不同淬火工艺制备ZrW2O8及其负热膨胀性能研究

以分析纯ZrO2和WO3粉体为原料,采用分步固相法制备出ZrW2O8粉体,冷压成型并在1200℃下烧结4 h后炉冷、空气冷、水冷和液氮淬冷处理.采用X射线衍射仪(XRD)、扫描电镜(SEM)和热膨胀仪对合成样品的晶体结构、断面形貌和热膨胀性能进行表征.试验结果表明:随着冷却速度的增加,ZrW2O8分解为ZrO2和WO3的比例降低,随炉冷却制备的ZrW2O8完全分解为ZrO2和WO3;空冷制备的ZrW2O8.部分分解为ZrO2和WO3;在水和液氮中淬火得到纯ZrW2O8.在室温到600℃的测试区间内,采用空冷、水和液氮淬冷制备的ZrW2O8.的负热膨胀系数分别为-3.96×10-5K-1、-4.49×10-6 K-1和-5.95×10-6 K-1.     

水热法制备负热膨胀性ZrW2O8粉体

用水热法并经570 ℃热处理6 h制备了ZrW2O8粉体,对水热法制备的前驱体进行了热重-差热分析.用X射线粉末衍射、扫描电子显微镜对ZrW2O8粉体的微观结构及形貌进行表征,结果表明:ZrW2O8粉体为单一α-ZrW2O8相,粉体颗粒为规则的长方体棒状,尺寸约为1.2μm×1.2μm×10μm.原位X射线粉末衍射分析表明:所得ZrW2O8粉体具有很好的负热膨胀特性,从室温到500 ℃,其热膨胀系数为-6.30×10-6 ℃-1;在150～175 ℃温度范围内发生了α-ZrW2O8向β-ZrW2O8相的转变.     

pH值对Bi2WO6粉体的微波水热法合成及光催化性能的影响

以Na2WO4·2H2O和Bi(NO3)3·5H2O为原料,采用微波水热法通过调节pH值在200℃合成出花簇状和片状Bi2WO6粉体.利用X射线衍射、场发射扫描电子显微镜、透射电子显微镜、选区电子衍射和高分辨透射电子显微镜等对Bi2WO6粉体进行了表征,并对合成粉体的光催化性能进行了研究.结果表明:pH值对Bi2WO6...     

负热膨胀填料钨酸锆

江苏大学材料学院以二氧化锆（ZrO2）和三氧化钨（WO3）为原料，采用化学固相分步法制备了钨酸锆（ZrW2O8）粉体。具体工艺过程为：将球磨好的ZrO2和WO3混合物30g（按Zr^4＋和W^6＋的量比为1：2），在600℃、800℃和900℃下分别保温4h、8h、12h，之后在硅钼炉中1200℃烧结4h，立即取出淬火，得到浅灰绿色的ZrW2O8。最后用球磨机细化，平均粒径达0．6μm，线膨胀系数约-5．02×10^-6／K。以所制得的负热膨胀系数钨酸锆和二氧化硅（SiO2）分别与E-51环氧树脂、     

铜包覆钨酸锆复合粉体的制备

用分步固相法合成高纯钨酸锆(ZrW2O8).通过X射线衍射(X-ray diffraction,XRD)仪检测物相结构.用扫描电子显微镜(scanning electron microscope,SEM)观察ZrW2O8颗粒形貌.经过粗化和一步敏化、活化工艺,用化学镀法在超声波辐照下对微米级ZrW2O8颗粒进行包覆.用XRD判断包覆粉体的成分组成.用SEM观察ZrW2O8颗粒镀覆结果.用差示扫描量热仪(thermogravimetry-differential scanning calorimetry,TG-DSC)对复合粉体进行了TG-DSC分析.结果表明:在超声波并在合适的镀液组成和工艺条件下实现了铜(Cu)均匀包覆ZrW2O8,在镀液中加入亚铁氰化钾[K4Fe(CN)6·3H2O]和2,2′-联吡啶(C10H8N2)双稳定剂可以有效消除或减少复合粉体中的氧化亚铜(Cu2O).     

滴定工艺对3Y-ZrO_2粉体制备的影响

本文以ZrOCl2·8H2O为锆源,Y2O3为稳定剂,NH3·H2O为沉淀剂,PEG1000为分散剂,通过共沉淀法在800℃制备出四方相含量为96%、粒径为50～70nm、分散性好的3Y-ZrO2粉体.利用XRD、SEM及TEM等测试手段研究了滴定工艺对3Y-ZrO2合成效果及粉体形貌的影响.     

