定位硅酸锌结晶釉析晶动力学研究

本文利用定位结晶法研究了氧化锌和硅酸锌两种晶种对硅酸锌结晶釉釉面晶花的影响,根据结晶动力学理论,对结晶釉中硅酸锌晶体的生长规律和结晶机理进行了探讨,并比较了不同晶种对硅酸锌晶体生长规律的影响.实验结果表明:采用氧化锌和硅酸锌作定位晶种的釉面晶花外观效果基本相同;釉熔体中硅酸锌晶体生长半径与保温时间成线性关系;不同的定位晶种对硅酸锌晶体的生长基本没有影响;结晶常数随着析晶保温温度的提高而增加,当析晶保温温度分别为1150 ℃,1100 ℃和1050 ℃时,所对应的结晶常数依次为1.0911,0.9996和0.7177;即使在同一析晶保温温度下,不同的保温时间段其结晶常数也不同.     

分形理论在硅酸锌系结晶釉研究中的应用

本实验对采用不同工艺条件(析晶温度、析晶保温时间、釉层厚度)制备出具有晶花形貌的硅酸锌系结晶釉,应用分形理论对其晶花形貌进行了研究.结果发现该结晶釉的晶花形貌具有良好的分形特征,并且分形与制备工艺存在一定关系:随着析晶温度的增加,分形维数值与析晶温度除了在1140 ℃时稍有波动,基本上是成反比例关系,结晶形貌的变化趋势由针状或棒状转化为叶片状或圆盘状;随着析晶保温时间的增加,分形维数值逐渐增大,结晶形貌由针微晶逐渐转化成放射状晶体,尺寸也有明显增大的趋势;随着釉层厚度的增加,结晶产物的分形维数明显减小.     

定位锌结晶釉的析晶动力学分析

本文以ZnO作为定位结晶剂在1100℃下制备了ZnSiO3结晶釉,测试了其在不同析晶保温时间下釉面晶花大小,并根据结晶动力学理论,对结晶釉中ZnSiO3晶花的生长规律和结晶机理进行了分析探讨.结果表明:当析晶保温时间超过30 min,晶花的形成速率随时间增加而显著提高,并在45 min到60 min范围内达到最大值;当析晶保温时间超过90 min,晶花形成速率随时间增加而快速下降,并在析晶保温时间超过150 min后,晶花基本上不再生长,形成速率达到稳定值.采用ZnO作定位晶种的釉面结晶稳定性好,釉面晶花大小与析晶保温时间符合S型生长曲线关系,可用Logistic函数拟合,本研究为实现锌结晶釉的可控生长提供了参考.     

Co2+掺杂Zn2SiO4结晶釉生长机理的研究

以高岭土、石英、钠长石、石灰石、氧化锌等矿物为原料,ZnO为晶核剂,并掺杂Co2+控温烧结Zn2 SiO4结晶釉.利用X射线衍射仪(XRD)分析样品物相,白度色差计测量釉料色度(L*、a*、b*),EDS能谱仪分析样品组成含量.采用Johnson-Mehl-Avrami (JMA)方程对釉的结晶动力学进行分析,探讨釉中晶体的生长机理.结果表明:高温时Co2+置换了Zn2SiO4结晶釉中的Zn2+.随着保温时间的延长,掺杂了Co2+的Zn2SiO4晶体颗粒不断长大,在1140℃下保温170 min晶花达到最大,其晶花面积均值为410.91 mm2.模拟动力学分析,釉中晶体的Avrami指数n1100℃ =0.82,n1140℃=1.23,n1180℃=1.12,表明晶体的形成由扩散机制向成核机制转变.拟合Arrhenius方程,晶体的活化能Ea=148.2 kJ/mol.     

CaO/CaF2对低温无铅硼釉性状的影响

通过合理调配CaF2和CaO的加入量,在1120℃温度下制备出了具有较好光泽度的透明无铅硼釉及较好白度的硼乳浊釉.用单因素法探讨了CaO和CaF2含量对低温无铅硼釉釉面透明度(乳浊度)、光泽度、流动性的影响.结果表明,CaO可以抑制无铅硼釉的分相,降低釉的乳浊度,提高透明度,增加流动性,但含量多时会降低釉的光泽度.CaF2比CaO具有更强的助熔作用,可以使石英充分熔融,但同时由于釉粘度的降低,会析出钙长石和硅灰石晶体,降低釉的透明度.     

