ZnO对Bi2 O3-B2 O3-ZnO低熔点玻璃结构与性能的影响

通过FTIR、Raman、27 Al NMR、XRD、DSC等测试方法,研究了ZnO含量对Bi2 O3-B2 O3-ZnO-SiO2-Al2 O3系统低熔点玻璃结构及热性能的影响.结果表明:当ZnO含量小于12wt％时,Zn2+与自由氧结合形成[ZnO4]四面体,增强网络结构,玻璃化转变温度增大,热膨胀系数减小;当ZnO含量大于12wt％时,锌氧多面体由四配位[ZnO4]转变为六配位[ZnO6],破坏网络结构,玻璃化转变温度减小,热膨胀系数增大;ZnO含量的提高和热处理温度的升高对玻璃析晶能力没有明显的促进作用.     

Y2O3对高分子网络凝胶法制备Li2O-Al2O3-SiO2系微晶玻璃性能的影响

以丙烯酰胺、N,N'-亚甲基双丙烯酰胺、碳酸锂、硝酸铝和正硅酸乙酯为原料,采用高分子网络凝胶法成功地制备出多组分氧化物Li2O-Al2O3-SiO2(LAS)微晶玻璃超微粉末,并掺杂了稀土氧化物Y2O3.将粉体压制烧结得到微晶玻璃块体.用IR,XRD,SEM等测试手段研究了掺杂对微晶玻璃组织与性能的影响,测定了微晶玻璃的热膨胀系数.实验表明:Y2O3使微晶玻璃的相变温度降低到900℃;掺杂后微晶玻璃的粒径减小;高分子网络凝胶法制备的Li2O-Al2O3-SiO2(LAS)微晶玻璃热膨胀系数达到10-7数量级,掺Y2O3使Li2O-Al2O3-SiO2(LAS)微晶玻璃的热膨胀系数提高.     

MgO,ZnO和BaO对Li2O-Al2O3-SiO2微晶玻璃结晶化和热膨胀性能的影响

通过传统熔融法制备了添加MgO,ZnO和BaO的Li2O-Al2O3-SiO2(Las)微晶玻璃.并通过微分热分析、X射线衍射和扫描电镜研究了MgO, ZnO和BaO对LAS玻璃的结晶化影响.测量了LAS的热膨胀系数(coefficient ofthermal expansion.CTE).结果表明:添加1.0%～1.5%质量分数,不同)MgO,1.0%～3.0%ZnO或1.5%～3.5%BaO的LAS微晶玻璃在500℃以下都表现出负的热膨胀性.随着MgO含量的减少,形成了β锂辉石固溶体(LiAlSi3O8)并导致CTE显著增大.当添加0.5%MgO时,从100~700℃具有0.5120×10-6℃到1.691 3×10-6/℃的正膨胀系数.     

氧化物添加剂对P2O5-ZnO-B2O3系低熔点玻璃物化性能的影响

作为绿色环保材料,无铅低熔点玻璃已经在电子元器件的封装和涂层等领域得到了广泛应用。以P2O5-ZnO-B2O3体系为基础玻璃,通过外加法研究氧化物添加剂（Fe2O3、MnO2、CuO、CeO2和Y2O3）对玻璃密度（ρ）、热膨胀系数（α）、特征温度（Tg和Td）及化学稳定性的影响。实验结果表明：使用适量的添加剂可以增大...     

