The Negative Thermal Expansion Property of NdMnO_(3) Based on Pores Effect and Phase Transition

A novel negative thermal expansion(NTE) material NdMnO_(3) was synthesized by solid-state method at 1 523 K. The crystal structure, phase transition, pores effect and negative expansion properties of NdMnO_(3) were investigated by variable temperature X-ray diffraction(XRD), scanning electron microscope(SEM) and variable temperature Raman spectra. The compound exhibits NTE properties in the orderly O' phase crystal structure. When the temperature is from 293 to 759 K, the ceramic NdMnO_(3) shows negative thermal expansion of-4.7×10^(-6)/K. As temperature increases, the ceramic NdMnO_(3) presents NTE property range from 759 to 1 007 K. The average linear expansion coefficient is-18.88×10^(-6)/K. The physical mechanism of NTE is discussed and clarified through experiments.

Statics, vibration, and buckling of sandwich plates with metamaterial cores characterized by negative thermal expansion and negative Poisson's ratio

This paper proposes a three-dimensional(3D)Maltese cross metamaterial with negative Poisson’s ratio(NPR)and negative thermal expansion(NTE)adopted as the core layers in sandwich plates,and aims to explore the relations between the mechanical responses of sandwich composites and the NPR or NTE of the metamaterial.First,the NPR and NTE of the metamaterial are derived analytically based on energy conservation.The effective elastic modulus and mass density of the 3D metamaterial are obtained and validated by the finite element method(FEM).Subsequently,the general governing equation of the 3D sandwich plate under thermal environments is established based on Hamilton’s principle with the consideration of the von Kármán nonlinearity.The differential quadrature(DQ)FEM(DQFEM)is utilized to obtain the numerical solutions.It is shown that NPR and NTE can enhance the global stiffness of sandwich structures.The geometric parameters of the Maltese cross metamaterial significantly affect the responses of the thermal stress,natural frequency,and critical buckling load.

Crystal structure and negative thermal expansion of solid solution Lu_2W_(3-x)Mo_xO_(12)

A new series of solid solutions Lu2W3-xMoxO12 （0.5≤r≤2.5） were successfully synthesized by the solid-state method. Their crystal structure and negative thermal expansion properties were studied using high-temperature X-ray powder diffraction and the Rietveld method. All samples of rare-earth ttmgstates and molybdates are found to crystallize in the same orthorhombic structure with space group Pnca and show the negative thermal expansion phenomena related to transverse vibration of bridging oxygen atoms in the structure. Thermal expansion coefficients （TEC） of Lu2W3_xMoxO12 are determined as -20.0× 10^-6 K^-1 for x=0.5 and -16.1×10^-6 K^-1 for x=2.5 but -18.6× 10^-6 and -16.9× 10^-6K^-1 for unsubstituted Lu2W3012 and Lu2M03012 in the identical temperature range of 200 to 800℃. High-temperature X-ray diffraction （XRD） data and bond length analysis suggest that the difference between W-O and Mo-O bond is responsible for the change of TECs after the element substitution in this series of solid solutions.

Negative thermal expansion of Ca2RuO4 with oxygen vacancies

Oxygen vacancies have a profound effect on the magnetic,electronic,and transport properties of transition metal oxides but little is known about their effect on thermal expansion.Herein we report the effect of oxygen defects on the structure formation and thermal expansion properties of the layered perovskite Ca2RuO4(CRO).It is shown that the CRO containing excess oxygen crystallizes in a metallic L-CRO phase without structure transition from 100 K to 500 K and displays a normal thermal expansion behavior,whereas those with oxygen vacancies adopt at room temperature an insulating S-CRO phase and exhibit an enormous negative thermal expansion(NTE)from 100 K to about 360 K,from where they undergo a structure transition to a high temperature metallic L-CRO phase.Compared to the L-CRO containing excess oxygen,the S-CRO structure has increasingly large orthorhombic strain and distinctive in-plane distortion upon cooling.The in-plane distortion of the RuO6 octahedra reaches a maximum across 260 K and then relaxes monotonically,providing a structure evidence for the appearance of an antiferromagnetic orbital ordering in the paramagnetic phase and the A_g phonon mode suppression and phase flip across the same temperature found recently.Both the L-and S-CRO display an antiferromagnetic ordering at about 150-110 K,with ferromagnetic ordering components at lower temperature.The NTE in S-CRO is a result of a complex interplay among the spin,orbital,and lattice.

