基于响应面法的原子层沉积高阻隔膜研究

目的 研究分析等离子辅助原子层沉积技术(ALD)技术在PET表面上沉积超薄Al2O3阻隔层的工艺优化。方法 采用单因素结合响应面设计试验法,对Al2O3/PET薄膜的沉积速率(GPC)进行优化,通过AFM分析得到薄膜的生长模式和表面粗糙度,最后用水蒸气透过率表征薄膜的阻隔性能。结果 最大GPC的沉积参数:TMA脉冲时间为0.17 s、吹扫时间为11 s、O2的脉冲时间为0.35 s、吹扫时间为10 s、沉积速率为0.215 nm/cycle;薄膜以层状生长模式生长,表面粗糙度均方根(RMS)为0.58 nm;沉积500个循环后薄膜的水透过率从7.456 g∙d/m²降低到0.319 g∙d/m²。结论 通过响应面法优化了ALD制备工艺参数,Al2O3在PET表面沉积100 nm左右时,水蒸气阻隔性提高了25倍。     

Investigation of self-assembly growth and thermal stability of Au nano-particles on atomic-layer-deposited Al2O3 film

在原子层淀积的Al₂O₃薄膜表面自组装生长Au纳米颗粒,研究了Au纳米颗粒的自组装过程和热稳定性. 结果表明,原子层淀积的Al₂O₃薄膜表面很容易吸附氨丙基三甲基硅烷(APTMS), 有利于Au纳米颗粒的自组装, 生长出的Au纳米颗粒尺寸为5--8 nm, 密度约为4×10¹¹cm^-2. 在300℃氮气中退火使Au纳米颗粒的尺寸增大, 但是没有改变APTMS的吸附状态和Au的化学组成. 当退火温度提高到450℃时, Au纳米颗粒发生明显的团聚, 且分布变得极不均匀.     

CuO-TiO_2复合助剂低温烧结氧化铝陶瓷的机理(Ⅱ)

固定CuO(0.4%)和TiO₂(4%)的添加量、改变TiO₂(0--32%)和CuO(0--3.2%)的添加量(质量分数, 下同), 研究了CuO--TiO₂复合助剂对氧化铝陶瓷烧结性能、微观结构、物相组成以及烧结激活能的影响, 以揭示复合助剂的低温烧结机理。结果表明, 在1150--1200℃TiO₂固溶入Al₂O₃生成Al₂Ti₇O₁₅相, 并生成大量正离子空位提高了扩散系数, 从而以固相反应烧结的作用机理促进了氧化铝陶瓷的致密化; TiO₂在Al₂O₃中的极限固溶度为2%--4%, 超过固溶极限的TiO₂对陶瓷烧结没有促进作用; 添加适量的CuO(0.4%)可将TiO₂在Al₂O₃中的固溶温度降低到1100℃以下, 并以液相润湿作用促进氧化铝陶瓷的致密烧结。陶瓷烧结激活能的计算结果定量地印证了上述烧结机理; 当在Al₂O₃中添加4%的TiO₂和2.4%的CuO, 可将烧结激活能降低到54.15 kJ ? mol-1。     

碳化硅与氧化铝界面化学稳定性研究

借助最新最权威基本的热力学数据,按化学平衡理论,分析SiC和Al₂O₃之间可能发生的化学反应,定量计算SiC中不同C活度、不同固相产物活度,不同温度下SiC和Al₂O₃间诸反应各气相产物分压和分压总和,精确分析SiC和Al₂O₃界面的热力学稳定性,提供一个大气压惰性气体环境SiC和Al₂O₃界面的热力学失稳判据,为SiC材料研究者提供可靠的参考资料。     

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。     

Al2O3颗粒粒径和含量对α-Al2O3/Cu复合镀层性能的影响

本文研究了复合电沉积法制备的α-Al₂O₃/Cu 复合材料的性能和磨损特征, 测定了Al₂O₃粒径在0. 5～ 5Lm, 含量在4～ 16% 时Al₂O₃/Cu 复合镀层的硬度和磨损率, 用扫描电镜对磨损形貌进行了分析, 并对其磨损机制进行了探讨。结果表明, 镀层中硬度随Al₂O₃含量增加呈线性增长, 且含大颗粒Al₂O₃镀层的硬度略高于小颗粒镀层,Al₂O₃颗粒含量和粒径大小对磨损率和磨损机制有显著影响。     