Y2O3掺杂对Al2O3-SiO2-P2O5系统玻璃结构和析晶性能的影响

采用高温熔融冷淬法制备了Al2O3-SiO2-P2O5（ASP）系统玻璃,用原位晶化法获得了磷酸盐微晶玻璃;用IR、DSC、XRD、SEM等测试方法表征了玻璃结构及析晶性能,讨论了稀土Y2O3掺杂对ASP玻璃结构和析晶性能的影响。结果表明：Y2O3处于ASP的玻璃结构空隙中,起网络修饰体的作用,并未改变玻璃的基本结构,但Y^3＋离子会加强玻璃中P-O^-键的伸缩振动。当Y2O3的掺杂量少于1．5wt％时,随着Y2O3含量的增加,玻璃的稳定性增强,析晶活化能升高;引入量为1．5wt％时,玻璃的稳定性最好,析晶活化能最大,玻璃不易析晶;掺杂量多于1．5wt％时,稳定性开始下降,析晶活化能降低。少量Y2O3掺杂并未改变玻璃析出的晶相种类,析出的主晶相仍为AlPO4,次晶相为Mg3（CO4）2,但玻璃中加入适量的Y2O3会减少次晶相Mg3（PO4）2的析出量。     

ZnO-B2O3-P2O5系封接玻璃的研究

采用熔融法制备了ZnO-B2O3-P2O5系无铅磷酸盐封接玻璃,研究了组成对玻璃结构、特征温度、热膨胀和化学稳定性的影响.结果表明:B2O3和P2O5为玻璃网络形成体,ZnO含量较低时可以参与到玻璃网络结构中,提高玻璃的稳定性;玻璃转变点Tg、熔制温度Tm、封接温度Ts、软化点Td都随P2O5/B2O3减小而增加;B2O3/ZnO是影响玻璃熔制温度的主要因素;ZnO含量对玻璃密度和热膨胀系数影响较大.ZnO-B2O3-P2O5系玻璃在中性环境下的化学稳定性较好.     

氧化物添加剂对P2O5-ZnO-B2O3系低熔点玻璃物化性能的影响

作为绿色环保材料,无铅低熔点玻璃已经在电子元器件的封装和涂层等领域得到了广泛应用。以P2O5-ZnO-B2O3体系为基础玻璃,通过外加法研究氧化物添加剂(Fe2O3、MnO2、CuO、CeO2和Y2O3)对玻璃密度(ρ)、热膨胀系数(α)、特征温度(Tg和Td)及化学稳定性的影响。实验结果表明:使用适量的添加剂可以增大玻璃密度;除Y2O3外,其它添加剂提高玻璃的热膨胀系数;MnO2、CuO和Y2O3显著降低玻璃的特征温度,但Fe2O3和CeO2的影响较小;加入适量添加剂能显著改善玻璃的化学稳定性,其中加Y2O3的耐酸性最好,加CeO2的耐碱性最好。     

CuO对ZnO-Bi2O3-B2O3系玻璃结构及热处理结果影响

本研究以ZnO-Bi2O3-B2O3系为基础,采用熔融-淬冷法制备玻璃,用FT-IR、DTA、DIL(膨胀仪)和XRD以及测量样品收缩率等,研究了添加CuO对该玻璃的结构、转变温度(Tg)、析晶情况、烧结及流散性的影响.FT-IR分析表明,随着玻璃中CuO含量增加,与[ZnO4]和[BiO6]结构有关的峰由517移到523 cm-1;但没有改变玻璃中[BO3]结构多于[BO4]的基本情况.DTA分析表明,该基础玻璃的Tg为447℃,第一结晶温度(Tc1)为604℃,第二结晶温度(Tc2)为820℃;添加0.5 wt.%CuO后,T和Tc2不变,Tc1降至523℃;XRD分析也发现添加CuO玻璃在530℃出现了较明显衍射峰.添加少量CuO,有助于玻璃致密化,使玻璃产生流散的温度降低,从而有利于封接.     

