Y1-xGdxBaCo4O7+δ的微结构和氧吸附性能

采用固相反应法制备了Y1–xGdxBaCo4O7+δ(x≤0.4)吸氧材料。利用X射线衍射(X-raydiffraction,XRD)和热重分析表征了样品的微结构和氧吸附性能。XRD结果表明:Gd掺杂量x≤0.2时,Y1–xGdxBaCo4O7+δ具有单相六方结构;x>0.2时,Y1–xGdxBaCo4O7+δ出现杂相。Rietveld精修XRD结果表明:Y1–xGdxBaCo4O7+δ(x≤0.2)样品的单胞参数和体积随Gd掺杂量增加而增大;Co—O键角变化不明显,Co—O键长变化较大,这使两种类型的CoO4四面体发生畸变。热重分析结果显示:从室温到1000℃,所有样品经历两次氧吸附过程,Gd掺杂的YBaCo4O7+δ最大吸氧量低于母相YBaCo4O7+δ的吸氧量,与氧的激活能有关。     

低介电常数(Mg_(1–x)Y_x)_2Al_4Si_5O_(18)陶瓷的制备与微波介电性能

采用传统陶瓷固相反应烧结法制备(Mg1–xYx)2Al4Si5O18陶瓷。Y3+掺杂产生液相烧结作用,使得堇青石陶瓷的烧结温度从1 450℃降低到1 325℃。结果表明:(Mg1–xYx)2Al4Si5O18陶瓷在0≤x0.05范围内,以(Mg,Y)2Al4Si5O18固溶体形式存在;在0.05≤x0.25范围内,以Mg2Al4Si5O18/Y2Si2O7复相陶瓷形式存在。Y3+能够改善(Mg1–xYx)2Al4Si5O18陶瓷的颗粒尺寸分布,并使陶瓷的气孔率降低。(Mg1–xYx)2Al4Si5O18陶瓷的相对介电常数由x=0的6.15提高到x=0.05的6.31;然后逐渐降低至x=0.25的5.90。品质因数Qf值由x=0的33 000 GHz提高到x=0.05的41 000 GHz,然后降低至x=0.25的24 000 GHz。谐振频率温度系数(0.05≤x0.25)值从–32×10–6/℃提高到–24×10–6/℃。     

(Mg1–xCax)2Al4Si5O18陶瓷的相演变与微波介电性能

采用固相烧结反应法制备(Mg1–x,Cax)2Al4Si5O18陶瓷。XRD测试结果表明:0≤x<0.2时,陶瓷以(Mg,Ca)2Al4Si5O18堇青石单一相固溶体形式存在;0.2≤x<0.8时,陶瓷以Mg2Al4Si5O18/CaAl2Si2O8两相复合形式存在;0.8≤x<1.0时,陶瓷以单一相(Ca,Mg)Al2Si2O8固溶体形式存在。SEM结果显示:Ca2+掺杂可以有效地降低堇青石陶瓷的气孔率与微裂纹,并能有效地控制Mg2Al4Si5O18/CaAl2Si2O8复相陶瓷的颗粒分布与晶粒尺寸。微波介电性能测试结果表明:0≤x≤0.4时,(Mg1–xCax)2Al4Si5O18陶瓷介电常数εr为7.0左右;0.6≤x≤1.0时,εr从7.0增加到8.6,然后又降低到6.9。随着x增加,品质因数Qf值从24100GHz降低到4400GHz。但是,在x=0.6时,由于[Si,AlO4]四面体中Al/Si原子排列的有序化,(Mg0.4,Ca0.6)2Al4Si5O18陶瓷Qf值(Qf=5500GHz)比两侧x值成分点Qf值有较大提高。(Mg1–x,Cax)2Al4Si5O18陶瓷谐振频率温度系数在整个x值范围内保持在–20×10–6～–35×10–6℃–1。     

