添加多晶硅废料制备SiC/Si3N4复相结合SiC耐火材料

以碳化硅、多晶硅废料、金属硅粉为原料,纸浆废液为结合剂,采用反应烧结工艺制备SiC/Si3N4复相结合SiC耐火材料.运用热力学分析了利用多晶硅废料代替部分工业金属硅粉和碳化硅细粉制备SiC/Si3N4复相结合SiC耐火材料的理论可行性.系统地分析了单质硅氮化机理,提出Si首先与N2中的微量氧反应形成气态SiO,至体系氧分压降至P(02)/pθ＜1 × 10-18.9,Si直接氮化.研究了多晶硅废料对材料物相组成和微观结构的影响.结果表明:利用多晶硅废料制备的SiC/Si3 N4复相结合SiC耐火材料性能优异;多晶硅废料的添加使反应生成的结合相由原先单一的Si3 N4变为Si3 N4和β-Sic,两结合相发挥各自的性能优势;多晶硅废料中的硅粉粒径小,活性大,与工业金属硅粉共存时能发生逐级氮化作用,增加了纤维状Si3N4含量,优化了材料结构.     

冰模板法制备反应结合多孔Si3N4/SiC复相陶瓷

以微米级SiC和Si粉为原料,采用冰模板法和氮化反应烧结法制备了孔道中修饰α-Si3N4、Si2N2O纳米线的β-Si3N4结合多孔SiC复相陶瓷.研究了反应烧结温度、SiC/Si比和固相含量对多孔陶瓷的物相结构、形貌、孔分布和压缩强度的影响.结果表明:多孔陶瓷具有层状定向通孔结构,孔隙率介于50; ～ 70;之间,孔径分布呈现双峰分布特点;当烧结温度达到1350℃以上时,在层状孔道中交织形成α-Si3N4和Si2N2O纳米线的网络结构.反应温度超过1450℃时,通过液态Si的氮化反应原位形成β-Si3N4结合相将SiC颗粒粘结起来;当浆料中Si含量由16wt;增加至33wt;时,多孔陶瓷的开气孔率从69.78;降至62.64;,而压缩强度由2.2 MPa提高到8.73 MPa;随着浆料固相体积含量从25;增加到45;,多孔陶瓷的气孔率从71.81;降至54.85;,同时压缩强度从4.99 MPa提高到24.16 MPa.     

降温速率对升级冶金硅定向凝固生长多晶硅少子寿命的影响

对经过前期提纯的冶金级硅料进行一次性定向凝固生长多晶硅铸锭,研究了长晶阶段降温速率对多晶硅少子寿命的影响。结果显示降温速率越低,获得多晶硅少子寿命越高,但降温速率低到一定程度时,少子寿命反而会降低。通过测试生长多晶硅硅锭曲率半径、晶体结构等数据,分析了该现象的产生原因。这将有助于升级冶金硅一次性定向凝固生长多晶硅铸锭的生产应用。     

定向凝固多晶硅铸锭炉石英坩埚的改进与热场优化

针对定向凝固多晶硅铸锭炉内温场的分布特点,利用COMSOL 5.0模拟软件优化设计了定向凝固多晶硅铸锭炉内部坩埚形状,并对优化后铸锭炉内的温场分布进行了详细分析.结果表明:将坩埚底面由平底结构改进为凸底结构,可优化铸锭坩埚内的温场分布,使长晶界面的等温线趋于水平分布,进而可有效解决中心区域结晶过早、边角区域结晶过慢和边角区热诱导缺陷、杂质密度大等铸锭过程中存在的基本问题.     

保温层结构对感应加热制备太阳能级多晶硅影响的数值模拟研究

定向凝固技术是制备太阳能级多晶硅的主要制备技术.在该技术路线之中,优化多晶铸锭炉的热场结构和控制硅熔体的对流形态是获得高品质多晶硅的有效途径之一.本文设计了三种热场保温层,通过分析不同保温层下坩埚内硅熔体的热场、流场、固液界面、氧含量等的变化,确定了优化的保温层结构.研究发现,在传统固化碳毡保温层中引入石墨层可以使多晶炉内形成两个“热源”,提高多晶炉的热效率,使其能耗降低了38.5;;在洛伦兹力的作用下硅熔体中仅存在一个上下贯通的涡流,有利于硅中杂质原子的挥发.同时,添加石墨保温层后固液界面的形状由“W”状转变为凹状,其上的氧含量有所降低,并且V/Gn值在整个固液界面范围内均大于临界值,可以有效抑制氧沉淀.可见,在感应加热多晶硅生长系统中,采用固化碳毡+石墨保温层时,有利于降低多晶硅的生产成本并提高多晶硅的品质.     