Na2O-Al2O3-B2O3玻璃的热学性质和红外光谱

制备了Na2OAl2O3B2O3系统低熔点玻璃,确定了Na2OAl2O3B2O3系统玻璃成玻范围,研究了玻璃的转变温度(Tg)、热膨胀系数(α)和玻璃的红外光谱,表明这种玻璃的熔化温度低、转变温度也较低、玻璃的热膨胀系数较大,在近红外区有一水分的吸收带,在中红外区有BO、AlO的特征吸收带,以及玻璃的Tg、α与玻璃组成的关系。     

TiO2对R2O-MgO-Al2O3-SiO2-ZrO2系微晶玻璃析晶及性能的影响

以花岗岩废渣为主要原料,用熔融法制备了添加TiO2的R2O-MgO-Al2 O3-SiO2-ZrO2(RMASZ)系微晶玻璃.采用X-射线衍射(XRD)、扫描电子显微镜(SEM)、电子万能材料试验机和显微硬度测试仪研究了TiO2对RMASZ系微晶玻璃的晶相组成、显微结构以及力学性能的影响.结果表明:当TiO2含量为0wt％、0.5wt％、1wt％时析出的主晶相为t-ZrO2和顽火辉石;当TiO2含量为2wt％和3wt％时析出假蓝宝石相,顽火辉石相减少.当TiO2为0.5wt％时晶粒细致均匀,其四点抗弯强度达到122.41 MPa,显微硬度为9.35 GPa.     

基于CaO-SiO2-Al2O3-Fe2O3-SO3系统的水泥熟料矿物研究

采用石灰石、硬石膏、粉煤灰、硅石为原料,研究了固定铝硫比（P=3.82）条件下,氧化铝含量为10%时,碱度系数和煅烧温度对CaO-SiO2-Al2O3-Fe2O3-SO3系统水泥熟料矿物烧成的影响。结果表明,碱度系数为1.2,煅烧温度范围为1375~1425℃时制得的水泥为高贝利特硅酸盐水泥;C4A3S分解生成了C3A,而非C12A7;在SO3和C3A存在的条件下,促进C3S在低温下形成,部分C3S在高温下分解为α＇-C2S;水泥熟料的矿物形貌未发生明显的变化。     

Enhanced plasticity by deformation-induced nanocrysallization in bulk amorphous Al2O3-ZrO2-Y2O3

Deformation of bulk amorphous Al₂O₃-ZrO₂ with different ratios of A/Z was investigated under compression at 500 °C. A20Z and A40Z exhibited brittle fracture and remained amorphous after compression; however, significant plastic deformation was achieved in A60Z and A80Z. Nanocrystallite of t-ZrO₂ were detected in A60Z and A80Z during the plastic deformation, and deformation-induced nanocrystallization in amorphous oxides was reported for the first time. Ductile transformation temperature was proposed as a criterion for the deformability of amorphous materials. The nanocrystallization improved the plasticity in turn, due to the easier formation of multiple shear bands at the interface between nanocrystallite and amorphous matrix. Crystallization activation energy was identified as a key factor dominating the deformation of amorphous oxides, and low crystallization activation energy could contribute to easy nanocrystallization, lower the ductile transformation temperature, and promote the plasticity. This work gave further understanding of plastic deformation in amorphous oxides.     

R2O对ZnO-Sb2O3-P2O5低熔玻璃性能的影响

借助IR、DTA等研究了碱金属氧化物R2O(R=Li,Na,K)对ZnO-Sb2O3-P2O5低熔玻璃结构及性能的影响。结果表明:不同种类碱金属氧化物的加入对玻璃的磷酸盐网络结构无明显影响,但K2O的引入提高了玻璃的转变温度(Tg)、软化温度(Ts)、析晶倾向和耐水性。R2O取代ZnO后破坏了玻璃的网络结构,导致玻璃的Tg及Ts温度和耐水性的降低,增加了玻璃的析晶倾向。在总碱量不变的条件下,借助混合碱效应,调节Li2O/(Li2O Na2O)摩尔比能够获得Tg及Ts温度更低的玻璃,同时耐水性也有所提高。对玻璃膨胀系数(α)的影响依次为K2O>Na2O>Li2O,且随R2O含量的增加而增加。此外混合碱效应对α的变化无明显影响。     