Ca4（1＋x）／5Mg（1＋x）／5Zr4Si2xP（6—2x）O24磷酸盐陶瓷材料的制备及力学性能

以化学纯CaCO3、4MgCO3·Mg（OH）2·5H2O、ZrO2、SiO2和（NH4）H2PO。微粉为原料,采用高温固相反应法合成了Ca4（1＋x）／5Mg（1＋x）／5Zr4Si2xP（6-2x）O24（CMZP）粉体,其中x=0、0．1、0．2、0．3。XRD测试结果表明在400℃下保温2h、1150℃下保温4h,能够合成单相的CMZP粉体,粉体千压成形后经冷等静压处理,在1350℃保温8h能烧结得到相对密度为97．5％的陶瓷试样,其平均抗弯强度为50MPa。     

均相法制备SnO_2-ZrO_2/ZST陶瓷及其Q值的研究

以ZrOCl2·8H2O和SnO2为原料,用均相共沉淀法制备纳米ZrO2包裹SnO2粉体(SnO2-ZrO2),再以SnO2-ZrO2粉体、SnO2、TiO2和ZrO2为原料,用固相法制备(Zr0.8Sn0.2)TiO4(ZST)陶瓷。TEM观察证明:SnO2-ZrO2粉体是纳米ZrO2包覆微米SnO2粉体。用该粉体制备的ZST陶瓷研究表明:SnO2-ZrO2粉体能降低ZST陶瓷烧结温度和改善介电性能。XRD和SEM分析表明,ZST陶瓷的主晶相是单相(Zr0.8Sn0.2)TiO4;用SnO2-ZrO2(Sn4+/Zr4+摩尔比为13.07∶1)取代SnO2的陶瓷显微结构呈现出发育良好的晶粒,分布均匀,气孔少。在烧结温度为1270℃时,得到了Q值为4390(10 GHz),εr为36.8,τf为-3.1×10-6/℃的微波介质陶瓷。     

Al2TiO5／ZrO2纳米复相陶瓷的制备及性能研究

以氧氯化锆((ZrOCl2·8H2O)、硫酸铝(Al2(SO4)3·18H2O)、硫酸氧钛(TiOSO4·2H2O)为初始原料,以氨水为沉淀剂,将液相共沉淀法得到的Al2TiO5/ZrO2纳米复合粉体前驱体,经1000℃焙烧2h,制备了ZrO2含量(w)为2%、5%、8%的Al2TiO5/ZrO2纳米复合粉体;复合粉体经造粒后以100Mpa压力成型试样,试样尺寸为53mm×10mm×10mm,经1350、1400、1450、1500℃2h制备了Al2TiO5/ZrO2(缩写AT/Z)纳米复相陶瓷试样。研究了ZrO2含量、烧结温度对试样的烧结性能、热膨胀性能、抗热震性能的影响,并借助XRD、SEM分析了试样的物相组成、显微结构。结果表明:随着ZrO2含量的增加和烧结温度的提高,试样的显气孔率减小,抗弯强度增大。烧结温度为1500℃、ZrO2含量(w)为5%的ATZ-54试样,抗弯强度最大,为103.2MPa;在1250℃的热膨胀率仅为0.08%,其热膨胀系数α约为0.65×10-6℃-1;AT/Z纳米复相陶瓷试样具有细晶镶嵌结构;从室温到1100℃急冷急热冲击31次后,试样表面仍保持完整,抗热震性能明显高于其他...     

微波法制备磷酸锆的研究

采用氧氯化锆为锆源、氟化铵为络合剂、磷酸为磷源,在低温（〈100℃）和常压条件下,微波辅助加热法在较短时间内制备得到规则的六角形片状结构Zr（HPO4）2·H2O（简写为α-ZrP）晶体。研究了不同反应物浓度下NH4F与ZrOCl2·8H2O摩尔比、磷酸与ZrOCl2·8H2 O摩尔比、反应时间、反应温度等因素对于合成磷酸锆晶体的影响。产物采用XRD、 SEM和FT-IR表征。以罗丹明B为降解对象,可见光下研究所制备磷酸锆的光催化性能。结果表明,当[ Zr^4＋]=0.02 mol/L, NH4 F/Zr=6和P/Zr=40,微波加热温度90℃,反应时间为30 min时制备的磷酸锆具有良好的光催化活性。     

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。     

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     

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.     

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.     

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.     

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 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.     

钛酸铝陶瓷及其研究进展

钛酸铝陶瓷以其独特的低膨胀和耐高温性能而倍受青睐,但其较低的强度及一定温度范围内的不稳定性制约了该材料的实际应用.本文简要阐述了钛酸铝的微观结构特征,并从添加剂的选择、材料合成工艺、材料烧结工艺等方面,系统介绍了前人在该领域所做的研究工作.最后在总结前人工作的基础上,对钛酸铝陶瓷研究的发展方向作了合理的预测和展望.     

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.     

热膨胀图法减少插板式烘炉热变形的几点措施

分析了涂装烘炉及相关部件热膨胀在工程实践中的处理过程,对不同构件的热变形,进行了分类和整理。提出了用绘制热膨胀分配图的方法来分析和解决炉体及炉内构件的热变形问题的思想,给出并详细阐述了4项具体措施。经工程实例验证,该方法取得了良好的效果,对于其他类型烘炉热变形问题的分析与解决,也有一定的借鉴作用。