元,分别加入不同质量比例的七水硫酸镁(MgSO4·7H2O)和芒硝(NaSO4·10H2O)混合均匀后加热融化,研究制备出的低共熔材料的相变温度、潜热释放平台及过冷和相分离变化情况.结果表明,七水硫酸镁和钾明矾在任意比例下的混合都能制得低共熔相变储热材料,共晶点在质量比5∶5附近,相变温度41.19℃,持续放热时间长,过冷度1.15℃,无相分离现象出现;而以芒硝与钾明矾混合制备低共熔相变储热材料,共晶点在质量比2∶8附近,相变温度50.10℃,过冷度1.2℃且无相分离现象出现.这两种处于共晶点成分(附近)的低共熔相变储热材料都是很有潜力的低温相变储热材料.     

CaLa2B10O19晶体生长及其定向

本文报道了一种稀土硼酸盐晶体,CaLa2B10O19(LCB),晶体生长及折射率的测量,确定了其结晶学轴(a,b,c)与物理学轴(X,Y,Z)之间的夹角关系.     

B2O3对6ST-4LA微波介质陶瓷结构与性能的影响

为降低0.6SrTiO3-0.4LaAlO3(简称6ST-4LA)微波介质陶瓷的烧结温度,采用固相反应法,研究了B2O3对其结构与性能的影响.结果表明:添加B2O3可有效地降低6ST-4LA陶瓷的烧结温度,由1550℃降至1450℃;主晶相仍为赝立方钙钛矿结构固溶体,但有第二相的出现,其含量随着B2O3添加量的增加先降低后升高.当B2O3添加量为0.50wt;在1450℃下烧结时,6ST-4LA陶瓷获得最佳微波介电性能:εr=44.46,Q·f=51127 GHz,τf=-2.3×106/℃.     

Ho~(3+)∶La_2CaB_(10)O_(19)晶体生长和光谱性能(英文)

采用顶部籽晶法生长Ho3+∶La2CaB10O19晶体。测试了晶体的X射线衍射谱图以及晶体器件的摇摆曲线,半峰宽为21.6 arcsec,晶体结晶质量良好。在室温下测试了吸收光谱、发射光谱和荧光寿命。应用Judd-Ofelt理论评价了Ho3+∶La2CaB10O19晶体的光谱性能。分别计算了Ho3+的唯象强度、谱线强度、辐射寿命、荧光分支比等参数。     

Dy3+掺杂对CaLaAl3O7晶体结构和发光性能的影响

采用高温固相法制备了CaLa1-xAl3O7∶ xDy3+(0≤x≤0.15)发光粉体,利用X射线衍射分析了材料的物相,计算发现:随Dy3+掺杂浓度的增加,晶胞体积线性减小.在348 nm光激发下,该系列样品发射谱为Dy3+的4f9组态内的特征发射峰,峰值波长分别为478 nm、577 nm和667 nm,总的发射呈现白色,色坐标计算值几乎相同,而且都处于白光区域内(色坐标(0.33,0.33)).CaLa1-xAl3 O7∶xDy3+材料发光强度随Dy3+浓度的增大呈现先增大后减小的趋势,在x=0.04时达到峰值.分析了材料在577 nm发射强度与Dy掺杂浓度的关系,并根据D.L.Dexter的相关理论得到:Dy3自身猝灭机理是电偶极-偶极相互作用.     

Elastic properties of the dithionates Na2S2O6 · 2 H2O,K2S2O6, Rb2S2O6, CaS2O6 · 4H2O and SrS2O6 · 4 H2O

Single crystals of the title compounds having optical quality and dimensions of several cm were grown from aqueous solutions. The elastic and thermoelastic constants were determined from ultrasonic resonance frequencies of thick plates. The true point symmetry of K₂S₂O₆ and Rb₂S₂O₆, which is screened by a hexagonal hypermorphy, could be clearly revealed to be trigonal (32) by the existence of the elastic constant c₁₄. In the case of CaS₂O₆ · 4H₂O and SrS₂O₆ · 4H₂O the constant c₁₄ of the specimens appeared too small to confirm the trigonal symmetry group required from electrooptic and non-linear optic effects unambiguously. The isotypy of K₂S₂O₂ and Rb₂S₂O₆ as well as that of CaS₂O₆ · 4H₂O and SrS₂O₆ · 4H₂O is confirmed by their elastic behaviour. The mean elastic stiffness of dithionates is closely related to that of the corresponding sulphates. In the vicinity of the second-order phase transition of K₂S₂O₆ near 235 K weak anomalies of the temperature derivatives of the longitudinal elastic stiffnesses are observed.     

