α-Si3N4晶须中缺陷与晶须生长气氛关系的研究

本文研究了用无定形氮化硅超细粉原位生长α-Si₃N₄晶须,晶须生长温度为1400～1450℃,恒温1～4h.讨论了在晶须生长过程中,不同的保护气氛对晶须质量的影响.当晶须在高纯N2气氛中生长时,得到的晶须中氮含量为32%～34%,氧含量为8%～6%,氯含量为0.1%左右.这类晶须中存在着大量的缺陷.当晶须在NH3气氛中生长时,得到的晶须中氮含量为39%左右,氧含量为1%,氯含量为0.01%,在这类晶须的透射电镜照片中几乎看不到缺陷.     

α－Si_3N_4晶须、晶柱与生长温度关系的研究

本文采用无定形氮化硅超细粉制备α－Ｓｉ_３Ｎ_４晶须和晶柱，并对生长温度对晶须中的缺陷的影响进行了研究。结果表明：晶须生长时能否得到完整的晶体，与其生长温度有关，只有某一温度范围（１４３０℃±３０℃）生长时，才能得到比较完整的晶体，晶须的生长温度太高或太低均会引起晶体生长的不完整性，晶须中会出现大量的缺陷，温度继续升高时，在晶须中又出现了晶粒，继而生长成晶柱。     

热处理对Bi2O3-B2O3-SiO2凝胶玻璃粉体结构与性能的影响

采用溶胶-凝胶法制备了一种Bi₂O₃-B₂O₃-SiO₂系玻璃粉体,在200 ℃、400 ℃、600 ℃和800 ℃温度下分别对凝胶玻璃粉体进行热处理,借助SEM、TEM、XRD、FT-IR、Raman、XPS、DSC、热膨胀仪及“纽扣”烧结实验分别测定了经不同温度热处理后玻璃粉体的结构与性能,分析了其结构变化对玻璃粉体转变温度T_g和烧结特性的影响。结果显示,在实验温度范围内,随热处理温度升高,Bi³⁺逐渐进入玻璃网络中,[BiO₆]八面体和[BiO₃]三角体、[BO₄]四面体和[BO₃]三角体分别与[SiO₄]四面体以顶角相连的方式构建玻璃网络结构。O1s和Bi4f的电子结合能逐渐增大,B1s的电子结合能减小,玻璃网络结构稳定性增强,导致玻璃转变温度T_g及玻璃膨胀软化点温度T_d升高、 润湿性降低且热膨胀系数略有降低。经600 ℃热处理后,玻璃粉体具有较优的烧结性能,T_g、T_d分别约为485 ℃及542 ℃,热膨胀系数α约为7.067×10-6/℃。     

超导Ag/Bi1.6Pb0.4Sr2Ca2Cu3O10-x复合氧化物摩擦磨损性能

为适应20℃～-200℃ 温度的适用范围,采用固相法制备了Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_10-x超导材料,用摩擦磨损试验机测试了Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_10-x从液氮温度至室温的摩擦学性能。结果表明 : 在室温 20℃下,Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_10-x与对偶件轴承钢盘对摩时,摩擦系数约为0.35,当温度降到超导转变温度以下时(液氮温度-170℃)摩擦系数大幅度降低,Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_10-x超导态摩擦系数为正常态值的一半,实验证明了电子激励对摩擦能量耗散的作用。为改善室温下Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_10-x摩擦学性能,掺杂不同质量分数 Ag作为润滑组元,制备了Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_10-x超导固体润滑复合材料,取得良好耐磨减摩效果。Ag掺杂不影响Ag/Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_10-x复合材料的超导性,在正常载荷和滑动速度下10 wt%Ag/ Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_10-x复合材料摩擦系数为0.2~0.3,磨损率为4.57×10-4 mm3·(N·m)-1。     

