共沉淀法制备负热膨胀性ZrW_2O_8粉体及其粒径控制初探

随着材料科学的不断发展,对材料性能的要求也越来越苛刻,其中最普遍的问题就是热膨胀,研究开发低热膨胀材料和零膨胀材料可以大大提高材料的性能,扩展材料的应用范围。为适应各个领域对热膨胀材料的特殊要求,负热膨胀(Negative thermalexpansion,简称NTE)材料成为材料研究领域一个新的分支。其实负热膨胀现象早就被发现存在于某些材料中,如:钙钛矿铁电体PbTiO3、半导体材料Si、冰、石英、堇青石2MgO·2Al2O·35SiO2和沸石等[1],但是这些材料的负热膨胀温度范围比较窄,且为各向异性,因此在实际运用中存在许多困难。直至1995年,美国俄勒…     

普鲁士蓝类化合物负热膨胀及机理

负热膨胀化合物可调控材料的热膨胀系数, 在复合材料、 精密仪器等方面具有重要的应用前景, 成为近年来化学、 物理和材料工程领域的研究热点之一. 因其晶体结构主要由—M—CN—M—含有双原子氰根(CN)链组成, 许多普鲁士蓝类化合物呈现反常的热膨胀性质. 本文综述了普鲁士蓝类负热膨胀化合物结构、 热膨胀机制与系数调控等方面的研究进展. 以氰根配体数量为分类主线, 将具有反常热膨胀性的氰根配体化合物分为氰化物、 六氰基和八氰基普鲁士蓝类化合物等进行介绍, 从局域结构和平均结构角度分析了N和C原子的横向振动对负热膨胀贡献的角度解释了机理, 从客体离子或分子嵌入的方法分析了热膨胀调控原理, 并对新型普鲁士蓝类负热膨胀化合物的设计及应用进行了展望.     

两种金属-有机钙钛矿材料的负热膨胀性质

通过变温单晶X射线衍射和透射电镜实验对2种金属-有机钙钛矿材料[C(NH2)3][Mn(HCOO)3](1)和[(CH2)3NH2][Mn(HCOO)3](2)进行表征,分析了其晶体结构和晶格常数随温度变化的关系,发现2种材料沿c轴方向都表现出负的热膨胀行为,其效应分别为:αc1=-1.2(1)×10~(-5)K~(-1),αc2=-6.1(11)×10~(-5)K~(-1)。采用一种"铰链"结构模型对这2种框架材料的负热膨胀机理进行了详细解释:温度升高会诱导框架中主体和客体铵基之间的氢键长度及键角发生改变,引起钙钛矿框架结构发生变形,进而导致其沿框架对角线方向(c轴方向)的负热膨胀行为。     

第一性原理计算钛酸铅A位掺杂对其负热膨胀性的影响

近年来,实验发现钛酸铅基材料具有负热膨胀性,且其热膨胀程度会受到掺杂元素的影响. 目前所研究的A位掺杂体系中,仅Cd原子掺杂能使钛酸铅负热膨胀性增强. 所以研究A位掺杂钛酸铅,比较Cd原子与其他原子在掺杂钛酸铅时化学键的异同,有助于深刻理解钛酸铅负热膨胀的本质. 本文利用第一性原理,分别优化了Sr、Ba、Cd掺杂钛酸铅的晶格常数,计算了它们的态密度和电荷密度. 结果表明Cd―O键的共价性强于Pb―O键,而Ba―O键和Sr―O键几乎呈离子性,Ba/Sr对Pb的替代削弱了化合物的共价性,降低了自发极化强度. 与实验测量的热膨胀系数对比可以发现,A位原子与氧原子之间的共价性增强,化合物负热膨胀程度升高;若A位原子与氧原子之间的共价性削弱,负热膨胀程度降低. 可见A位原子与氧原子之间的共价性影响了钛酸铅基化合物负热膨胀性.     