In2W3O12陶瓷的相变特性及其负热膨胀性能（英文）

以分析纯In2O3和WO3为原料,采用固相反应法制备In2W3O12陶瓷。利用X射线衍射仪、场发射扫描电子显微镜、热重分析仪、差示扫描量热仪和热机械分析仪对样品的物相组成、微观结构、相变和热膨胀特性进行了表征。结果表明:在900℃烧结6h可制备出纯的单斜相In2W3O12陶瓷,In2W3O12陶瓷断面晶粒均匀,平均尺寸为4～6μm。In2W3O12陶瓷在253.34℃发生单斜相到斜方相的相转变,单斜相的In2W3O12陶瓷显示正热膨胀,在27～249℃,其平均热膨胀系数为16.51×10-6℃-1,斜方相的In2W3O12陶瓷显示负热膨胀,在273～700℃,其平均热膨胀系数为-3.00×10-6℃-1。     

用于固体氧化物燃料电池的Zn掺杂BaZr0.7Pr0.1Y0.2O3-δ质子导体电解质的制备与性能

采用柠檬酸–硝酸盐燃烧法制备了质子导体固体氧化物燃料电池(SOFC)电解质材料BaZr0.7Pr0.1Y0.2O3–δ(BZPY)和BaZr0.7Pr0.1Y0.16Zn0.04O3–δ(BZPYZn)。研究了Zn掺杂对材料烧结、热膨胀系数和电性能的影响;利用X射线衍射仪和扫描电子显微镜对样品物相和微观结构进行了表征。结果表明:BZPYZn经1 100℃煅烧5h后呈单一的钙钛矿结构。随烧结温度的升高(从1 300℃到1400℃),BZPYZn陶瓷体的晶粒尺寸增大,而孔隙率减小;1350℃保温5h烧结的BZPYZn陶瓷样品的相对密度达到97.3%;500～800℃范围内,离子电导率介于10–3～10–2S/cm之间。室温至1 000℃范围内,样品的热膨胀系数为9.2×10–6/K,表明其与电极材料(Ni)的热匹配性好。预示BZPYZn有望成为良好的质子传导型中温SOFC电解质材料。     

Ca3–xMgxYb2Ge3O12(0≤x≤3)石榴石的A位Rattling效应与微波介电性能

微波介质陶瓷是5G/6G通讯技术的关键基础材料，具有高品质因数(Q×f)、低介电常数(ε_r)以及近零谐振频率温度系数(τ_f)的材料已逐渐成为研究与开发的重点。通过固相反应法制备了系列Ca_3–xMg_xYb₂Ge₃O₁₂ (0≤x≤3)石榴石陶瓷。当0≤x≤2时，样品为正石榴石结构，相对介电常数ε_r逐渐从10.3增加至11.8，品质因数Q×f值逐渐从98 000 GHz降低到78 000 GHz，谐振频率温度系数τ_f在(-40～-56)×10^–6/℃之间波动。当22+进入A位，ε_r迅速增大(～13.5),Q×f值显著降低(～19 800 GHz)，τ_f值则从负急剧转变为正(+70.5×10^–6/℃)，可归之于A位Mg²⁺的Rattling效应以...     

Y1-xGdxBaCo4O7+δ的微结构和氧吸附性能（英文）

采用固相反应法制备了Y1-xGdxBaCo4O7+δ(x≤0.4)吸氧材料。利用X射线衍射(X-ray diffraction,XRD)和热重分析表征了样品的微结构和氧吸附性能。XRD结果表明:Gd掺杂量x≤0.2时,Y1-xGdxBaCo4O7+δ具有单相六方结构;x>0.2时,Y1-xGdxBaCo4O7+δ出现杂相。Rietveld精修XRD结果表明:Y1-xGdxBaCo4O7+δ(x≤0.2)样品的单胞参数和体积随Gd掺杂量增加而增大;Co—O键角变化不明显,Co—O键长变化较大,这使两种类型的CoO4四面体发生畸变。热重分析结果显示:从室温到1 000℃,所有样品经历两次氧吸附过程,Gd掺杂的YBaCo4O7+δ最大吸氧量低于母相YBaCo4O7+δ的吸氧量,与氧的激活能有关。     