(Al2O3)f/Al复合材料在强界面结合下的疲劳损伤模式

在拉-拉载荷下测定了(Al₂O₃)_f/Al复合材料的疲劳寿命(S-N)曲线。通过夭折试验以及SEM疲劳断口和纵截面组织结构分析,研究了复合材料的疲劳损伤模式。研究结果表明,(Al₂O₃)_f/Al复合材料的疲劳极限为750MPa,远高于SCS-6碳化硅纤维增强钛基复合材料。该复合材料兼有钛基和树脂基纤维复合材料疲劳损伤的特点,高应力下由单个裂纹的起源和生长导致复合材料的失效;低应力下,疲劳损伤模式包括纤维劈裂、众多基体裂纹和单个基体裂纹的横向扩展。其中纤维劈裂是主控机制。其更高的疲劳极限可归因于低应力下纤维的纵向劈裂。     

片状Al2O3对Al2O3/FEP复合材料热导率的影响

通过混炼工艺制备了片状Al₂O₃填充聚全氟乙丙烯(FEP)复合材料,以颗粒状Al₂O₃为对比样品,研究了片状Al₂O₃形状和尺寸对 FEP基复合材料热导率的影响,利用SEM观察了FEP基复合材料的微观形貌。结果表明：在低填充量下,Al₂O₃颗粒在FEP基体中呈“海岛”状分布,没有形成连续的导热网链,但其热导率明显提高;复合材料拉伸强度与断裂伸长率随Al₂O₃含量的增加而减小;低填充量时复合材料热导率的提高主要来自Al₂O₃的微细片状结构,这种微细片状结构一方面提高了有效导热路径,另一方面增加了颗粒与基体之间接触面积,因此有利于热导率的提高。     

MgO/Al2O3比对MgO-Al2O3-SiO2系统玻璃分相与析晶的影响

采用高温熔融法制备了具有不同MgO/Al₂O₃比的堇青石微晶玻璃。采用差热分析仪(DTA)、X射线衍射仪(XRD)、扫描电子显微镜(SEM)等测试技术研究了MgO/Al₂O₃比对该系统玻璃分相和析晶的影响。结果表明:当SiO₂含量不变时,随着MgO/Al₂O₃比的减小,分相形貌由连通的蠕虫状逐渐变为孤立的球形结构,且分相粒子尺寸逐渐减小,从200~300 nm减小至30~50 nm。当MgO/Al₂O₃比从3降到1,析晶峰温度由997 ℃升至1 105 ℃,析晶的难度逐渐提高。当MgO/Al₂O₃比为3时,MgO-Al₂O₃-SiO₂系统玻璃经950 ℃热处理后即产生大量分相,经1 050 ℃热处理后在分相液滴中析出大量堇青石晶体,且堇青石优先在富Mg相中析出。提高MgO/Al₂O₃比有利于MgO-Al₂O₃-SiO₂系统玻璃在分相中析晶,反之,则会降低系统的分相和析晶能力。     

SiO2玻璃原位反应合成Al/Al2O3复合材料

利用SiO₂玻璃具有易近成型、致密及各向同性的特点,通过SiO₂玻璃与铝熔体间的反应合成了Al/Al₂O₃复合材料,克服长期以来在合成Al/Al₂O₃复合材料时均采用颗粒反应物的局限。反应产物是一种组织均匀致密的Al 与Al₂O₃互为网络的Al/Al₂O₃陶瓷基复合材料。反应温度升高,整个反应产物中的Al的体积分数上升。Al/Al₂O₃复合组织在三维空间的真实形态中存在着Al相被Al₂O₃完全包围的形态,证明了网络状Al₂O₃组织形成的烧结机理。与合成Al/Al₂O₃的其它工艺相比,本工艺可在1000℃的较低温度进行,并具有反应速度快、断裂韧性和抗弯强度值高的特点。     

Y2O3与Gd2O3共掺杂SrZrO3热障涂层材料的热物理性能

采用固相反应法合成了5mol%Y2O3与5mol%Gd2O3共掺杂SrZrO3(Sr(Zr0.9Y0.05Gd0.05)O2.95,SZYG)粉末.采用X射线衍射(XRD)和差示扫描量热仪(DSC)分别研究了SZYG粉末在1450℃长期热处理后以及200~1400℃范围内的相稳定性.采用高温热膨胀仪测量了SZYG块材的热膨胀系数,结果表明:通过Y2O3与Gd2O3共掺杂改性可以明显抑制SrZrO3的相转变.在1000℃下SZYG块材的热导率是～1.36 W/(m.K),与SrZrO3和8YSZ块材相比降低~35%SZYG分别与8YSZ和Al2O3在1250℃热处理24 h表现出很好的化学相容性.     