第一性原理计算钛酸铅A位掺杂对其负热膨胀性的影响

近年来,实验发现钛酸铅基材料具有负热膨胀性,且其热膨胀程度会受到掺杂元素的影响.目前所研究的A位掺杂体系中,仅Cd原子掺杂能使钛酸铅负热膨胀性增强.所以研究A位掺杂钛酸铅,比较Cd原子与其他原子在掺杂钛酸铅时化学键的异同,有助于深刻理解钛酸铅负热膨胀的本质.本文利用第一性原理,分别优化了Sr、Ba、Cd掺杂钛酸铅的晶格常数,计算了它们的态密度和电荷密度.结果表明Cd―O键的共价性强于Pb―O键,而Ba―O键和Sr―O键几乎呈离子性,Ba/Sr对Pb的替代削弱了化合物的共价性,降低了自发极化强度.与实验测量的热膨胀系数对比可以发现,A位原子与氧原子之间的共价性增强,化合物负热膨胀程度升高;若A位原子与氧原子之间的共价性削弱,负热膨胀程度降低.可见A位原子与氧原子之间的共价性影响了钛酸铅基化合物负热膨胀性.     

壳聚糖基层状硅酸盐纳米复合材料

壳聚糖基层状硅酸盐纳米复合材料是采用简单的溶液插层法,将壳聚糖及其衍生物插层进入层状硅酸盐的纳米层间而获得的有机无机纳米杂化材料。该材料偶合了壳聚糖及其衍生物和层状硅酸盐的协同优势,为壳聚糖的研发应用开辟了新方向和新途径。本文在对壳聚糖和层状硅酸盐的特性及应用进行简单介绍的基础上,重点综述了壳聚糖基层状硅酸盐纳米复合材料的制备方法、插层机理及应用现状,并提出了目前存在的主要问题。     

无机材料在骨质文物加固保护中的应用

传统上,合成高分子树脂是骨质文物加固保护中常用的材料,但长期的应用实践表明此类材料存在耐候性不良、与骨质文物兼容性差等问题。近年来,耐候性优良且与骨质文物兼容性好的无机保护材料的研究逐渐兴起,也引起了越来越多文物保护工作者的关注。本文就骨质文物无机加固保护材料及其作用机理和应用研究现状进行了系统的介绍与评述。     

顶杆法热膨胀仪在材料研究中的应用

利用顶杆法膨胀仪,探讨了材料结构、密度与热膨胀的关系,用其它实验方法交叉结合对材料的相变进行了研究,并通过热膨胀曲线确定某些材料的特定工艺参数,实验证实了热膨胀在材料热学性能研究领域中是一种非常简捷、可靠、实用的工具之一     

LiTi2O4用作锂离子电池负极的研究进展

LiTi2O4具有长的嵌锂反应循环寿命、较低的电位和良好的导电性,是继碳素材料和Li4Ti5O12之后的又一新型锂离子电池负极材料,有望在大电流和动力锂离子电池中得到较大的应用.本文介绍了LiTi2O4负极材料的晶体结构、物理特性、制备方法、电化学性能及其应用研究进展,并分析了其微观导电机理.     

碳材料修饰铋系光催化剂及其应用

可见光半导体光催化剂具有高效利用太阳能从而解决能源及环境问题的优势,引起光催化及其他领域人们的关注.铋系光催化剂多属于窄带隙半导体材料,能够吸收太阳光谱中的大量可见光.此外,铋系光催化剂独特的层状晶体结构及较深的价带位置决定了其具有较高的催化活性,成为近年来半导体光催化领域研究的热点.碳基质材料由于具有比表面积大、热和化学稳定性高以及导电能力强等物理化学性质而被人们广泛研究.将碳材料与铋系半导体进行复合,两者之间的协同效应能够增强对反应物的吸附量,拓宽对太阳光的吸收范围,加速电子/空穴对的分离,从而提高催化活性.此外,碳材料修饰的铋光催化剂更易被分离及回收利用,可有效降低应用成本,具有潜在的应用前景.本文对近年来利用碳基质材料修饰铋系光催化剂的类型、制备方法、结构与性能、作用机理及其应用研究进行了综述,提出了目前利用碳材料修饰铋系光催化剂在材料设计、机理研究及应用等方面存在的主要问题,并对其未来发展方向进行了展望.     