Characterization of the negative thermal expansion material Zr_(1-x)Hf_xW_2O_8

The oxide ZrW_2O_8 displays unusual property of isotropic negative thermalexpansion in a large wide temperature range, which makes it have a number of important potentialapplications. The cubic Zr_(1-x)Hf_xW_2O_8 (x velence 0,0.3, 0.5, 0.7, and 1.0) were synthesized bystandard solid state reaction technique. The high and low temperature X-ray diffraction analysisindicate that the substitution of the Hf^(4+) for Zr^(4+) only leads to reducing the latticeconstants, and the changes of negative thermal expansion coefficients are not obvious. The linearexpansion coefficients of Zr_(1-x)Hf_xW_2O_8 (x velence 0,0.3, 0.5, 0.7, and 1.0) are about -6 X 10^(-6) K^(-1) in the temperature range of 298 to 973 K, while that of Zr_(0.5)Hf_(0.5)W_2O_8 is -9.6X 10^(-6) K_(-1) from 83 to 298 K. The phase transition temperatures from alpha-ZrW_2O_8 tobeta-ZrW_2O_8 structure were also determined by X-ray diffraction method. Thermogravimetric analysis(TGA) exhibits that Zr_(1-x)Hf_xW_2O_8 is not hygroscopic in air.

Semi-empirical estimation for enhancing negative thermal expansion in PbTiO_(3)-based perovskites

Generally,most materials expand when heated and contract when cooled,whereas negative thermal expansion(NTE)materials are very rare.As a typical NTE material,PbTiO_(3) and related compounds have drawn particular interest in recent years.The discovery of an enhanced NTE system in PbTiO_(3) is beneficial to deepen our understanding of its mechanism and regulate its properties.At present,the method of discriminating an enhanced NTE material based on PbTiO_(3) is not universal.Here,we propose a semi-empirical method through evaluating the average lattice distortion in related systems to estimate the relative coefficient of thermal expansion conveniently.The rationality of the method was verified by the analysis of the 0.6PbTiO_(3)-0.4Bi(Ga_(x)Fe_(1-x))O_(3) system.So far,all PbTiO_(3)-based compounds with enhanced NTE conform well to this method.This method provides the possibility to find more enhanced NTE PbTiO_(3)-based materials.

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）0.83W2.25P0.83O12-δ is synthesized by the high-temperature, solid-state reaction and fast-quenching 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.

Phase Transition and Negative Thermal Expansion Property of ZrMnMo_3O_(12)

A novel material of ZrMnMo3012 with negative thermal expansion is presented. The phase transition temperature and coemcient of thermal expansion （CTE） are investigated by temperature-dependent x-ray diffraction and Raman spectra. It is shown that ZrMnMo3012 adopts monoclinic structure with space group P21/a （No. 14） from 298 to 358K and transforms to orthorhombic with space group Pnma （No. 62） above 363K. The linear CTE obtained from the results of XRD refinement is -2.80 × 10-6 K-1 from 363 to 873 K. The CTE of the bulk cylinder ceramic measured by a thermal dilatometer is -4.7× 10-6 K-1 from 373 to 773K approximatively.

Tailoring of thermal expansion and phase transition temperature of ZrW_(2)O_8 with phosphorus and enhancement of negative thermal expansion of ZrW_(1.5)P_(0.5)O_(7.75)

ZrW_(2)O_(8)is a typical isotropic negative thermal expansion material with cubic structure.However,quenching preparation,pressure phase transition and metastable structure influence its practical applications.Adopting P to part-substitute W for ZrW_(2-x)P_(x)O_(8-0.5x)has decreased the sintering temperature and avoided the quenching process.When x=0.1,ZrW_(1.9)P_(0.1)O_(7.95)with a stable cubic structure can be obtained at 1150℃.The thermal expansion coefficient is tailored with the P content,and phase transition temperature is lowered.When x=0.5,thermal expansion coefficient attains-13.6×10^(-6)℃^(-1),ZrW_(1.5)P_(0.5)O_(7.75)exhibits enhance negative thermal expansion property.The difference of electronegativity leads to the decrease of phase transition temperature with the increase of P content.The different radii of ions lead to new structure of materials when P substitutes more.The results suggest that the P atom plays the stabilization role in the crystal structure of ZrW_(2-x)P_(x)O_(8-0.5x).

