Negative thermal expansion: Mechanisms and materials

Negative thermal expansion (NTE) of materials is an intriguing phenomenon challenging the concept of traditional lattice dynamics and of importance for a variety of applications. Progresses in this field develop markedly and update continuously our knowledge on the NTE behavior of materials. In this article, we review the most recent understandings on the underlying mechanisms (anharmonic phonon vibration, magnetovolume effect, ferroelectrorestriction and charge transfer) of thermal shrinkage and the development of NTE materials under each mechanism from both the theoretical and experimental aspects. Besides the low frequency optical phonons which are usually accepted as the origins of NTE in framework structures, NTE driven by acoustic phonons and the interplay between anisotropic elasticity and phonons are stressed. Based on the data documented, some problems affecting applications of NTE materials are discussed and strategies for discovering and design novel framework structured NET materials are also presented.     

热收缩化合物——负热膨胀性及成因

文章综述了负热膨胀化合物、负热膨胀机理与应用等方面的进展.负热膨胀是最近十多年来新兴的研究领域,目前已经发现较多化合物具有负热膨胀性能,它们广泛分布在类似ZrW2O8开放式框架结构化合物、磁性合金、反钙钛矿结构的Mn3AX、PbTiO3基铁电化合物、纳米颗粒等领域.在负热膨胀机理研究方面,原子热振动机理研究相对充分,成功地解释了一部分框架式结构化合物负热膨胀机理;然而,较多负热膨胀起源与非振动机理相关,如：物质磁性、铁电性、电子作用、纳米尺寸效应等.文章最后从实际应用角度出发对未来负热膨胀材料研究进行了展望.     

Negative thermal expansion in NbF_3 and NbOF_2:A comparative theoretical study

Thermal expansion control is always an obstructive factor and challenging in high precision engineering field. Here,the negative thermal expansion of Nb F_3 and Nb OF_2 was predicted by first-principles calculation with density functional theory and the quasi-harmonic approximation(QHA). We studied the total charge density, thermal vibration, and lattice dynamic to investigate the thermal expansion mechanism. We found that the presence of O induced the relatively strong covalent bond in Nb OF_2, thus weakening the transverse vibration of F and O in Nb OF_2, compared with the case of Nb F_3.In this study, we proposed a way to tailor negative thermal expansion of metal fluorides by introducing the oxygen atoms.The present work not only predicts two NTE compounds, but also provides an insight on thermal expansion control by designing chemical bond type.     

Inelastic neutron scattering study of lattice dynamics in α-ZnCl<Subscript>2</Subscript>

Inelastic neutron scattering experiments have been carried out to measure the phonon density of states in polycrystalline α-ZnCl₂ at Dhruva, Trombay. Lattice dynamical calculations, based on an interatomic potential model, are accomplished to study phonons associated with this otherwise extremely hygroscopic compound. Our calculated data are found to be well-compatible with the available measured ones.     

Zero thermal expansion in metal-organic framework with imidazole dicarboxylate ligands

Exploring new abnormal thermal expansion materials is important to understand the nature of thermal expansion. Metal-organic framework (MOF) with unique structure flexibility is an ideal material to study the thermal expansion. This work adopts the high-resolution variable-temperature powder x-ray diffraction to investigate the structure and intrinsic thermal expansion in Sr-MOF ([Sr(DMPhH₂IDC)₂]_n). It has the unique honeycomb structure with one-dimensional (1D) channels along the c-axis direction, the a-b plane displays layer structure. The thermal expansion behavior has strong relationship with the structure, ZTE appears in the a-b plane and large PTE along the c-axis direction. The possible mechanism is that the a/b layers have enough space for the transverse thermal vibration of polydentate ligands, while along the c-axis direction is not. This work not only reports one interesting zero thermal expansion material, but also provides new understanding for thermal expansion mechanism from the perspective of the structural model.     