(Fe1-xNix)ZrF6固溶体晶体结构与可调控的热膨胀性质

绝大部分物质具有热胀冷缩的基本性质,然而近年来的研究发现一些化合物具有反常的负热膨胀性质,其为有效调节物质热膨胀系数(CTE)提供了可行性,尤其调控各向同性化合物热膨胀性质是一个重要的研究方向。本文以双ReO₃结构的固溶体(Fe_1-xNi_x)ZrF₆为研究对象,对(Fe_1-xNi_x)ZrF₆固溶体的制备、晶体结构以及热膨胀调控开展了深入研究。(Fe_1-xNi_x)ZrF₆固溶体呈现全程固溶特性,通过Ni²⁺对Fe²⁺进行化学替代的方法实现了(Fe_1-xNi_x)ZrF₆热膨胀系数在大范围内的有效调控(−3.24×10⁻⁶– +18.23 × 10⁻⁶ K⁻¹,300–675 K),尤其,在(Fe_0.5Ni_0.5)ZrF₆化合物中得到了零膨胀性能。作为一种典型的框架结构化合物,晶胞中F原子横向热振动的差异是导致各自不同热膨胀差异的本质原因。该研究给我们提供了一个基于开放式框架结构化合物的热膨胀调控方法。     

Dilatometric studies of Y2W3O12 with added Al2O3

Y₂W₃O₁₂ exhibits negative thermal expansion along the three crystallographic directions due to the transverse thermal vibrations perpendicular to the Y-O-W linkage. It is highly hygroscopic and forms a trihydrate structure at room temperature. Dilatometric studies of Y₂W₃O₁₂ show large thermal expansion hysteresis due to large grain size and a large initial positive thermal expansion due to the removal of water molecules. Al₂O₃ has been added to Y₂W₃O₁₂ upto 10 wt% in an attempt to overcome the hygroscopicity and reduce the particle size and thereby the thermal expansion hysteresis. Thermo gravimetric, dilatometric and electron microscopic studies are presented to support these observations. Dedicated to Professor C N R Rao on his 70th birthday     

Interpenetration as a Mechanism for Negative Thermal Expansion in the Metal–Organic Framework Cu3(btb)2 (MOF‐14)

Metal–organic framework materials (MOFs) have recently been shown in some cases to exhibit strong negative thermal expansion (NTE) behavior, while framework interpenetration has been found to reduce NTE in many materials. Using powder and single‐crystal diffraction methods we investigate the thermal expansion behavior of interpenetrated Cu₃(btb)₂ (MOF‐14) and find that it exhibits an anomalously large NTE effect. Temperature‐dependent structural analysis shows that, contrary to other interpenetrated materials, in MOF‐14 the large positive thermal expansion of weak interactions that hold the interpenetrating networks together results in a low‐energy contractive distortion of the overall framework structure, demonstrating a new mechanism for NTE.     

Switching Between Giant Positive and Negative Thermal Expansions of a YFe(CN)6-based Prussian Blue Analogue Induced by Guest Species

The control of thermal expansion of solid compounds is intriguing but remains challenging. The effect of guests on the thermal expansion of open-framework structures was investigated. Notably, the presence of guest ions (K⁺) and molecules (H₂O) can substantially switch thermal expansion of YFe(CN)₆ from negative (α_v=−33.67×10⁻⁶ K⁻¹) to positive (α_v=+42.72×10⁻⁶ K⁻¹)—a range that covers the thermal expansion of most inorganic compounds. The mechanism of such substantial thermal expansion switching is revealed by joint studies with synchrotron X-ray diffraction, X-ray absorption fine structure, neutron powder diffraction, and density functional theory calculations. The presence of guest ions or molecules plays a critical damping effect on transverse vibrations, thus inhibiting negative thermal expansion. An effective method is demonstrated to control the thermal expansion in open-framework materials by adjusting the presence of guests.     