Er2W3O12陶瓷的制备及其负热膨胀性能研究

以分析纯Er2O3和WO3为原料,采用固相法制备Er2W3O12陶瓷,并利用X射线衍射仪(XRD)、场发射扫描电镜(FESEM)和热重分析仪(TG)对其结构组分、断面形貌和吸湿特性进行表征.采用热膨胀仪和变温XRD对Er2W3O12陶瓷的负热膨胀特性进行表征.结果表明:在950 ℃烧结6 h制得的Er2W3O12陶瓷结构致密.Er2W3O12材料在室温下容易吸湿,在120 ℃完全失去吸湿水,表现为正交相的Er2W3O12陶瓷,具有良好的负热膨胀性能,其在138~700 ℃的平均热膨胀系数为-7.94×10-6 K-1.变温XRD分析发现:Er2W3O12陶瓷沿三个晶轴方向均表现为负热膨胀,在100~600 ℃温度区间内,Er2W3O12陶瓷的热膨胀系数为-7.81×10-6 K-1.     

白光发光二极管用Eu:(Y_(0.9)La_(0.1))_2O_3透明陶瓷的制备及性能

以Y2O3为原料、La2O3为烧结助剂,采用真空烧结法制备了(Y1-xLax)2O3透明陶瓷。研究了La2O3添加量对Y2O3陶瓷致密化行为的影响,确定La2O3的最佳添加量(摩尔分数)为10.0%。在此基础上制备了不同掺杂量(摩尔分数)的Eu:(Y0.9La0.1)2O3透明荧光陶瓷,研究了Eu3+掺杂浓度对陶瓷显微结构、光学性能及光谱特性的影响。结果表明:随着掺杂量的增加,Eu:(Y0.9La0.1)2O3陶瓷(1 765℃×50 h)的晶粒尺寸变化较小。其中,0.3%Eu:(Y0.9La0.1)2O3陶瓷的晶粒尺寸均匀(约为177.6μm),厚度为1 mm的陶瓷样品在800 nm处的直线透过率为62%。随着Eu3+掺杂浓度的增加,Eu:(Y0.9La0.1)2O3陶瓷的各个激发峰与发射峰强度变强。当激发波长为466 nm时,发射主峰位于红光波段611 nm处,属于Eu3+离子的5D0→7F2跃迁。研究表明Eu:(Y0.9La0.1)2O3透明陶瓷在白光发光二极管上具有潜在的应用价值。     

Y_2O_3掺杂对La_2Zr_2O_7陶瓷结构与热物理性能的影响

用Y2O3掺杂La2Zr2O7制备(La1–xYx)2Zr2O7(x=0,0.1,0.2,x为摩尔分数)陶瓷材料,利用X射线衍射仪、扫描电子显微镜、激光导热仪以及热膨胀仪分别对其物相结构、显微形貌、热导率及热膨胀性能进行表征。结果表明,(La1–xYx)2Zr2O7为立方烧绿石结构,显微结构致密,在室温至1 450℃范围内具有良好的高温相稳定性。La2Zr2O7掺杂小离子半径Y3+可提高其热膨胀系数(x=0.2),降低热扩散系数,并在高温下表现出类似于玻璃的超低热导率。1 000℃时,La1.6Y0.4Zr2O7的热导率为1.28 W/(m·K),平均热膨胀系数达到9.7×10–6/K。     

添加剂对NZP族低热膨胀陶瓷热学性质的影响

以NZP族低热膨胀陶瓷Ca1-xBaxZr4(PO4)6(0≤x≤1)系列中的零膨胀组成Ca0.85Ba0.15Zr4P6O24为例,着重研究了不同添加剂对该零膨胀陶瓷的热膨胀异向性、平均热膨胀系数和导热性能的影响规律。实验结果表明,在烧结过程中添加质量分数1%SiO2或3%SiC均能够降低Ca0.85Ba0.15Zr4P6O24的热膨胀异向性,但与此同时,第二相的加入使Ca0.85Ba0.15Zr4P6O24的热膨胀系数有所上升。质量分数为1%～7%SiC晶须的加入反而导致NZP族陶瓷导热性能进一步降低,原因是SiC抑制了晶粒生长。     

Synthesis of NaTi2(PO4)3 by the Inorganic–Organic Steric Entrapment Method and Its Thermal Expansion Behavior