On the Crystallographic Polytypes SrAl12O19 (BaFe12O19)–BaFe18O27

Crystallography Reports - A crystallographic analysis of SrAl12O19 (isostructural to BaFe12O19) and BaFe18O27 showed that the structures of both polytypes contain almost identical cationic and...     

CaO-MgO-Al2O3-Fe2O3-B2O3-SiO2系微晶釉的制备

通过引入B2O3以降低烧成温度,利用赤泥中的Fe2O3为着色剂,在1150℃左右低温烧成制备了CaO-MgO-Al2O3-Fe2O3-B2O3-SiO2系微晶釉.赤泥的加入量为20;左右时,釉面具有良好的装饰效果和显微硬度.利用XRD、SEM研究了釉的物相及显微组织.结果表明,釉中析出的微晶是普通辉石,微晶的含量随MgO及CaO的含量增加而增加,而提高Al2O3含量则抑制微晶的析出.     

Fe2O3-CO3O4共掺杂MgO-Al2O3-SiO2体系的红外辐射性能研究

采用固相反应法制备Fe2O3-Co3O4共掺杂MgO-Al2O3-SiO2体系的复合陶瓷材料,并通过XRD、SEM、XPS以及红外辐射测试等方法研究了样品的结晶行为与红外辐射性能.结果表明:Fe2 O3和Co3 O4共掺杂MgO-Al2 O3-SiO2体系后离子分布改变并生成混合尖晶石,从而引起品格畸变,从而有效提高材料的红外辐射性能.材料的红外发射率与其晶格畸变程度具有相同的变化趋势,并随Fe2 O3与Co3O4质量之比(R)的增加呈非线性变化.当R=3∶2时,材料在8 ～ 14 μm波段的辐射率可达0.92.     

Crystal and molecular structures of O,O-propan-1,3-dithionobenzoate (2TBZ-A), O,O-2,2-dimethylpropan-1,3-dithionobenzoate (2TBZ-B), and O,O,O,O-pentaerythritoltetrathionobenzoate (4TBZ)

The crystal and molecular structures of three thionobenzoates have been determined: O,O-propan-1,3-dithionobenzoate (2TBZ-A) is tetragonal witha=13.086(2),c=19.048(2) Å, space groupI4₁/a,Z=8; O,O-2,2-dimethylpropan-1,3-dithionobenzoate (2TBZ-B) is monoclinic witha=13.851(5),b=12.428(3),c=10.996(4) Å,=104.01(4)°, space groupP2₁/c,Z=4; and O,O,O,O-pentaerythritol-tetrathionobenzoate (4TBZ) is triclinic witha=15.423(4),b=10.924(3),c=10.698(2) Å,=112.43(2),=100.64(2), =104.57(2)°,Z=2, space groupP¯1. The structures were all solved by direct methods and refined by least squares toR=0.046 for 886 reflections (2TBZ-A),R=0.075 for 1458 reflections (2TBZ-B) andR=0.075 for 2975 reflections (4TBZ),I>3(I) in each case, CuK radiation, =1.5418 Å. The minimum S---CH₂ intramolecular distances in these three structures are significantly larger than the minimum corresponding distance in O,O,O-propan-1,2,3-trithionobenzoate (3TBZ) (Moore and Palmer, 1990), thus providing a possible explanation of why 2TBZ-A, 2TBZ-B, and 4-TBZ are inert with respect to pyrolitic solid-state isomerization; whereas 3TBZ readily undergoes thermally induced rearrangement (Das, 1978; Hedgley, 1981).     

Crystal structure of catena-poly[diaqua(μ-iminodiacetato-N,O,O′: O″)cobalt(II)]

The crystal structure of the [Co(C₄H₅NO₄)(H₂O)₂] complex has been determined by X-ray diffraction analysis (λMo, R = 0.0237 for 768 reflections). The crystals are orthorhombic, a = 14.345(1) Å, b = 5.234(1) Å, c = 9.780(1) Å, Z = 4, d _calcd = 2.045 g cm^?3, and space group Pca2₁. The donor atoms (one N and two O atoms) of the iminodiacetate ion (Ida) are located on the same octahedron face around the Co atom [Co-N, 2.120(3) Å; Co-O, 2.063(3) and 2.151(3) Å]. The O atoms of two water molecules are in the trans positions relative to the O atoms of the carboxylate groups [Co-O, 2.126(3) and 2.157(3) Å]. The sixth coordination site is occupied by the O atom of the adjacent Ida ion [Co-O, 2.054(3) Å], which results in the formation of infinite chains in the structure.     