Cr2O3微粉加入量对Al2O3-Cr2O3质耐火材料性能的影响

以电熔铬刚玉和白刚玉为主要原料,用Cr₂O₃微粉部分替代电熔铬刚玉细粉,研究了Cr₂O₃微粉加入量对Al₂O₃-Cr₂O₃质耐火材料常温和高温性能、物相组成和显微结构的影响。结果表明,随着Cr₂O₃微粉加入量的增加,原位形成了(Al_1-xCr_x)₂O₃固溶体,促进了烧结,材料的显气孔率先降低后升高,且(Al_1-xCr_x)₂O₃固溶体的晶格常数呈线性增加,符合Vegard定律。材料的常温抗折强度和常温耐压强度随Cr₂O₃微粉加入量的增加先升高后降低,在Cr₂O₃微粉加入量为15%(质量分数)时强度达到最大值。而当Cr₂O₃微粉加入量为20%(质量分数)时,由于有挥发现象,材料显气孔率上升,强度下降。材料高温抗折强度随Cr₂O₃微粉加入量的增加而增加,材料的残余强度保持率呈先降低后升高的趋势。     

La2 O3对SiO2-Al2 O3-CaO-MgO系统玻璃结构与性能的影响

采用高温熔融法制备了SiO2-Al2 O3-CaO-MgO系统玻璃,研究添加La2 O3对SiO2-Al2 O3-CaO-MgO系统玻璃密度、耐碱性、弹性模量以及析晶上限温度的影响,并借助红外光谱对玻璃的结构进行研究。结果表明：随着La2 O3含量从0升高至5wt%,玻璃的网络结构发生改变;玻璃的密度和摩尔体积均增大;玻璃的耐碱性能降低;弹性模量从90.5 GPa增加至93.6 GPa后降低,最大值对应的La2 O3含量为3wt%;析晶上限温度从1224℃降低至1209℃后增加至1212℃,最后趋于不变,在La2 O3添加含量为2wt%时达到最低温度。     

SiO2-CaO-Al2O3-B2O3微晶釉在平板式中温固体氧化物燃料电池密封中的应用

平板式中温固体氧化物燃料电池(intermediate temperatlure solid oxide ruel cells,ITSOFC)在600～850℃温度下运行,电解质两侧的燃料气体(Hz)和氧化气体(Oz)必须加以分离,这要求金属双极板和陶瓷电解质高温气密封接。两者之间的密封材料应该与双极板和电解质很好的浸润粘附,达到气密要求;还会产生高温蠕变或粘滞流动以消除使用中因热膨胀系数差异引起的热应力。为了保证电池长期安全稳定的运行,还要求密封材料保持尺寸稳定性,与双极板和电解质材料有良好的化学稳定性。采用SiO2-Cao-A12O3-B2O3系统微晶釉制备出一种适用于850℃工作的ITSCIFC密封材料。该系列微晶釉在850～900℃与ZrO2电解质和不锈钢双极板材料充分浸润粘附,在850℃保证高温尺寸稳定性和化学稳定性的前提下,能够提供一种“软”密封,通过粘滞流动很好的满足了应力释放的要求。经过近100h,10次循环密封实验(400～850℃)证明,该材料适用于850℃工作的ITSOFC的密封。     

Design and development of SiO2-Al2O3-B2O3-Na2O based glass sealant for the glass-metal joint

SiO₂-Al₂O₃-B₂O₃-Na₂O based glass sealant compositions were designed for the development of GMJ using extreme vertices methodology. The effect of the glass sealant individual constituent on wettability, Glass transition temperature (T_g), Crystallization temperature (T_c), thermal conductivity, and density was analyzed with the help of analysis of variance technique (ANOVA). The increase in SiO₂ constituent in glass sealant decreased the spreading area (mm²) of glass sealant and increased the value of contact angle (θ) formed by glass sealant over the SS304 metal substrate. The T_g and T_c of glass sealant also increased as SiO₂ content increased. The addition of B₂O₃ and Na₂O in glass sealant system reduced the T_g and T_c of glass sealant. The developed regression model was validated and it was observed that the experimental and predicted results nearly matched with an error less than 5% in most of the cases.     