Three-phase cyanate ester composites with fumed silica and negative-CTE reinforcements

Three-phase cyanate ester adhesives have been developed using a bisphenol E cyanate ester resin, fumed silica, and negative-CTE (coefficient of thermal expansion) reinforcements: short carbon fiber or zirconium tungstate (ZrW₂O ₈ ). Fumed silica was used to impart thixotropic behavior on the resin and decrease settling in the adhesives. The cured composites were evaluated using various thermal analysis techniques for their thermal-mechanical properties. Composites with short carbon fiber showed enhanced modulus and decreased thermal expansion (70% reduction for 20 vol%) and showed little phase separation. While settling of the dense ceramic particles could not be completely eliminated for the zirconium tungstate composites through rheological modification of the adhesive with added fumed silica, a reduction in CTE of 84% was achieved in the composite (58 vol%) compared to the neat resin. In addition, the effect of thermal history on the cure and temperature induced ZrW₂O₈ phase transitions, and their corresponding influence on thermal strains vs. temperature, are examined by thermomechanical analysis.     

Determination of thermal expansion coefficient of a monofilament polyamide fiber using digital image correlation

Coiled polymer actuators are a type of artificial muscles that are a promising development in the field of smart materials. The coefficient of thermal expansion of monofilament polyamide fibers is a crucial parameter for understanding the actuation of coiled fibers. The main purpose of this work is to develop a new methodology for estimating the coefficient of thermal expansion and the transition temperature of monofilament polymer fibers. In the experimental procedure, axial deformations of monofilament polyamide fiber samples were induced by temperature variations using a controlled thermal system. These deformations were determined from images of polyamide samples using the digital image correlation method. Two different approaches based on distinct temperature conditions were conducted. An alternative model with three parameters, including the coefficient of thermal expansion, was introduced to describe the thermal-mechanical behavior of monofilament polyamide fibers. Moreover, polyamide samples were also characterized using four conventional methodologies. Results indicated that the coefficient of thermal expansion changed of a modest negative value to a large negative value and this transition occurred around the glass transition temperature of the polyamide. The thermal expansion curves demonstrate good repeatability and all estimated parameters were in accordance with literature, indicating that the proposed approach can be suitable for the proposed study. This investigation may help in understanding of the intrinsic thermal-mechanical behavior of polymeric monofilaments employed as actuators.     

Heat capacity calorimetry

Experimental heat capacity measurements of α-ZrW₂O₈, and zeolitic polymorphs of SiO₂, BEA and MFI, have been made from 0.6 to 400 K. Measurements on β-ZrMo₂O₈ have been made from 8 to 400 K. Analysis of the results yields evidence for very low frequency modes in all four materials. These modes are responsible for negative thermal expansion behavior in α-ZrW₂O₈ and β-ZrMo₂O₈. Negative thermal expansion has been observed in some pure SiO₂ zeolites, but no studies have been made to look for it in BEA and MFI. The appearance of low frequency modes in these two zeolites suggests that temperature dependent structural investigations would be worthwhile. These modes are lower in energy than the Boson peak in vitreous silica. This revised version was published online in August 2006 with corrections to the Cover Date.     

Elastically Flexible Crystals have Disparate Mechanisms of Molecular Movement Induced by Strain and Heat

Elastically flexible crystals form an emerging class of materials that exhibit a range of notable properties. The mechanism of thermal expansion in flexible crystals of bis(acetylacetonato)copper(II) is compared with the mechanism of molecular motion induced by bending and it is demonstrated that the two mechanisms are distinct. Upon bending, individual molecules within the crystal structure reversibly rotate, while thermal expansion results predominantly in an increase in intermolecular separations with only minor changes to molecular orientation through rotation.     

The role of rigid unit modes in negative thermal expansion

The rigid unit mode (RUM) model provides a valuable computational method to investigate correlations of transverse thermal motions of atoms important in negative thermal expansion (NTE) materials. We report here detailed RUM calculations of ten framework oxide structures that have been studied for their negative (or ultra low) thermal expansion properties. The results negate any simple and direct correlation between presence or absence of RUMs in a structure and its NTE property. All the structures considered can be viewed as networks of polyhedral connected by corners only. All evidence supports the importance the transverse motion of the atoms at the corners, but NTE does not correlate well with the presence RUMs for the polyhedra.