用粉煤灰和高岭土混合原料合成β-Sialon粉体

以粉煤灰、高岭土混合物为原料,采用碳热还原氮化法制备了不同z值的β-Sialon粉体.研究了原料组成(Si/Al值)、活性炭配量以及反应温度对合成产物物相的影响.利用X射线衍射仪分析产物物相的组成,用扫描电子显微镜对产物的显微形貌进行分析.结果表明,当原料中Si/Al值为1.5,配炭量过量100;时,在1450℃保温6h条件下,可以合成主要物相为Si3Al3O3N5(β-Sialon,z=3)的粉体,粉体的显微形貌呈现纤维状;当原料中Si/Al值为1.7,配炭量过量150;时,在1450℃保温6h条件下,可以制备主要物相为Si4Al2O2N6(β-Sialon,z=2)的粉体,粉体的显微形貌呈现纤维状和板状.     

反应温度和锆英石添加量对石英碳热还原氮化产物的影响

本研究中选用石英和焦炭为原料、天然锆英石为添加剂,采用XRD、SEM和EDS等分析方法,研究了反应温度和锆英石添加量对石英碳热还原氮化产物影响.研究结果表明:在0.13 MPa的流动氮气气氛中,反应温度在1450～1550℃时,石英的碳热还原氮化产物中含有Si2N2O、β-SiC和β-Si3N4物相;当反应温度为1600℃时,石英的碳热等在1600℃条件下,石英碳热还原氮化产物主要含有柱状β-Si3N4和少量纤维状β-SiC物相;当添加10wt;的天然锆英石时,产物的主要成分为β-Si3N4 、ZrN以及少量βSiC物相;当锆英石添加量为20wt;到50wt;时,产物中不仅含有β-Si3N4和ZrN物相,还存在c-ZrO2,m-ZrO2,Si2N2O及β-SiC等物相.     

固体废弃物铝灰和粉煤灰原位合成Spinel-Sialon复相材料的研究

本文利用铝灰和粉煤灰为原料,经原位铝热还原氮化法合成了Spinel-Sialon复相材料。通过XRD、SEM、EDS等分析手段,研究了合成温度和还原剂铝的添加量对合成产物物相及微观形貌的影响。结果表明:合成Spinel-Sialon的优化工艺参数为铝的添加量为过量100%、合成温度为1550℃,保温时间3 h,合成得到发育良好的柱状β-Sialon及八面体形的镁铝尖晶石。合成温度、还原剂铝的添加量均是影响氮化产物的重要因素。随着温度的升高或还原剂铝的添加量增多,Al2O3越来越少,β-Sialon和镁铝尖晶石均增多,且β-Sialon的Z值增大,MgAl2O4转变成富铝尖晶石。     

基于粉煤灰原料的β-Sialon粉体制备及其微波烧结性能

以粉煤灰为主要原料,采用碳热还原氮化法合成β-Sialon粉体,再以该粉体为主要原料,添加适量Y2 O3烧结助剂,利用微波无压烧结技术研究β-Sialon陶瓷的微波烧结行为.结果表明:活性炭与粉煤灰质量比值(m./mf)为0.43,氮气流量为0.5 L/min,合成温度为1450℃,保温6h条件下,获得显微形貌为粒状,z=2的β-Sialon粉体;在微波烧结温度为1500℃,保温时间为20 min条件下,获得试样的密度为2.86 g/cm3,相对密度为92.3;,HV0.5为1528.     

添加锆英石、B4C和焦粉对铝碳质耐火材料抗氧化性能影响

在Al2O3-C质耐火材料中添加锆英石、B4C和焦炭,通过高温原位反应生成了ZrC-ZrB2-SiC复合非氧化物耐高温物相.采用XRD分析了不同锆英石、B4C和焦炭的添加量与不同烧成温度下反应产物的物相组成,并采用XRD与SEM进一步研究了含有ZrC-ZrB2-SiC复合非氧化物的铝碳质耐火材料的抗氧化性能及其抗氧化的机理.结果表明:当锆英石-焦炭-B4C混合粉体的加入量为20;,在1550 ℃保温3 h能在铝碳质耐火材料的基质中原位合成ZrC-ZrB2-SiC复合非氧化物,制备得到相应的铝碳质复合耐火材料.ZrC-ZrB2-SiC复合非氧化物在氧化条件下可生成玻璃相,形成致密保护层能够阻止其进一步氧化,从而显著提高铝碳质材料的抗氧化性能.     