Crystalline pure NaTi₂(PO₄)₃ (NTP) powder was synthesized at 700°C using a simple and low energy, hybrid inorganic–organic, steric entrapment method. Sodium nitrite (NaNO₂) and ammonium phosphate dibasic ((NH₄)₂HPO₄) dissolved in water, whereas titanium (IV) isopropoxide (Ti[OCH(CH₃)₂]₄) hydrolyzed in water. Ethylene glycol (HOCH₂CH₂OH) was used as a polymeric entrapper and hydrolysis of the Ti source was hindered by its dissolution in isopropyl alcohol. The resulting NTP powder was characterized by thermogravimetric analysis/differential thermal analysis, X‐ray diffractometry, scanning electron microscopy, specific surface area by Brunauer–Emmett–Teller nitrogen absorption, and particle size analysis. Furthermore, C, H, N were measured by the classical Pregl‐Dumas method. The thermal expansion behavior in all {hkl} pole directions was also determined by in situ high‐temperature X‐ray diffraction using synchrotron radiation and was found to be in agreement with other published studies.     

复合氧化物材料的负热膨胀机理

介绍了相转变、桥氧原子的横向热振动、刚性多面体的旋转耦合、固体内压转变、相界面弯曲、阳离子迁移等六种模式的负热膨胀机理。并对其应用前景和发展趋势进行了预测     

零膨胀单向混杂纤维复合材料的研究

本文推导了单向混杂复合材料热膨胀系数的理论估算公式,并进行了实验验证.研究了单向混杂复合材料热膨胀系数随混杂比、混杂界面数及铺层顺序等参数变化的规律.另外,也对部分零膨胀单向混杂复合材料的铺层结构进行了预测.研究结果对复合材料在航空航天上的应用有重要的意义.     

Anomalous thermal expansion behavior in Er1-xCaxMnO3

Perovskite Er_1-xCa_xMnO₃ (x = 0, 0.1, 0.2, 0.25, 0.3, 0.4, 0.5) was synthesized using a solid-state method. Thermal expansion behavior was tested using a thermal dilatometer and high-temperature X-ray diffraction (XRD). The experimental results indicated the doping contents of Ca (x) in the Er_1-xCa_xMnO₃ have a dramatic effect on their thermal expansion behavior. The samples of Er_1-xCa_xMnO₃ (x = 0.1,0.2 and 0.25) exhibit positive thermal expansion (PTE) characteristics while Er_0.7Ca_0.3MnO₃ (x = 0.3) exhibits a negative thermal expansion (NTE) property with a thermal expansion coefficient of −3.1 × 10⁻⁶ K⁻¹ in room temperature (RT) −750 K. In addition, Er_0.6Ca_0.4MnO₃ (x = 0.4) exhibits NTE properties only at RT–500 K, and Er_0.5Ca_0.5MnO₃ (x = 0.5) exhibits PTE properties at RT–750 K. The thermal shrinkage mechanism is the Jahn–Teller effect of the Mn³⁺ ions and the double exchange of Mn³⁺–O–Mn⁴⁺ in Er_0.7Ca_0.3MnO₃. This phenomenon causes Mn–O octahedral distortion and oxygen vacancy, causing Er_0.7Ca_0.3MnO₃ to become anisotropic. This feature results in the elastic deformation of Er_0.7Ca_0.3MnO₃ during heating, which consumes the void and displays NTE at macro level.     

Negative thermal expansion of (Al1/3Fe1/3Cr1/3)2(Mo1/2W1/2)3O12 (AFCMW) and low thermal expansion of AFCMW-(Co1/2Ni1/2)(Mo1/2W1/2)O4 with high entropy