稀土Dy和Ce共掺杂La2Zr2O7新型热障涂层用陶瓷材料

用化学沉淀法制备了稀土Dy和Ce共掺杂La2Zr2O7新型热障涂层用陶瓷粉末Lal.7Dy0.3(Zr0.8CeZr0.2)2-O7(LDCZ).通过X射线衍射、扫描电镜、高温膨胀仪、DSC和激光热导仪对粉末相结构、不同煅烧温度下的相组成、微观结构,高温相稳定性,热膨胀系数和导热系数进行了分析.结果表明,稀土共掺杂的La1.7Dy0.3(Zr0.8CeZr0.2)2O7保持了烧绿石结构,120℃时粉末为无定形的混合氧化物,900℃时转化为复合氧化物,1200℃时转变为单一的烧绿石相;高温下LDCZ无明显相变;添加Dy和Ce不仅可提高锆酸镧的热膨胀系数,使其高于8YSZ的热膨胀系数,并可使其导热系数较La2Zr2O7降低25%以上,达到1.28～1.07W/m.K.     

热障涂层用Nd2O3-CeO2-ZrO2陶瓷粉末制备及其性能研究

采用化学沉淀法制备了热障涂层用Nd2Zr2O7(NZ)以及CeO2-Nd2O3-ZrO2(NCZ)陶瓷粉末.通过电感耦合等离子体原子发射光谱(ICP-AES),X射线衍射、DSC及霍尔流速计对粉末化学组成、相组成,高温相稳定性和流动性能进行了研究.通过高温膨胀仪、DSC和激光热导仪分别测定其热膨胀系数和导热系数.结果表明,掺杂的NCZ粉末保持了NZ的烧绿石相结构, 120℃时粉末为无定形的混合氧化物,900℃时转化为复合氧化物,1200℃时转变为单一的锆酸钕烧绿石相;高温下NCZ无明显相变;在高于1400℃的温度下煅烧后,NCZ的流动性得到显著改善;添加CeO2可提高锆酸钕的热膨胀系数,而对其导热系数和比热系数的影响不大.     

Barrier properties of Al2O3 and alucone coatings and nanolaminates on flexible biopolymer films

Thin atomic layer deposited (ALD) Al₂O₃ coatings are efficient barriers against gases and vapors. Al₂O₃ coatings are, however, brittle and straining them generates defects that impair barrier properties. Flexibility of ALD-grown Al₂O₃ coatings on biopolymer substrates can be improved by separating thinner Al₂O₃ layers with inorganic-organic alucone layers. The number and size of defects were smaller for these nanolaminates compared to the thick Al₂O₃ films after straining, and hence straining deteriorated the oxygen barrier properties less when applied to the laminates than when applied to the Al₂O₃ coatings.     

Barrier layer and grain boundary effects in Nd/Zr doped BaTiO3 ceramics

Gradient structures with barrier layer characteristics and core-shell morphology have been developed in BaTiO₃ ceramics with Nd₂O₃ and ZrO₂ as co-dopants. Features include reduced Curie temperatures and anisotropic stress gradients, resulting from an oxidized surface layer and reduced interior, developed during air sintering. Co-doping was typically carried out through solution milling of the BaTiO₃ powders with nitrate precursors of the dopant oxides, spray drying and sintering of the pressed pellets in air ambient at 1300-1320 °C/60-90 min with furnace cooling. Structural characterization, as well as dielectric and d.c. resistance measurements of the pellets, as-sintered and after removing equal amounts of material from both surfaces, revealed the existence of an oxidized surface layer and barrier layer microstructures consisting of graded regions of oxidized insulating surfaces over partially oxidized or conducting grain interiors. In this complex structure, the ZrO₂ segregates to the grain boundary region, forming a core-shell structure, with Nd₂O₃ partitioning between the BaTiO₃ and ZrO₂ phases. The overall system was modeled in terms of an equivalent circuit and the analysis indicates that the dielectric constant and the loss behavior are strongly impacted by both the surface and grain boundary barrier characteristics, with the surface barrier effects having the more dominant effect on the dielectric properties of the doped compositions. Indications are that fine-tuning of the system to optimize the grain boundary effect could lead to extraordinary dielectric constant effects which could potentially be utilized in high energy storage devices.     