基础成分配比对白云鄂博尾矿微晶玻璃结构及性能的影响

以白云鄂博二次选后尾矿和粉煤灰为主要原料,采用熔融法制备得到了CaO-MgO-Al2O3-SiO2系尾矿微晶玻璃.制备流程包括熔融、退火、核化及晶化过程.其中玻璃熔融温度为1450℃,核化温度为720℃,晶化温度为850℃.利用XRD研究了基础玻璃成分配比对微晶玻璃结构的影响.结果表明基础玻璃成分配比直接决定微晶玻璃的主晶相形成.随着基础玻璃成分配比的变化,微晶玻璃可能形成辉石相、钙长石相、镁铁尖晶石相或磁铁矿相.当其他元素固定,CaO/MgO和CaO/Al2O3比值的减小会导致微晶玻璃由辉石相转变为镁铁尖晶石相和钙长石相.而当SiO2/CaO比值大于2时,主晶相则由辉石相转变为磁铁矿相.DTA测试结果表明CaO有利于析晶温度的降低,而MgO、Al2O3和SiO2相对提高了析晶温度.力学性能测试表明抗折强度、密度、耐酸碱度与微晶玻璃主晶相有直接关系.主晶相为辉石相的微晶玻璃具有更高的抗折强度、密度和耐酸性.     

景德镇明清以来低温黄釉的显微结构

本课题以景德镇明清以来低温黄釉样品为研究对象,采用电子探针-能谱组合、透射电镜等仪器对样品断面进行显微结构分析,研究了景德镇低温黄釉的显微结构演变情况,发现景德镇低温黄釉主要有黄釉下施底釉和黄釉下无底釉两大类,并进一步分析了底釉的存在对黄釉品质的影响情况.研究得出黄釉与底釉、胎的中间层所析出晶体主要为铅长石,白釉、底釉与胎中间层所析出晶体主要为钙长石;同时,还发现民国黄釉表面存在一层细小的烧绿石型黄色Pb2Fe0.5Sb1.5O6.5晶体.     

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.     

CaO和ZrO2对Ba2TiSi2O8极性玻璃陶瓷晶化和压电特性的影响

本文采用恒温场晶粒定向晶化工艺制备了Ba2TiSi2O8(BTS)极性玻璃陶瓷.以1.2BaO-1.0TiO2-2.6SiO2为基础玻璃,分别加入20;摩尔CaO和10;摩尔ZrO2,研究添加氧化物对Ba2TiSi2O8极性玻璃陶瓷的晶化和压电性能的影响.实验表明,加入CaO和ZrO2都影响主晶相的析出过程,特别是,加入ZrO2使玻璃陶瓷中产生BaZrSi3O9第二相.同时,测试结果显示,加入20;摩尔CaO有利于BTS晶体的定向析晶;而加入ZrO2不利于BTS晶体的定向析晶.     

钨基陶瓷结晶釉的快速结晶制备及其光催化性能探索

本文通过对钨基陶瓷结晶釉材料进行了快速结晶制备,所得釉层晶相为WOP2O7结构.通过扫描电镜分析发现其表面具有显著地结晶化特征形貌,进一步结合EDS能谱分析发现其表面形貌有钨基结晶釉相和底釉相两种结构构成.在光催化性能探索中发现该釉层材料在紫外可见光照射下展现出一定的催化降解罗丹明B溶液的能力,为陶瓷结晶釉材料的功能化价值提升提供了参考.     

提拉法生长高质量氟化镁单晶

设计了适合提拉法生长氟化镁单晶体的温场,采用提拉法成功生长出了直径100 mm的高质量氟化镁单晶.晶体内无气泡等宏观缺陷、无开裂;通过精密退火处理后,晶体透过率达到95;,平均应力双折射小于0.5 nm/cm.上述结果表明采用提拉法可以生长高质量的氟化镁单晶.     