EPR and magnetic susceptibility studies of B2O3–Bi2O3–Gd2O3 glasses

Glasses of the xGd₂O₃ · (100 − x)[B₂O₃ · Bi₂O₃] system with 0.5 ⩽ x ⩽ 10 mol% were studied by electron paramagnetic resonance (EPR) and magnetic susceptibility measurements. Data obtained show that for low gadolinium oxide contents of the samples (x ⩽ 3 mol%) the Gd³⁺ ions are randomly distributed in the host glass matrix and are present as isolated and dipole–dipole coupled species. For higher gadolinium oxide contents of the samples (x > 3 mol%) the Gd³⁺ ions appear as both isolated and antiferromagnetically coupled species. The EPR spectra of the glasses reveal resonance sites with an unexpected high crystalline field in addition to the ‘U’ spectrum, typical for Gd³⁺ ions in disordered systems. This absorption line is due to Gd³⁺ ions that replace Bi³⁺ ions from the host glass matrix and could play the network unconventional former role in the studied glasses.     

Structural properties of Cr2O3–Fe2O3–P2O5 glasses,Part I

The structural properties of xCr₂O₃–(40 − x)Fe₂O₃–60P₂O₅, 0 ⩽ x ⩽ 10 (mol%) glasses have been investigated by Raman and Mössbauer spectroscopies, X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The Raman spectra show that the addition of up to 5.3 mol% Cr₂O₃ does not produce any changes in the glass structure, which consists predominantly of pyrophosphate, Q¹, units. This is in accordance with O/P ≈ 3.5 for these glasses. The increase in glass density and T_g that occurs with increasing Cr₂O₃ suggests the strengthening of glass network. The Mössbauer spectra indicate that the Fe²⁺/Fe_tot ratio increases from 0.13 to 0.28 with increasing Cr₂O₃ content up to 5.3 mol%, which can be related to an increase in the melting temperature from 1423 to 1473 K. After annealing, the 10Cr₂O₃–30Fe₂O₃–60P₂O₅ (mol%) sample was partially crystallized and contained crystalline β-CrPO₄ and Fe₃(P₂O₇)₂. The SEM and AFM micrographs of the partially crystallized sample revealed randomly distributed crystals embedded in a homogeneous glass matrix. EDS analysis indicated that the glass matrix was rich in Fe₂O₃ (39.6 mol%) and P₂O₅ (54.9 mol%), but contained only 5.5 mol% of Cr₂O₃. These results suggest that the maximum solubility of chromium in these iron phosphate melts is 5.5 mol% Cr₂O₃.     

Evolution of nanocrystalline BaBi2Nb2O9 in Li2B4O7–BaO–Bi2O3–Nb2O5 glass system

Transparent glasses and glass nano crystal composites (GNCs) of various compositions in the system (100 − x)Li₂B₄O₇–x(BaO–Bi₂O₃–Nb₂O₅) (where x = 10, 20, and 30 in molar ratio) were fabricated via splat-quenching technique. The glassy nature of the as-quenched samples was established by differential thermal analyses. X-ray powder diffraction and transmission electron microscopic (TEM) studies confirmed the formation of layered perovskite BBN via a fluorite like phase. TEM studies revealed the presence of 10 nm sized spherical crystallites of fluorite like BaBi₂Nb₂O₉ phase in the glassy matrix of Li₂B₄O₇ (LBO). The influence of composition on the dielectric and the optical properties (transmission, optical band gap) of these samples has been investigated.     

BaBPO5和(H3O)Zn(H2O)2BP2O8·H2O的低温溶剂热合成及表征

以乙醇为溶剂,在低温条件下合成出了两种手性硼磷酸盐化合物BaBPO5(1)(T=120℃,t=5d)和(H3O)Zn(H2O)2BP2O8·H2O (2)(T=80℃,t=5d).XRD单晶衍射仪测定了化合物的结构,结果表明:(1)属三方晶系,P3221空间群,a=b=7.1162(3)(A),c=6.9979(6),(A)=3,该晶体含有一维线性链状阴离子结构;(2)属六方晶系,P6122空间群,a=b =9.513(2)(A),c=15.906(8),(A)=6.该晶体具有三维骨架结构.实验结果表明使用乙醇作溶剂可以极大降低硼磷酸盐的合成温度,进而有助于获得手性硼磷酸盐化合物,这为手性硼磷酸盐的合成提供了一种新思路.