Lattice dynamics of strontium tungstate

We report here measurements of the phonon density of states and the lattice dynamics calculations of strontium tungstate (SrWO₄). At ambient conditions this compound crystallizes to a body-centred tetragonal unit cell (space group I4₁/a) called scheelite structure. We have developed transferable interatomic potentials to study the lattice dynamics of this class of compounds. The model parameters have been fitted with respect to the experimentally available Raman and infra-red frequencies and the equilibrium unit cell parameters. Inelastic neutron scattering measurements have been carried out in the triple-axis spectrometer at Dhruva reactor. The measured phonon density of states is in good agreement with the theoretical calculations, thus validating the interatomic potential developed.      

Sc2－xGaxW3O12体系负热膨胀性能研究

通过固相反应法,在1100 ℃下成功制备出了系列Ga掺杂Sc_2-xGa_xW₃O₁₂（x=0, 0.05, 0.1, 0.2, 0.3, 0.5, 0.8）固溶体.X射线粉末衍射结构精修表明,Ga以替代Sc的形式成功进入Sc_2-xGa_xW₃O₁₂晶格,但不能获得端元组分Ga₂W₃关键词： 负热膨胀 热膨胀系数 Rietveld结构精修     

Inelastic neutron scattering and lattice dynamics of GaPO<Subscript>4</Subscript>

We report here measurements of phonon spectrum and lattice dynamical calculations for GaPO₄. The measurements in low-cristobalite phase of GaPO₄ are carried out using high-resolution medium-energy chopper spectrometer at ANL, USA in the energy transfer range 0–160 meV. Semiempirical interatomic potential in GaPO₄, previously determined using ab-initio calculations have been widely used in studying the phase transitions among various polymorphs. The calculated phonon spectrum using the available potential show fair agreement with the experimental data. However, the agreement between the two is improved by including the polarisability of the oxygen atoms in the framework of the shell model. The lattice dynamical models are also exploited for calculations of various thermodynamic properties of GaPO₄.     

Ho2AlFe14Mn2化合物的负热膨胀性质

利用x射线衍射及磁测量手段研究了Ho2AlFe16-xMnx系列化合物的结构.结果表明，该系列化合物具有Th2Ni17型结构；随着x的增加，化合物的单胞体积呈现非线性的变化，结合磁测量结果分析认为，在化合物的磁相变点附近存在较大的正的本征磁致伸缩.在160—285K温度范围内对Ho2AlFe14Mn2化合物进行的变温x射线衍射研究表明，该化合物在其居里点附近(220—270K)具有负热膨胀性质，其平均热膨胀系数为-14×10-4/K. 关键词： Ho2AlFe16-xMnx化合物 负热膨胀 本征磁致伸缩     

Negative thermal expansion and photoluminescence in solid solution(HfSc)_(0.83)W_(2.25)P_(0.83)O_(12-δ)

A solid solution of(HfSc)_(0.83)W_(2.25)P_(0.83)O_(12-δ)is synthesized by the high-temperature, solid-state reaction and fastquenching method. It is shown that it possesses an orthorhombic structure with space group Pmmm(47) and exhibits negative thermal expansion(NTE) property with low anisotropy in thermal expansion. The coefficients of thermal expansion(CTEs) for a, b, and c axes are-1.41 × 10~(-6) K~(-1),-2.23 × 10~(-6) K-1, and-1.87 × 10~(-6) K-1, respectively. This gives rise to volume and linear CTEs of-3.10 × 10-6 K-1 and-1.03 × 10-6 K-1, respectively. Besides, it exhibits also intense photoluminescence from 360 nm to about 600 nm. The mechanism of NTE and the correlation of the PL with axial thermal expansion property are discussed.     