Y2O3添加量对Al2O3/ZrO2共晶陶瓷显微组织及力学性能的影响

为探索第三组元Y₂O₃添加对Al₂O₃/ZrO₂共晶陶瓷显微组织与机械性能的影响,本文利用低温度梯度的高温熔凝法制备了直径为20 mm的Al₂O₃/ZrO₂(Y₂O₃)共晶陶瓷块体,采用SEM、EDS及XRD技术对共晶陶瓷进行微结构分析,并利用维氏压痕法对其硬度和断裂韧性进行测试。SEM结果表明,凝固组织由群集的共晶团结构组成,随着Y₂O₃添加量的增加,共晶团形态由胞状转变为枝晶状,内部相间距在1~2 μm范围内变化。力学测试表明,Y₂O₃摩尔分数小于1.1%时,由于组织内部存在低硬度m-ZrO₂及微裂纹缺陷,故陶瓷硬度较低,约为(9.53±0.22 )GPa;当Y₂O₃摩尔分数为1.1%时,陶瓷硬度最大,约为(18.05±0.27)GPa;当Y₂O₃的摩尔分数大于1.1%时,由于共晶团边界区内气孔缺陷及粗大组织增多,引起陶瓷硬度值略有下降。低Y₂O₃摩尔分数添加时,陶瓷断裂韧性相对较高,约为(6.30±0.16)MPa·m^1/2,这与其内部存在大量微裂纹缺陷有关;随着Y₂O₃添加量的增加,陶瓷的微裂纹数量减少、边界区内缺陷增多,断裂韧性降低。     

纳米-Al2O3/SiO2加入量对MgO-Al2O3-SiO2复相陶瓷烧结机理的影响

为了探究纳米-Al₂O₃/SiO₂加入量对MgO-Al₂O₃-SiO₂复相陶瓷烧结行为的作用机理。以微米级MgO、纳米级Al₂O₃和SiO₂为主要原料制备陶瓷基复合材料。通过XRD和 SEM等检测手段对烧后试样的物相组成和微观结构进行测试与表征,重点研究Al₂O₃/SiO₂的加入对复相陶瓷物相组成、微观结构及烧结性能的影响。结果表明:随着Al₂O₃/SiO₂加入量的增大,试样烧后相对密度和烧后线变化率呈先增大后减小再增大的趋势,加入15%Al₂O₃/SiO₂(质量分数)的试样经1 500 ℃烧结后,其相对密度可以达到94%。引入的Al₂O₃/SiO₂与基体中的MgO生成镁铝尖晶石与镁橄榄石相,原位反应伴随的体积膨胀,抵消部分烧结过程中的体积收缩。Al₂O₃/SiO₂加入量为75%(质量分数)的试样经1 400 ℃烧结后,基体中有大量堇青石相生成,随着煅烧温度提高到1 500 ℃,堇青石分解所产生的高温液相促进了试样的烧结收缩。     

超导PbO/YBa2Cu3O7-δ复合氧化物摩擦磨损性能

为适应从低温到高温宽温范围的使用条件,用溶胶-凝胶法制备了YBa₂Cu₃O_7-δ超导材料,用摩擦磨损试验机测试了YBa₂Cu₃O_7-δ从室温至液氮温度的摩擦学性能。结果表明：室温20℃下,YBa₂Cu₃O_7-δ与对偶件不锈钢盘对摩时,摩擦因数在0.5左右,当温度降到超导转变温度以下时（液氮温度-196℃）摩擦因数大幅度降低,YBa₂Cu₃O_7-δ超导态摩擦因数是正常态值的一半,实验直接证明了电子激励对摩擦能量耗散的作用。为改善室温下YBa₂Cu₃O_7-δ摩擦学性能, 掺杂不同质量分数PbO作为润滑组元,制备了PbO/YBa₂Cu₃O_7-δ超导固体润滑复合材料,取得良好效果。PbO掺杂不影响PbO/YBa₂Cu₃O_7-δ复合材料的超导电性,在正常的载荷和滑行速度下15%PbO/YBa₂Cu₃O_7-δ复合材料摩擦因数为0.2至0.3,磨损率为4.35×10-4 mm3·（N·m）-1,分析了PbO/ YBa₂Cu₃O_7-δ复合材料减摩耐磨机制。     

CaO对17Ni/(10NiO-NiFe2O4)金属陶瓷的致密化及力学性能的影响

采用冷压-烧结技术制备了CaO掺杂的17Ni/(10NiO-NiFe₂O₄)金属陶瓷惰性阳极。研究了CaO的添加量和烧结温度对17Ni/(10NiO-NiFe₂O₄)金属陶瓷的物相组成、 致密度和力学性能的影响。结果表明, CaO含量在小于5.0wt%范围内, 烧结样品由Ni、 NiO和NiFe₂O₄组成。CaO掺杂对17Ni/(10NiO-NiFe₂O₄)金属陶瓷具有明显的助烧作用。当烧结温度为1250℃时, CaO掺杂量为1.0wt%的样品致密度达到最大值97.87%, 继续增加CaO掺杂量将导致材料致密度的下降。当烧结温度从1250℃提高到1350℃时, 当CaO掺杂量小于0.5wt%时, 样品的致密度随烧结温度的提高而增加; 当CaO掺杂量大于或等于0.5wt%时, 样品的致密度随烧结温度的提高而降低。提高烧结温度和添加CaO均能促进陶瓷相晶粒长大。样品在1250℃烧结时, 其抗弯强度在CaO掺杂量为1.0wt%时达到极大值为150.66MPa。     