反应热压烧结制备SiC/ZrB2复相陶瓷及其性能表征

以二硼化锆、硅和活性碳为原材料,在1850℃、20 MPa条件下,采用反应热压烧结工艺制备出了SiC/ZrB2陶瓷基复合材料.研究了添加剂(硅和活性碳)含量对ZrB2陶瓷烧结行为和力学性能的影响.借助X射线衍射和扫描电镜分析了复合材料的物相组成和微观结构.研究结果表明:添加剂可以显著提高复合材料的烧结致密度和力学性能.复合材料的XRD衍射图谱中只有ZrB2和SiC的衍射峰.当添加剂含量为12wt;时,复合材料的弯曲强度和断裂韧性分别达到584MPa和7.25MPa ·m1/2.显微结构分析表明,致密度的提高、晶粒粒径的减小以及断裂模式的转变是复合材料力学性能提高的主要原因.     

Si3N4-TiC和Si3N4-TiN复相导电陶瓷的制备及电加工性能研究

以TiC和TiN粉为导电相,利用热压烧结制备了Si3N4-TiC和Si3N4-TiN复相导电陶瓷.比较了TiC和TiN对Si3N4陶瓷相组成、致密度、显微结构、力学性能、导电性能及电火花加工性能的影响.结果表明:高温下TiN与Si3N4具有良好稳定性,烧结后获得Si3N4-TiN复相导电陶瓷,然而高温下TiC却与Si3N4反应形成了TiC0.5N0.5和SiC,烧结后获得Si3 N4-TiC0.5N0.5-SiC复相导电陶瓷.虽然TiN和TiC的引入对Si3N4的硬度和断裂韧性的影响没有明显差别,然而TiC的引入可以更好的改善Si3N4的致密化、导电性能及电火花加工性能;与以TiN为导电相所制备的Si3N4基导电陶瓷相比,以TiC为导电相所制备的Si3N4基复相导电陶瓷电火花加工后表面的粗糙度值和材料去除率更低.     

TiB2、CNT双相增韧碳化硼复合陶瓷及其性能研究

在1 500 ℃的真空条件下,通过液相渗硅法(liquid silicon infiltration, LSI)制备了碳化硼/二硼化钛-碳纳米管(B₄C-TiB₂-CNT)陶瓷复合材料,对其成分、形貌、性能和增韧机理进行了分析表征和研究。结果表明:复合材料的主要组成相为B₁₂(C, Si, B)₃、SiC和Si。二硼化钛和碳纳米管显著提高了液相渗硅烧结碳化硼陶瓷的力学性能,在TiB₂和CNT的添加量分别为10%和0.4%时,复合陶瓷的弯曲强度和断裂韧性达到了(390±18) MPa和(5.38±0.38) MPa·m^1/2,分别比B₄C陶瓷高了31%和53%。本文的研究从片状SiC颗粒和CNT的拔出、TiB₂的颗粒增韧以及裂纹的偏转等方面解释了B₄C-TiB₂-CNT复合材料的增韧机理。     

石墨坩埚厚度对感应加热制备太阳能级多晶硅影响的数值模拟研究

定向凝固法制备的多晶硅是目前主要的光伏原材料,制备过程中热场结构和硅熔体对流形态对于生长高质量的多晶硅极为重要,本文利用专业晶体生长软件CGSim对制备太阳能级多晶硅用真空感应铸锭炉中的石墨坩埚进行改进并进行了数值模拟,分析了不同石墨坩埚厚度的变化对热场、流场、固液界面、硅晶体应力场以及和V/G值的影响.结果表明,当石墨坩埚厚度为20 mm,可获得良好的对流形态、平坦的固液界面、合理的V/G值等,有利于节约多晶硅的生产成本并提高多晶硅的品质,为生产实践中工艺方案优化及缺陷分析等提供重要的理论依据.     

水基流延成型和热压烧结制备碳化硼陶瓷及性能研究

以工业碳化硼粉末为原料、采用Si3N4磨球磨损法引入Si3N4烧结助剂,采用水基流延成型和热压烧结方法制备了碳化硼陶瓷.研究了氧含量、分散剂、pH值等因素对B4C陶瓷浆料分散性能的影响,采用XRD、SEM等对碳化硼陶瓷的物相、显微结构和第二相分布进行了表征,并测试了样品的维氏硬度、断裂韧性、抗弯强度和弹性模量.结果表明:经醇洗后的碳化硼粉末中氧化硼含量降低,有利于B4C陶瓷浆料的分散稳定.采用球磨磨损引入了Si3N4粉,在B4C基体中通过原位反应形成第二相SiC和BN,SiC和BN第二相颗粒在B4C基体中弥散分布均匀.在2100 ℃热压烧结样品的维氏硬度、抗弯强度、断裂韧性和弹性模量分别达到30.2 GPa、596.5 MPa、3.36 MPa·m1/2和362.3 GPa.     

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).     

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.     

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.