反应温度对低品位铝矾土和钛铁矿制备β-Sialon/Ti(C,N)复相粉体的影响

以低品位铝矾土和钛铁矿为原料,焦炭为还原剂在不同温度下进行碳热还原氮化反应(CRN),制备β-Sialon/Ti(C,N)复相粉体,其中钛铁矿与铝矾土的质量比为50∶50,同时对反应产物进行XRD物相分析和SEM显微形貌分析.结果显示:原料反应的最佳温度为1250℃,在此温度下产物物相主要为β-Sialon(z=3)、α-Al2O3 Ti(C,N)和单质铁;在低于此温度下产物主要为莫来石,在较高温度下反应产物主要为AlN.反应产物中,p-Sialon微观形貌呈柱状,AlN主要以片状形态存在,单质铁主要以球状形态存在.     

利用稀土尾矿合成Ca-α-Sialon陶瓷粉体的工艺研究

以包钢稀土尾矿为主要原料,适量氧化铝粉、氧化钙调整组分,原料经12 mol/L盐酸,80℃下酸洗,利用碳热还原氮化法获得了柱状Ca-α-Sialon相.烧成温度1500℃,保温时间6 h,氮气流量0.8 L/min条件下,生成产物中Ca-α-Sialon相含量最高,晶粒生长状况良好.     

碳热还原氮化法制备β-Sialon粉体的研究

采用山西大同土为主要原料,利用碳热还原氮化法(CRN)制备了β-Sialon材料,并利用SEM、XRD等检测手段对其进行了检测分析.研究了温度、N2流量、保温时间以及配碳量等因素对制备β-Sialon的影响,采用正交设计的方法确定了反应的最佳工艺参数,并在此基础上讨论了α-Si3N4晶种对生成产物的影响.实验结果表明,烧结温度为1500℃,氮气流量为1 L/min,保温时间为2 h,配碳量为0.8化学计量时可以生成较多的β-Sialon相.SEM微观形貌表明具有一定长径比的β-Sialon柱状晶呈均匀分布.此外,加入3;的晶种α-3N4可促使晶粒大小均匀并获得高品质细密结构的粉体.     

碳热原位合成SiC_w/Al_2O_3复相陶瓷粉体的制备工艺及反应机理

本文以高岭土和纳米碳黑颗粒为原料,采用碳热还原原位合成工艺制备SiC_w/Al_2O_3复相陶瓷粉体.通过研究合成温度、保温时间、原料配比以及氩气流量对合成产物的影响,借助XRD、SEM等技术手段进行测试表征,得到了合成工艺的最优参数,并探讨了碳热还原反应的机理.实验结果表明:高岭土与碳黑的摩尔比为1∶ 8,氩气流量为80 mL/min,在1500 ℃下保温2 h,可获得纯净的SiC_w和Al_2O_3复相陶瓷粉体,SiC晶须的平均直径为300 nm左右,长度大于6 μm,长径比大于20,SiC晶须表面光洁,与氧化铝颗粒呈均匀分布.碳热还原高岭土合成SiC_w/Al_2O_3,包括碳热还原SiO_2 与碳热还原莫来石两个阶段,碳化硅晶须的生成遵循气-固(V-S)生长机理.     

Ca-Si-Al-O玻璃合成Ca-α-SiAlON:Eu荧光粉及其发光性能研究

以Ca-Si-Al-O玻璃为主要原料,通过添加Eu_2O_3,采用碳热还原氮化法合成出Ca-α-Si Al ON∶Eu荧光粉体。借助X射线衍射仪(XRD)、扫描电子显微镜(SEM)、紫外-可见分光光度计和荧光分光光度计等手段,对合成Ca-α-Si Al ON∶Eu的物相组成、显微结构及发光性能进行表征。结果表明:(1)以Ca O,Al_2O_3,Si O_2为原料,合成的Ca-SiAl-O非晶玻璃具有Si O4四面体与Al O4四面体相互连接的架状结构;(2)以Ca-Si-Al-O玻璃为主要原料,通过添加Eu_2O_3,在1450℃碳热还原氮化合成出呈棱柱状形貌的Ca-α-Si Al ON粉体,其中Eu离子在Ca-α-Si Al ON中实现了良好的固溶;(3)合成的Ca-α-Si Al ON∶Eu在紫外-可见光部分具有较强的吸收,在420 nm的激发下,发射光谱的峰值波长为~570 nm,实现了黄绿光发射,归属于Eu~(2+)的4f~65d-4f~7跃迁。     