烧成温度对Al2O3/Ni复合材料的致密化、物相组成和显微结构的影响

首先采用非均相沉淀合成出Ni包裹Al₂O₃粉体,然后热压烧结包裹粉体制备了Al₂O₃/Ni复合材料。本文作者主要研究了不同烧成温度对复合材料致密化、物相组成和显微结构的影响。结果表明:在1400℃保温1h,烧结体获得了最大相对密度,而致密度随Ni含量的增加反而降低;高于1350℃时,除Al₂O₃和Ni相外,在烧结体的表层生成一种由Al,Ni,O,C四种元素组成的新相;随着温度的升高,包裹层的纳米Ni颗粒聚合、长大,并退缩至三角晶界处,在适当的烧结温度(1400℃),少数小的纳米Ni颗粒被卷入Al₂O₃晶内,大的位于三角晶界,当烧成温度为1450℃时,不仅观察到Al₂O₃/Ni界面存在空隙,也发现了Al₂O₃晶粒异常长大现象。     

Fe2+、Fe3+对CaO-Al2O3-SiO2-MgO系微晶玻璃析晶性能的影响规律

为了利用大量的含铁铝硅酸盐固体废弃物制备具有高附加值的微晶玻璃,采用DTA、XRD、SEM、 EDS等手段研究了Fe₂₊、Fe₃₊对CASM系微晶玻璃析晶性能的影响,结果表明,Fe₂₊在微晶玻璃中与Mgz+的 作用相同,取代以网络外体形式存在的Al₃₊,使得微晶玻璃的析晶温度逐渐下降,而对析晶能力几乎没有影 响,并当Fe₂₊掺入量为2%时,主晶相由铝黄长石转变为镁黄长石,在7.5%时,进一步转变为透辉石．Fe₃₊掺 量小于7.5%时,起到补充S14不足的作用,当大于7.5%时,部分Fe₃₊起到与Fe₂₊、Mg₂₊相同的作用,使得 析晶温度呈先升后降的变化,在掺量为7.5%时,铝黄长石主晶相才开始转变为镁黄长石,在10%对,转变为 透辉石,且析晶能力得到大幅提升．随着Fe₂₊和Fe₃₊含量增加,虽然微晶玻璃中主晶相的变化顺序相同,但 Fe₂₊具有降低微晶玻璃析晶温度的作用,而一定量的Fe₃₊可作为晶核剂提高微晶玻璃的析晶能力     

自石灰石矿粉中直接提取CaCO3晶须的碳化-分解法研究

提出一种自石灰石矿粉中直接提取CaCO_3晶须的碳化-分解方法。该方法能够以天然石灰石矿粉为原料,通过水溶性碳酸的作用溶解出Ca(HCO_3)_2,进而在升温条件下通过Ca(HCO_3)_2的分解反应得到形貌规整的棱锥状CaCO_3晶须。扫描电镜观测与X射线衍射分析显示,Ca(HCO_3)_2分解温度对CaCO_3晶须微观形貌的影响显著,晶须长度与长径比随分解温度的升高均呈上升趋势,但分解温度超过80℃会导致文石晶相向方解石晶相转化。实验结果表明,80℃、2h条件下,Ca(HCO_3)_2分解产物中文石晶相含量较高,晶须几何形貌更为合理,其平均长度为14.61 μm、长径比为8.10。     

Effect of pulse duration on characteristics of modulated radio-frequency SiH4/N2/NH3 discharges

A one-dimensional fluid model is developed to investigate the behavior of plasma in the afterglow of pulsed voltage modulated SiH₄/N₂/NH₃ discharges at radio-frequency (400 kHz), which are used for the deposition of silicon nitride (SiN_x) films. The model incorporates particle balances, electron energy balance, and Poisson's equation, allowing the equations solved self-consistently. The current work is an attempt to understand the effect of duty cycle on the characteristics of silicon nitride (SiN_x) films. Therefore, the influences of duty cycle on the plasma density, electron temperature, and ion energy at the powered electrode were carefully discussed. We find that by decreasing the duty cycle, the negative ions can be able to escape during the off-time, and the positive ion energy is effectively decreased. On the other hand, the positive ion density is slightly decreased.     