Rheological behavior of the CaO-Al2O3-based mold fluxes with different Na2O contents

The CaO-Al₂O₃-based mold flux is expected during the casting of aluminum containing advanced high strength steels. In this study, the rheological behavior of the CaO-Al₂O₃-based mold fluxes with different Na₂O contents was investigated. The results show that the viscosity in the range of 1423–1573 K reduced sharply when the Na₂O content increased from 0 wt % to 10 wt %, but the tendency slowed down with further increasing Na₂O from 10 wt % to 15 wt %. The activation energy for viscous flow also decreased from 237.76 ± 4.88 kJ/mol to 180.37 ± 7.10 kJ/mol with increasing Na₂O. The structure analyses show that the melt networks were mainly constructed by [SiO₄]^4--tetrahedral, [AlO₄]⁵-tetrahedral and Si-O-Al structural units. These networks were depolymerized with the addition of Na₂O since the charge compensation effect from Na⁺ was relativity weaker comparing with the network breaking effect from O²⁻. In addition, the break temperature of the mold fluxes also decreased from 1406 K to 1198 K due to the more precipitation of low melting point Ca₂Al₂SiO₇, rather than MgAl₂O₄ in the mold flux, during the cooling cycle.     

K2O含量对B2O3-Al2O3-Na2O玻璃结构及物理性能的影响

选取B_2O_3-Al_2O_3-Na_2O三元玻璃系统,研究改变玻璃系统中K_2O的含量对硼酸盐低熔点封接玻璃性能的影响。通过XRD、DTA等手段对玻璃样品的膨胀系数、转变温度、软化温度、电阻率、介电常数等性能进行了测试。结果表明:在B_2O_3-Al_2O_3-Na_2O三元玻璃系统中,随着K_2O含量的增加,硼酸盐玻璃的膨胀系数呈先下降后上升的趋势,在K_2O含量位于5 mol%左右时,硼酸盐玻璃的膨胀系数小幅下降,这是硼反常现象的体现。K_2O含量在7～8 mol%左右时,膨胀系数出现最低值。玻璃的体积电阻率和介电常数的变化也存在着硼反常现象,随着K_2O含量的增加,均呈现先下降再上升后又下降的趋势。玻璃的转变温度T_g和软化温度T_f的变化趋势基本一致,均呈现先下降后上升再下降的趋势。     

High temperature failure modes of In2O3 thin films and improved thermal stability using Al2O3/ZrO2 protective layers

The limiting temperature of an In₂O₃ thin film sensor is much lower than its melting point. Herein, the failure modes of In₂O₃ thin films at high temperatures, including sublimation and changes in composition, have been studied. The edge and surface layer sublimation rates increased dramatically at 1350 °C, indicating that it is the limiting temperature of no-protection In₂O₃ films. In addition, oxygen atoms will escape from In₂O₃ thin films at high temperatures, forming oxygen vacancies. As the main current carrier type in In₂O₃, the increasing number of oxygen vacancies affects the resistance of In₂O₃ thin film sensors. To solve these problems and promote the high temperature performance of In₂O₃ thin films, protection methods based on Al₂O₃ and ZrO₂ layers have been investigated. The ZrO₂ protective layer alleviated the serious considerable sublimation of In₂O₃ thin films at high temperatures, and the Al₂O₃ protective layer was beneficial for reduction the escape of oxygen atoms. Finally, different protection layers were evaluated by in-situ resistivity measurements of In₂O₃ thin films at high temperatures. The resistance of the In₂O₃ thin film resistor with a protective multilayer consisting of Al₂O₃ and ZrO₂ remained stable at 1360 °C, verifying the protection method effectively increased the thermal stability of In₂O₃ thin films.