First-principles coexistence simulations of supercooled liquid silicon

We perform first-principles coexistence simulations of the low-density and the high-density phases of supercooled liquid silicon and find a negative slope for the coexisting line in the temperature-pressure plane. Electron density maps and electron-localization function plots of the two phases of silicon show marked differences. The calculated differences suggest more localized electrons in the low-density liquid compared to the high-density liquid, coming from an increased population of covalent bonds, which further explain the calculated negative slope in the two phase coexistence regime. This is consistent with the presence of a pseudo-gap in low-density liquid silicon, absent in the high-density liquid which shows a metallic behavior.     

Triethyl ammonium salt of O,O′-bis(p-tolyl)dithiophosphate, [Et3NH]+[(4-MeC6H4O)2PS2]−

Triethyl ammonium Salt of O,O′-bis(p-tolyl)dithiophosphate and O,O′-bis(m-tolyl)dithiophosphate have been obtained by reaction of p- and m-cresol, respectively with P₂S₅ in toluene and have been characterized by elemental analysis, IR, ¹H and ³¹P NMR spectroscopy. The molecular structure of O,O′-bis(p-tolyl)dithiophosphate has been determined. Crystal data: [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻: Monoclinic, P2₁/c, a=15.2441(9) ?, b=10.415(2) ?, c=3.9726(9) ?, β=91.709(7)°, V=2217.5(1) ?⁻³, Z=4.Supplementary materials Additional material available from the Cambridge Crystallographic Data Centre (CCDC no. 600927 for [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻ comprises the final atomic coordinates for all atoms, thermal parameters, and a complete listing of bond distances and angles. Copies of this information may be obtained free of charge on application to The Director, 12 Union Road, Cambridge CB2 2EZ, UK (fax: +44-1223-336033; email: deposit@ccdc.cam.ac.uk or www:http://www.ccdc.cam.ac.uk).     

Crystal structures of thecis andtrans isomers of dithiahexahydro[3.3]metacyclophane

Structures of both thecis andtrans isomers of dithiahexahydro[3.3]metacyclophane, ?C₆H₄?CH₂SCH₂?C₆H₁₀?CH₂SCH₂?, have been determined, wherecis andtrans refer to the attachments to the cyclohexane ring. Thecis form crystallizes in the monoclinic space groupP2₁/c witha=8.4299(11)Å,b=21.772(2)Å,c=8.9724(13)Å, β=116.574(11)^o, andZ=4. Thetrans isomer packs into the monoclinic space groupP2₁ witha=8.159(16)Å,b=10.185(5)Å,c=9.558(2)Å, β=112.435(18)^o, andZ=2. The cyclohexane ring of thecis isomer is in the chair conformation, while the cyclohexane of thetrans isomer is found in a twisted boat conformation.     

CTAB与SDBS对碳酸锶粒子生长形态调控及机理研究

以表面活性剂CTAB和SDBS为化学添加剂,采用化学共沉淀法对碳酸锶晶体的生长形态进行调控,成功地制备出了实心的树枝状和花瓣为空心的花状碳酸锶粉体,并用X射线衍射(XRD)、扫描电子显微镜(SEM)和傅里叶变换红外光谱(FT-IR)等分析手段对样品进行了表征;最后重点对化学添加剂可能产生的影响机理进行了初步的探讨.结果表明,CTAB和SDBS在晶体生长的过程中能起到显著的影响作用,两者对粒子分散性能的作用效果相反,而且后者对晶体(013)和(213)晶面表面能降低的贡献明显大于前者.     

Crystal structure of Zn4Na(OH)6SO4Cl·6H2O

The structure of Zn₄Na(OH)₆SO₄Cl·6H₂O, a secondary mineral from Hettstedt, Germany, was determined by single-crystal X-ray diffraction. The crystals are hexagonal,a=8.413(8),c=13.095(24) Å, space group $P\bar 3$ , Z=2. The structure was refined to R=0.0554 and R_w=0.0903 for 970 reflections with I≥3σ(I). The structure can be described as zinc hydroxide layers perpendicular toc, from which sulfates and chlorides extend. The layers are held together by a system of hydrogen bonds involving hexaaquo Na⁺ ions which occupy the interlayer space.     