Phonon density of states of tetracyanoethylene from coherent inelastic neutron scattering at Dhruva reactor

Inelastic neutron scattering experiments to determine phonon density of states of coherent scattering samples of polycrystalline complex solids are generally intensity-limited and therefore are feasible only at high flux facilities. Phonon density of states of the monoclinic phase of tetracyanoethylene at 300 K, obtained using the medium resolution triple axis spectrometer at the new Indian medium flux reactor Dhruva are reported here. The raw data is converted to the “neutron weighted” phonon density of states by applying suitable corrections. Comparison made with results from a theoretical calculation based on a semirigid molecule model of lattice dynamics is fair. Results from Dhruva are also consistent with that obtained (to be published) at the high flux pulsed neutron source (ISIS) of the Rutherford Appleton Laboratory in United Kingdom.     

具有负膨胀性能的磁性材料

文章综述了国内外近些年来在各种磁性材料研究中发现的具有显著异常热膨胀行为的磁性化合物,其中包括反钙钛矿结构类型的Mn3AX,Th2Zn17结构类型的R2Fe17-xMxCy和钙钛矿结构类型的R1-xAxMnO3等系列。运用磁学理论,定性分析了负膨胀产生机理,并从实际应用角度对今后此类材料的进一步研究提出了展望     

具有负膨胀性能的磁性材料

文章综述了国内外近些年来在各种磁性材料研究中发现的具有显著异常热膨胀行为的磁性化合物,其中包括反钙钛矿结构类型的Mn3AX,Th2Zn17结构类型的R2Fe17-xMxCy和钙钛矿结构类型的R1-xAxMnO3等系列。运用磁学理论,定性分析了负膨胀产生机理,并从实际应用角度对今后此类材料的进一步研究提出了展望     

Fe2-xYxMo3O12系列材料的相变及负膨胀性研究

本文对Fe2-xYx(MoO4)3(x=0.0,0.2,0.4,0.5,0.6,0.8,1.0,1.2,1.4,1.6,1.8,2.0)系列材料的相变及负膨胀性能进行了研究.通过对Fe2-xYx( MoO4)3系列材料的XRD和拉曼谱的分析发现,当x≤0.4时Fe2-xYxMo3O12在常温下是单斜结构;当x≥0.5时...     

Zero and controllable thermal expansion in HfMgMo_(3-x)W_xO_(12)

HfMgMo_(3-x)W_xO_(12) with x = 0.5, 1.0, 1.5, 2.0, and 2.5 are developed with a simple solid state method. With increasing the content of W, solid solutions of Hf Mg Mo3-xWx O12 crystallize in an orthorhombic structure for x≤2.0 and a monoclinic structure for x2.0. A near-zero thermal expansion(ZTE) is realized for HfMgMo_(2.5)W_(0.5)O_(12) and negative coefficients of thermal expansion(NCTE) are achieved for other compositions with different values. The ZTE and variation of NCTE are attributed to the difference in electronegativity between W and Mo and incorporation of a different amount of W, which cause variable distortion of the octahedra and softening of the MoO_4 tetrahedra, and hence an enhanced NCTE in the a- and c-axis and reduced CTE in the b-axis as revealed by Raman spectroscopy and x-ray diffraction.     

Effects of Al particles and thin layer on thermal expansion and conductivity of Al-Y_2Mo_3O_(12) cermets

Low thermal expansion composites are difficult to obtain by using Al with larger positive thermal expansion coefficient(TEC) and the materials with smaller negative TECs. In this investigation, Y_2Mo_3O_(12) with larger negative TEC is used to combine with Al to obtain a low thermal expansion composite with high conductivity. The TEC of Al is reduced by 19%for a ratio Al:Y_2Mo_3O_(12) of 0.3118. When the mass ratio of Al:Y_2Mo_3O_(12) increases to 2.0000, the conductivity of the composite increases so much that a transformation from capacitance to pure resistance appears. The results suggest that Y_2Mo_3O_(12) plays a dominant role in the composite for low content of Al(presenting isolate particles), while the content of Al increases enough to contact each other, the composite presents mainly the property of Al. For the effect of high content Al, it is considered that Al is squeezed out of the cermets during the uniaxial pressure process to form a thin layer on the surface.     