微波辅助水热条件对二乙胺合成SAPO-11晶体结构与性质的影响

以二乙胺为模板剂,利用微波辅助水热合成法制备了SAPO-11晶体,研究了水热温度和时间对合成产物晶体结构性质的影响。采用XRD、FT-IR、SEM、BET和NH3-TPD等手段对SAPO-11晶体的物相组成、骨架结构、微观形貌、孔结构及表面酸性进行了分析表征。研究结果表明,不同水热条件对SAPO-11晶体结构性质影响较大。反应温度低于180℃时,合成样品仅存SiO2物相,无SAPO-11晶相生成;反应温度高于200℃时,部分SAPO-11晶体二次生长致使晶粒均匀度和比表面积大幅下降;反应时间大于1 h时,SAPO-11晶体生长易转晶生成少量AlPO4-5和CFSAPO-1(C)杂晶相;在反应温度200℃,反应时间1 h条件下制备得到的纯相SAPO-11球形晶粒表面具有弱酸特征,比表面积、孔容和平均孔径分别达199.4 m2·g-1,0.15 cm3·g-1和2.92 nm。     

梯度掺杂的YVO4-Nd∶YVO4复合晶体

利用改进的提拉法生长了一种新型YVO₄-Nd∶YVO₄ 复合晶体,在晶体中部实现了Nd³⁺的0.10%~0.25%(原子数分数)浓度梯度掺杂。晶体中, Nd³⁺掺杂区的弱吸收系数较未掺杂区大,表现出界面吸收现象。观测了复合晶体对泵浦光的吸收和温度分布,发现晶体沿轴向的泵浦吸收相对均匀,温度梯度相对较小。未镀膜的复合晶体样品在1 064 nm波段显示了良好的连续激光性能,光-光转换效率为37.0%,斜效率为40.9%。     

System of Mathematical Models for the Analysis of Industrial FZ-Si-Crystal Growth Processes

A system of coupled mathematical models and the corresponding program package is developed to study the interface shape, heat transfer, thermal stresses, fluid flow as well as the transient dopant segregation in the floating zone (FZ) growth of large silicon crystals (diameter more than 100mm) grown by the needle-eye technique. The floating zone method with needle-eye technique is used to produce high-purity silicon single crystals for semiconductor devices to overcome the problems resulting from the use of crucibles. The high frequency electric current induced by the pancake induction coil, the temperature gradients and the feed/crystal rotation determine the free surface shape of the molten zone and cause the fluid motion. The quality of the growing crystal depends on the shape of the growth interface, the temperature gradients and corresponding thermal stresses in the single crystal, the fluid flow, and especially on the dopant segregation near the growth interface. From the calculated transient dopant concentration fields in the molten zone the macroscopic and microscopic resistivity distribution in the single crystal is derived. The numerical results of the resistivity distributions are compared with the resistivity distributions measured in the grown crystal.     

Effects of aromatic core and flexible terminal chain structures on the properties of luminous liquid-crystalline gold(i) complexes for functional materials

ABSTRACT

Luminescent liquid-crystalline (LC) Au complexes with various aromatic cores and flexible terminal chains were synthesized. The aromatic core aspect ratio crucially affected the LC temperature range and melting point of the complexes. Moreover, branched flexible chains reduced the melting point, thus expanding the LC temperature range. In the crystalline and LC phases of the complexes, fluorescence was quenched by the aggregation-caused quenching effect, but phosphorescence was enhanced by the crystallization-induced phosphorescence effect. However, no phosphorescence was observed in the isotropic phase. Thus, not only aggregation but also regularity of molecular aggregates is necessary for the observed crystallization-induced phosphorescence effect.     

轻烧MgO的活性对合成镁铝尖晶石晶体结构及性能的影响

以不同活性的轻烧MgO和α-Al2 O3微粉为原料,通过固相烧结法合成镁铝尖晶石,研究轻烧氧化镁的活性对镁铝尖晶石物相组成、晶胞参数、微观结构及烧结性能的影响并探讨其机理.利用XRD和HighScore Plus分析合成试样的物相组成和晶胞参数,利用SEM表征合成试样的微观结构.结果表明:高活性轻烧MgO具有更高的缺陷能,可以加快烧结反应的进行,降低MgAl2 O4的合成温度;高活性轻烧MgO可以促进MgAl2 O4晶体发育,MgO活性越高,生成的MgAl2 O4晶胞参数和晶胞体积越大,晶粒发育更为完全.     

Structural characterization of the glassy phase in majolica glazes by Raman spectroscopy: A comparison between Renaissance samples and replica processed at different temperatures

Tin-opacified lead glaze, prepared according to Renaissance recipes, has been fired at different temperature from 300 °C to 990 °C, and investigated by Raman scattering. A chemometric treatment and a systematic curve-fitting procedure have been applied in the range of 700–1250 cm⁻¹ in order to monitor quantitatively the structural changes of the silicate network that occurred with firing. The results obtained on model glazes are compared with Raman spectra collected on various Renaissance potteries. This method is suggested for non-invasive surface analysis of ancient glazes aimed at the characterization of processing techniques.     