Synthesis and Crystal Structure of 5-[2-(6-bromonaphthalenyloxymethyl)]-3-(4-morpholinomethyl)-1,3,4-oxadiazole-2(3<Emphasis Type="Italic">H</Emphasis>)-thione

Abstract  The title compound, C₁₈H₁₈BrN₃O₃S, a derivative of 1,3,4-oxadiazole, crystallizes in the triclinic space group P-1 with unit cell parameters a = 6.8731(3), b = 8.9994(4), c = 15.7099(6) ?, α = 92.779(3)°, β = 130.575(3)°, γ = 107.868(4)°, Z = 2. The dihedral angle between the mean planes of the planar naphthyl and morpholine (chair) rings with the planar oxadiazol ring is 50.1(8) and 76.8(6)°, respectively. The planar naphthyl ring is twisted 52.2(5)° with the mean plane of the morpholine ring. A group of four intermolecular close contacts are observed between a bromine atom and hydrogen atoms from the closely packed naphthyl, morpholine and oxy–methyl groups in the unit cell. These molecular interactions in concert with an additional series of π–π stacking interactions that occur between the center of gravity of the two 6-membered rings of the naphthalene group influence the twist angles of each of these three groups. A MOPAC AM1 calculation of the conformation energy of the crystal structure [226.0128(9) kcal] compared to that of the minimum energy structure after geometry optimization [29.9744(1) kcal] reveals a significantly reduced value. The twist angles of the three groups above also change after the AM1 calculation giving support to the influence of both intermolecular C–H···Br short-range interactions and Cg π–π stacking interactions on these angles which therefore play a role in stabilizing crystal packing. Graphical Abstract  Crystal structure of 5-{[(6-bromonaphthalen-2-yl)oxy]methyl}-3-(morpholin-4-ylmethyl)-1,3,4-oxadiazole-2(3H)-thione, C₁₈H₁₈BrN₃O₃S, is reported and its geometric and packing parameters described and compared to a MOPAC computational calculation. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Crystal structure of irisolidone from the flowers of Pueraia lobata

Irisolidone (5,7-dihydroxy-6,4′-dimethoxyisoflavone) was isolated from the flowers of Pueraia lobata and its crystal structure was examined by X-ray single crystal diffraction. The crystal structure of irisolidone is monoclinic, space group P2₁/c with a = 15.491(9) ?, b = 7.895(4) ?, c = 13.321(7) ?, β = 110.546(9)° and Z = 4. Hydrogen bonding and aromatic π–π stacking assemble the title compound into a three-dimensional networking structure.     

Synthesis of spinacine and spinacine derivatives: crystal and molecular structures of Nπ-hydroxymethyl spinacine and Nα-methyl spinaceamine

The natural amino acid L-Spinacine (4,5,6,7-tetrahydro-1H-imidazo[4,5-c]pyridine-6-carboxylic acid) has been synthesized following a new pathway which gives a chemically and optically pure product with an excellent yield. The crystal structures of a synthetic intermediate, N^π-hydroxymethyl-spinacine, and a spinacine derivative, N^α-methyl-spinaceamine, have been investigated through X-ray diffraction: Spi(πMeOH)·H₂O, monoclinicP2 _i,a=8.571(1),b=6.682(1),c=8.588(1) Å, and β=94.67(1)^o. Spm(αMe)·2HCl·H₂O, triclinicP l,a=7.492(4),b=10.799(3),c=7.040(2) Å, α=91.88(2), β=98.36(3) and γ=73.34(3)^o. Spi(πMeOH) crystallizes with a water molecule and displays a zwitterionic character. The carboxylate group is in equatorial position and forms a short electrostatic interaction of 2.618(2) Å between one of its oxygens and the protonated nitrogen of the tetrahydropyridine ring. The crystal packing is assured by strong O?H???O, O?H???N, N?H???N intermolecular hydrogen bonds and C?H???O close contacts. The biprotonated compounds Spm(αMe) crystallizes with two Cl^? anions and a water molecule. The positive charge on the imidazole ring is delocalized on the conjugated moiety N=C?N. The crystal is built up by clusters formed by two biprotonated Spm(αMe) molecules, four Cl^? anions and two water molecules linked together by hydrogen bonds.