ZrV2-xPxO7固溶体的相变与热膨胀性质的研究

本文采用固相烧结法制备了ZrV2-xPxO7@=0,0．2,0．4,0．6,0．8,1）系列材料．粉末X射线衍射（XRD）分析表明,所制备材料的结构为单一立方相．应用变温拉曼光谱研究该材料相变,变温拉曼光谱研究结果表明,材料起始相变温度随着P5＋替代V5＋量的增加逐渐降低,x=0,0．4,0．8,1对应的相变温度分别为383K,363K,273K,213K．热膨胀测试结果表明：随着P替代量的增加正一负膨胀转变温度先降低后增加,x=0,0．2,0．4,0．6,0．8,1对应的正一负膨胀转变温度分别为429K,403K,372K,390K,398K和435K．本文指出了该系列材料存在两个相变过程,为设计和制备ZrV2O7基室温附近的负热膨胀材料奠定了良好的基础．     

Phonon dispersion in aluminium arsenide and antimonide

The phonon dispersion curves for aluminium arsenide and antimonide have been investigated by using a deformation bond approximation model. The results obtained from this model are compared with the experimental values wherever it is available. Since there is no complete experimental phonon dispersion curves for AlAs, we could not compare our calculated results, but the results of AlSb have been compared with the inelastic neutron scattering measurements at 15 K. However, we compare the phonon frequencies of AlAs and AlSb at critical points of the Brillouin zone obtained by our calculations and Raman spectroscopy measurements. This model predicts the phonon modes satisfactorily in all the symmetry directions of the Brillouin zone (BZ). The spectrum has similar features as observed in other III–V compound semiconductors.     

Crystal electric field excitations in ferromagnetic CeTX compounds

A ferromagnetic ground state was identified for the compounds CeCuGe (T_C=10 K), CeCuSi (T_C=15 K) [F. Yang, et al., J. Appl. Phys. 69 (1991) 4705] and CeAuGe (T_C=10 K) [R. Pottgen, J. Magn. Magn. Mater. 152 (1996) 196]. The observed saturation magnetic moment values at low temperatures for all three compounds are considerably less than the theoretically expected value g_JJ=2.14μ_B for the free Ce³⁺ ion involving the entire six-fold J=5/2 multiplet, and thus provide a first indication of partial lifting of the f-electron level degeneracy in these compounds. Specific heat data yield crystal electric field (CEF) excitation energies (Δ_Sch) equivalent to 140 K for CeCuGe, 110 K for CeCuSi and 280 K for CeAuGe. To confirm the presence of CEF excitations directly, we have carried out inelastic neutron scattering (INS) measurements on all three compounds, using the HET spectrometer at ISIS Facility. Here, we present a detailed analysis of the INS spectra of CeCuSi on the basis of a CEF model and the detailed analysis of the INS of the other two compounds will be reported elsewhere.     

Isotropic negative thermal expansion and its mechanism in tetracyanidoborate salt CuB(CN)4

The control of thermal expansion is essential in applications where thermal stability is required from fiber optics coatings, high performance fuel cell cathodes to tooth fillings. Negative thermal expansion (NTE) materials, although rare, are fundamental for this purpose. This work focuses on studying tetracyanidoborate salt CuB(CN)₄, an interesting cubic-structure material that displays large isotropic NTE. A joint study of synchrotron x-ray diffraction, temperature-dependent Raman spectroscopy, and lattice dynamics calculations was conducted, showing that not only low-frequency optical modes (transverse thermal vibrations of N and C atoms) but also the acoustic modes (the vibrations of Cu atoms as a collective torsion of the neighboring atoms), contribute to NTE. As a result, new insights were gained into the NTE mechanism of CuB(CN)₄ and related framework materials.