AlPO4环境障碍涂层材料水氧腐蚀性能研究

采用溶胶凝胶法合成了一种AlPO₄环境障碍涂层材料,测定了其热膨胀系数,在1350℃、50vol% H₂O/50vol%O₂、1.013×10⁵ Pa、气体流速0.085cm/s的水氧耦合环境中研究了其抗水氧腐蚀性能,并利用X射线衍射仪、能谱分析仪和扫描电子显微镜分析了材料组成和微观结构.结果表明,AlPO₄与C/SiC复合材料热膨胀基本匹配,抗水氧腐蚀性能良好.主要存在的问题是AlPO₄分解引起的失重,二氧化硅会加速其分解.     

热障涂层陶瓷层材料LnMgAl11O19(Ln=La,Nd)粉体的性能

用共沉淀法制备LaMgAl₁₁O₁₉粉体,证明了提高沉淀温度和pH值可使前驱粉体的性能明显提高。应用差热分析和X射线法研究了磁铅石相的生成温度和粉体的结晶度;使用Scherrer 公式并结合XRD谱计算了晶粒尺寸;用扫描电镜观察了各工艺参数的前驱粉体在1500℃时效5 h后的形貌;使用Malvern ZEN3600粒度仪和Manual measurement软件分析了粉体硬团聚的尺寸分布;用Nd₂O₃, Gd₂O₃, Sm₂O₃替代La₂O₃,研究了制备多种镁基六铝酸盐粉体的可行性。结果表明：在pH值为11.5、沉淀温度为60℃条件下制备的前驱粉体,其完全相变为纯LaMgAl₁₁O₁₉粉体的初始温度为1440℃,比在常温下沉淀的前驱粉体降低了150℃,磁铅石相的生成效率明显提高。在1500℃时效5 h的粉体其晶粒为纳米尺度。提高沉淀温度和pH值有利于减小晶粒尺寸和降低粉体的热导率。采用相同工艺参数可制备出纯NdMgAl₁₁O₁₉粉体,其晶粒尺寸略大于LaMgAl₁₁O₁₉粉体的尺寸。     

Self-Consistent Calculation of the Self-Trapping Barrier for a Hole in the CuO2 Plane

We study the behavior of an extra hole added to the ground state of the antiferromagnetically ordered CuO₂ plane. Both the Cu--O hybridization and the O--O transfer are taken into account. As has been shown previously (V. Hizhnyakov and E. Sigmund, Physica C 156, 655 [1988]), the energetically most favorable situation is given when a localized state is formed in which the antiferromagnetic order is locally destroyed and a small ferromagnetic cluster is built up. We show that due to the increase of the magnetic energy induced by the spin–flip process (E _s0.15 eV), the localized and the metastable free-hole states are separated by a barrier of energy (E _b0.05 eV), which can reveal itself in various kinetic phenomena.     

Magnetic coupling in La0.67Ca0.33MnO3/La0.67Sr0.33CoO3/La0.67Ca0.33MnO3 sandwiches

La_0.67Ca_0.33MnO₃ (LCMO)/La_0.67Sr_0.33CoO₃ (LSCO)/LCMO trilayer films are fabricated on single-crystal substrates NdGaO₃ (110) and the interlayer coupling are investigated. Compared with LCMO single layer, sandwiches showed the enhanced metal-insulator transition temperature of LCMO layers. The magnetoresistance is dependent on spacer thickness and the peak value dramatically decreases when LSCO layer is thick enough because of shorting by the LSCO layer. The magnetic coercivity H_C shows a nonmonotonic behavior with changing spacer layer thickness and the waist-like hysteresis indicates that there is an indirect exchange coupling between the top and bottom LCMO layers across the spacer layer.     

Varistor properties of ZnO-Pr6O11-CoO-Cr2O3-Y2O3-In2O3 ceramics

The varistor properties of the ZnO-Pr₆O₁₁-CoO-Cr₂O₃-Y₂O₃-In₂O₃ ceramics were investigated for different concentrations of In₂O₃. The increase of In₂O₃ concentration slightly increased the sintered density (5.60-5.63 g/cm³) and slightly decreased the average grain size (3.4-2.9 μm). The breakdown field increased from 6023 to 14822 V/cm with increasing concentration of In₂O₃. The nonlinear coefficient increased from 17.6 to 44.6 for up to 0.005 mol%, whereas the further doping caused it to decrease to 36.8. In₂O₃ acted as an acceptor due to the donor concentration, which decreases in the range of 1.02 × 10¹⁷ to 0.24 × 10¹⁷/cm³ with increasing concentration of In₂O₃.