A₂Mo₃O₁₂ (A-Al, Fe, Cr) have large negative thermal expansion (NTE) coefficients and structural stability but high phase-transition temperatures (PTTs). Herein, we prepared (Al_1/3Fe_1/3Cr_1/3)₂(Mo_1/2W_1/2)₃O₁₂ (AFCMW), and found it to have a low NTE coefficient and a low PTT. Furthermore, combination of AFCMW with (Co_1/2Ni_1/2)(Mo_1/2W_1/2)O₄ (CNMW) afforded an AFCMW–CNMW composite with a low thermal expansion (LTE). We determined that the PTT reductions in A₂Mo₃O₁₂ are largely due to the high-entropy effect resulting from the introduction of different ions into its A and M sites. Moreover, we found that the low LTE of the AFCMW–CNMW composite is attributable to the opposite thermal expansion behaviours of AFCMW and CNMW. We suggest that the suppressed thermal expansion during the phase transition process of the AFCMW–CNMW composite could be derived from the high-entropy effect resulting from its increased diversity of polyhedra, the influence of Co²⁺ and Ni²⁺ dopants, and CNMW-induced lattice distortion.     

Structural,optical, and thermodynamic properties of an LiCa2Mg2As3xV3−3xO12 solid-solution garnet

A series of LiCa₂Mg₂As_3xV_3−3xO₁₂ garnet powders (x = 0, 0.25, 0.50, 0.667, 0.75, and 1) were synthesized using solid-state reaction from mixed precursor powders. A complete solid-solution series was found between the endmembers. Energy-dispersive spectroscopy confirmed the homogeneity of the synthesized garnets. The compositions reversibly melted between 1000 and 1160°C and had low sintering temperatures between 650 and 900°C. Thermal diffusivity, heat capacity, thermal conductivity, density, lattice parameter, thermal expansion, index of refraction, and dispersion were measured from room temperature to 800°C.     

Negative thermal expansion properties of Cu1.5Mg0.5V2O7

Cu_1.5Mg_0.5V₂O₇ was prepared by a solid state method. Its phase, microstructure, thermal expansion property, and Raman spectra were analyzed in detail. Results show that Cu_1.5Mg_0.5V₂O₇ maintains a monoclinic crystal structure and exhibits an excellent linear negative thermal-expansion property with coefficient of thermal expansion of ?8.72?×?10^?6?K^?1 over a wide temperature range of 153–673?K. The mechanism underlying the negative thermal expansion of Cu_1.5Mg_0.5V₂O₇ involves the coupling effect of the tetrahedron caused by the lateral vibration of the bridge oxygen atom and the tensile effect of the tetrahedron, The partial collapse caused by the loss of the oxygen atoms also plays an important role in the mechanism.     

燃烧法合成高纯度负热膨胀材料ZrW2O8粉体

采用燃烧法在较低温度下成功合成了各向同性的负热膨胀材料ZrW2O8粉体.用X射线衍射、扫描电镜、红外光谱综合分析和研究了反应过程中炉温、硼酸和尿素含量、W6 与Zr4 的摩尔比对合成ZrW2O8纯度的影响.结果表明:燃烧法可以合成高纯度、粒径为0.5μm的ZrW2O8粉体.燃烧法合成高纯ZrW2O8的最佳条件是:炉温为500℃,硼酸的摩尔分数为10%,(NH2)2CO与(NH4)5H5[H2(WO4)6]·H2O ZrOCl2·8H2O的质量比为2∶1,(NH4)5H5[H2(WO4)6]·H2O与ZrOCl2·8H2O的摩尔比为1∶3.2.所合成的ZrW2O8在50～700℃之间的线膨胀系数a=-5.08×10-6/℃,其线膨胀系数与温度的关系符合方程dL/L0=-1.4×10-2-4.5×10-4T(50℃≤T≤700℃).     

具有潜在负热膨胀性和负压缩性的三角形构筑模块的有限元分析(英文)

研究了由3个粱焊接而成的三角形系统构成的二维单元的热膨胀和压缩特性,与每个梁相比,该三角形构件具有不同的性质(热膨胀和弹性 模量).结果表明:当三角形构件的底边热膨胀大于两侧边时,这种二角形系统可在一维方向上硅示负热膨胀(即当三角形梁以楔形结构形成时,会产 生三角形缩短效戍)和负压缩特性.更引起人们兴趣的足:线热膨胀特性与三角形构件的底边和侧边材料的相对刚性(弹性模量)有关.压力变化对这种 构件存在影响.与侧边梁刚性相比,构件的线性压缩率变化与底边梁刚性存在主要关系.