Thermal behavior of biogenic apatite crystals in bone: An X‐ray diffraction study

The thermal behavior of the bovine bone mineral and synthetic stoichiometric hydroxyapatite was investigated by X‐ray diffraction. The bone samples in solid (planar oriented pieces) and in powder form were examined to elucidate how the microstructural and textural properties of bone mineral are modified under heating. As could be expected, the thermal behavior of the bone mineral depends not only on the structural distortions, but also on the crystal habit, texture and ordering of biocrystals in tissue. The temperature growth of biogenic apatite crystals, unlike synthetic hydroxyapatite, is seen to be nonmonotonic and multi‐staged. At 600 to 700°C the biomineral crystallites grow rapidly due to disappearance of the mosaic structure as the lattice imperfections are annealed. After heating between 700°C and 900°C the bone mineral appears to be composed of roughly equidimensional ≥200 nm crystals. The further growth of the crystals in the range from 900 to 1300°C occurs by the mass transport mechanism, supporting the idea that the bone mineral is not a discrete aggregation of crystals, but rather a continuous mineral phase with direct crystal‐crystal bonding. Estimates are presented to show the important role of the surface mass transport mechanism in the growth of apatite crystals. The material obtained by heating a cortical bone fragment between 900°C and 1300°C turns out to be composed of two crystal types: crystals oriented along the bone axis (major morphology) and those of differing shape and orientation (minor morphology). The heating‐induced variations in the longitudinal and transverse dimensions of differing‐morphology crystals are found to be coherent. Small amounts of CaO, MgO and other crystalline phases are seen to be formed in the bone mineral under heating. © 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

Aurivillius结构Bi2MoxW1-xO6铁电功能晶体的生长与性质表征

本文采用固相反应法探索了Aurivillius结构Bi₂Mo_xW_1-xO₆体系的合成条件以及能够形成固溶体的成分范围,探索了Bi₂Mo_xW_1-xO₆晶体的助熔剂法生长体系,并对晶体的结构、变温介电性质和电阻率进行了测定和分析。Bi₂Mo_xW_1-xO₆体系中Mo的占比x可以在0~1的范围内连续变化,采用固相反应法可以在500~870 ℃范围内的不同温度合成纯的Bi₂Mo_xW_1-xO₆铁电相。采用Li₂B₄O₇-Bi₂O₃(摩尔比2∶1)作为助熔剂生长得到了厘米级Bi₂WO₆单畴晶体,厚度不小于2 mm,最大尺寸则达到了约40 mm。在n(Bi₂O₃)∶n(MoO₃)∶n(WO₃)∶n(Li₂B₄O₇)=1∶1∶1∶1(摩尔比)体系中生长得到了厚度约1 mm的Bi₂Mo_0.15W_0.85O₆厘米量级单畴晶体,结构解析表明Bi₂Mo_0.15W_0.85O₆属于正交晶系,Aba2(No.41)空间群。变温介电性质测试表明,Bi₂Mo_0.15W_0.85O₆晶体的介电常数ε₃₃由Bi₂WO₆晶体的70提高到了102,介电弛豫现象发生的温度由Bi₂WO₆晶体的430 ℃降到了330 ℃附近。变温电阻率测试表明,Bi₂WO₆与Bi₂Mo_0.15W_0.85O₆晶体的电阻率均随温度升高而降低,在100 ℃以下,Bi₂WO₆的电阻率高于Bi₂Mo_0.15W_0.85O₆晶体,且随温度升高,二者电阻率的差距在逐渐缩小。     

CaO对MgO-Al2O3-SiO2系微晶玻璃结构与性能的影响

以化学纯试剂为原料,采用熔融法制备MgO-Al2O3-SiO2(MAS)系微晶玻璃.利用DSC、XRD、SEM等及理化性能测试手段研究了不同CaO含量对微晶玻璃析晶行为、物相组成、显微结构及理化性能的影响.结果表明:一定含量的CaO可以降低析晶活化能,促进玻璃析晶;随CaO含量的增加,微晶玻璃主晶相由假蓝宝石向α-堇青石转变,晶体形貌由棒状晶转变为枝状晶,晶粒尺寸呈先减后增的趋势;当CaO含量为3wt;时微晶玻璃热膨胀系数和相对介电常数(εr)达到最低,分别为3.89×10-1℃-1和10.09(1 MHz);当不外添CaO时微晶玻璃Vickers硬度达到最大,为10.52 GPa.