Fabrication of hexagonal GaN on the surface of β-Ga2O3 single crystal by nitridation with NH3

The fabrication of GaN on the surface of a bulk β-Ga₂O₃ single crystal by nitridation with NH₃ was investigated for the purpose of using it as a substrate for GaN epitaxial growth. A β-Ga₂O₃ single crystal was prepared using a floating zone furnace with double ellipsoidal mirrors, and its polished (100) plane was nitridated in NH₃ atmosphere at 850 °C for 5 h. It was found that hexagonal GaN with preferred in-plane orientation was produced on the surface of β-Ga₂O₃, and the thickness of nitride layers was approximately 50 nm. High resolution transmission electron microscopic observation indicated that the synthesized GaN was composed of the aggregation with single crystalline GaN particles, whose size ranged from ∼ 5 nm to ∼ 50 nm, and dislocation or defect was not observed in a GaN particle. This method could be expected as a new route to fabricate a substrate for epitaxial growth of III-nitride materials instead of using a bulk GaN single crystal.     

BN含量对多孔BN/Si3N4陶瓷结构和性能的影响

以氮化硅(Si₃N₄)为基体, 氮化硼(BN)为添加剂, 叔丁醇为溶剂, 采用凝胶注模成型与无压烧结工艺(温度为1750 ℃、保温时间为1.5 h、流动N₂气氛), 成功制备出具有一定强度和低介电常数的多孔BN/Si₃N₄陶瓷。在浆料中初始固相含量固定为15%体积分数的基础上, 研究了BN含量对多孔Si₃N₄陶瓷材料的气孔率、物相组成及显微结构的影响, 分析了抗弯强度、介电常数与结构之间的关系。结果表明, 通过改变BN含量可制备出气孔率为55.1%~66.2%的多孔Si₃N₄陶瓷; 多孔BN/Si₃N₄复合陶瓷的介电常数随着BN含量的增加而减小, 为3.39~2.25; 抗弯强度随BN含量提高而有所下降, BN质量分数为2.5%时, 抗弯强度最高, 为(74.8±4.25) MPa。     

Nitridation enhancing effect of ZrO2 on silicon powder

The nitridation behavior of silicon powder with added Zr compounds was studied in order to assess the catalytic effect of zirconium on the formation of reaction bonded silicon nitride, using high purity silicon powder and monoclinic zirconia as starting materials. Thermogravimetric analysis revealed that the addition of ZrO₂ to Si powder reduced the temperature of the main nitridation reaction, and increased the amount of silicon converted to silicon nitride at a given temperature. On the other hand, the nitridation rate at higher temperatures (1380-1400 °C) indicated similar values for both pure Si and Si with ZrO₂ additions.     

Hydrogen etching of Si3N4 layers with plasma assisted hot wire CVD

In order to develop sustainable processes for clean manufacturing environment for thin film or other solar cell production, we studied the hydrogen etching of silicon nitride (Si₃N₄) films on flat crystalline silicon (c-Silicon) substrates. With an arrangement primarily constructed for hot wire CVD (HWCVD) deposition of thin silicon films also cleaning processes with atomic hydrogen were studied with a simplified three wire assembly. The three filaments could be biased independently by different potential. A variation of hydrogen pressure and flow was performed to find out conditions of high etching rates for the Si₃N₄ layers. The etching rate was simply determined by measuring the time for total removal of the film, since this could be easily detected by the change of the anti-reflection property. Etching rates of 0.1 nm/s have been obtained under 15 Pa and a flow of 50 sccm. An intensive study was carried out of the direct current (DC) plasma hot wire CVD conditions.     

Growth studies and characterization of silicon nitride thin films deposited by alternating exposures to Si2Cl6 and NH3

We deposited silicon nitride films by alternating exposures to Si₂Cl₆ and NH₃ in a cold-wall reactor, and the growth rate and characteristics were studied with varying process temperature and reactant exposures. The physical and electrical properties of the films were also investigated in comparison with other silicon nitride films. The deposition reaction was self-limiting at process temperature of 515 and 557 °C, and the growth rates were 0.24 and 0.28 nm/cycle with Si₂Cl₆ exposure over 2 × 10⁸ L. These growth rates with Si₂Cl₆ are higher than that with SiH₂Cl₂, and are obtained with reactant exposures lower than those of the SiH₂Cl₂ case. At process temperature of 573 °C where the wafer temperature during Si₂Cl₆ pulse is 513 °C, the growth rate increased with Si₂Cl₆ exposure owing to thermal deposition of Si₂Cl₆. The deposited films are nonstoichiometric SiN, and were easily oxidized by air exposure to contain 7-8 at.% of oxygen in the bulk film. The deposition by using Si₂Cl₆ exhibited a higher deposition rate with lower reactant exposures as compared with the deposition by using SiH₂Cl₂, and exhibited good physical and electrical properties that were equivalent or superior to those of the film deposited by using SiH₂Cl₂.     

微波烧结LiCo1/3Ni1/3Mn1/3O2电磁场与温度场的仿真模拟

分析了微波烧结的原理和特点,利用COMSOL Multi-physics模拟软件对矩形微波炉进行了仿真模拟,研究了微波烧结正极材料LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2时电磁场与温度场的分布,测量了粉末样品LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2的介电常数,并与模拟结果相对照.研究表明:微波在烧结LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2样品时,炉腔内电磁场的分布受到影响,微波炉内表面的电场强度减弱;材料内部温度场的分布不均匀,材料的下半部分温度较高;同时,在仿真模拟计算过程中,求得LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2在微波中烧结到不同温度时的能量损耗,根据李赫德涅凯法则计算出其对应的相对介电常数,发现在20~620℃,相对介电常数随温度的上升而变大.根据实验测得的复合介电常数,求出对应温度点LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2的相对介电常数.利用Origin对仿真模拟计算和实验求得的两组相对介电常数数据进行拟合对比,发现实验求得的LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2的相对介电常数与仿真模拟计算所得数据趋势吻合.     

温度对燃烧包覆LiMn2O4/ZnO及其电性能的影响

通过葡萄糖辅助低温燃烧制备ZnO包覆型LiMn2O4,利用X射线衍射仪、扫描电子显微镜、循环伏安、交流阻抗以及恒流充放电测试等手段,研究了温度对产物晶体结构、微观形貌及电化学性能的影响。XRD结果表明所有产物均为单相尖晶石型LiMn2O4结构。SEM结果表明产物的颗粒尺寸随温度的升高而增大。电化学性能测试表明400℃和500℃制备的LiMn2O4/ZnO具有相对优异的电化学性能,室温1C条件下首次放电比容量分别为119.3mAh/g、116.3mAh/g,循环100次后容量保持率分别85.6%、87.8%。尖晶石LiMn2O4电极的阻抗谱特征与温度有关,电池的电化学性能主要受电荷转移电阻(Rct)影响。     

无压烧结Ti3SiC2/铝基复合材料组织与性能

MAX相具有独特的层状晶体结构,不但具备常用铝基复合材料外加陶瓷颗粒的性能特征,同时具有可与石墨媲美的摩擦性能.本文以Al粉、Si粉和典型MAX相Ti_3SiC_2为原料,采用冷压成型-无压烧结方法制备了Ti_3SiC_2/Al-Si复合材料,并通过金相显微镜、X射线衍射仪(XRD)、扫描电镜(SEM)、能谱仪(EDS)等分析手段,研究了烧结温度、Si元素含量对复合材料组织与性能的影响.研究表明:随着烧结温度从500℃提高到700℃,复合材料致密度先上升后下降,摩擦系数先降低后上升,硬度逐渐增大至最大值并基本保持稳定;随着Si质量分数从0增加到20.7%,复合材料的致密度逐渐降低,硬度逐渐增大,摩擦系数先降低后增大,晶粒尺寸随之下降,12.5%Si晶粒最为细小;烧结温度为650℃,Si元素质量分数为12.5%的铝基复合材料具有最低的摩擦系数0.18,相应的硬度为62 HV,致密度为92.12%.XRD物相和扫描电镜组织分析表明,复合材料的主要相组成为Al、Ti_3SiC_2,及由界面反应产生的Al_4C_3和Al的氧化产物Al_2O_3.