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 NbF_(3)and NbOF_(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 NbOF_(2),thus weakening the transverse vibration of F and O in NbOF_(2),compared with the case of NbF_(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.

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 cubicstructure 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.

Negative thermal expansion and phase transition of low-temperature Mg_(2)NiH_(4)

The negative thermal expansion(NTE) phenomenon is of great significance in fabricating zero thermal expansion(ZTE) materials to avoid thermal shock during heating and cooling. NTE is observed in limited groups of materials, e.g., metal cyanides, oxometallates, and metalorganic frameworks, but has not been reported in the family of metal hydrides. Herein, a colossal and continuous negative thermal expansion is firstly developed in the low-temperature phases of LT1-and LT2-Mg_(2)NiH_(4) between 488 K and 733 K from in-situ transmission electron microscope(TEM) video, with the volume contraction reaching 18.7% and 11.3%, respectively. The mechanisms for volume contraction of LT1 and LT2 phases are elucidated from the viewpoints of phase transformation, magnetic transition, and dehydrogenation, which is different from common NTE materials containing flexible polyhedra units in the structure. The linear volume shrinkage of LT2 in the temperature of 488-553 K corresponds to the phase transition of LT2→HT with a thermal expansion coefficient of -799.7 × 10^(-6) K^(-1) revealed by in-situ synchrotron powder X-ray diffraction. The sudden volume contraction in LT1 between 488 and 493 K may be caused by the rapid dehydrogenation of LT1 to Mg_(2)Ni. The revealed phenomenon in single composite material with different structures would be significant for preparing zero thermal expansion materials by tuning the fraction of LT1 and LT2 phases.

Simple chemical synthesis and isotropic negative thermal expansion in MHfF_(6)(M=Ca,Mn,Fe,and Co)

The rapid progress of modern technologies has accelerated the prominence of thermal expansion mismatch between materials,and tunable thermal expansion materials will be a powerful safeguard against this challenge.Here,isotropic MHfF_(6)(M=Ca,Mn,Fe,and Co)compounds with tunable thermal expansion have been produced via a low-cost synthetic method and investigated.By utilizing temperature dependent X-ray diffraction(XRD)and Raman spectroscopy,combined with first principles calculations,it was revealed that the transverse thermal vibrations of the F atoms are dominated by low-frequency phonons with negative Grüneisen parameters and are therefore the origin of the negative thermal expansion(NTE).Very interestingly,with the increase of the M atomic number,the metal…F atomic linkages become stiffer,reducing the number of vibrational modes with negative Grüneisen parameters,so that the strong NTE can be gradually adjusted to moderate NTE and to near zero thermal expansion.The present study achieves the tunable thermal expansion in a new compound family and shed light on the internal mechanism from the perspective of lattice vibrational dynamics.

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.

Preparation of Negative Thermal Expansion ZrW_2O_8 Powders and Its Application in Polyimide/ZrW_2O_8 Composites

Negative thermal expansion （NTE） ZrW2O8 powders were prepared by step-by-step solid-state reaction with ZrO2 and WO3 powders. The coefficient of thermal expansion （CTE） of the as-prepared ZrW208 was around -5.08×10^-6 K^-1 at 20-700℃. Different amounts of ZrW208 powders were added in BTDA-ODA polyamic acid to form polyimide/ZrW2O8 composites （PI/ZrW2O8）. With the increment of ZrW2O8, experimental results show that ZrW2O8 powders can significantly enhance the thermal stability of the composites, and reduce the thermal expansion. A 50 wt pct ZrW2O8 addition can give rise to a 31% reduction of CTE. It is suggested that the PI/ZrW2O8 composites have potential applications in high performance microelectronic devices.

Effect of Microstructure Scale on Negative Thermal Expansion of Antiperovskite Manganese Nitride

The negative thermal expansion （NTE） properties of the antiperovskite manganese nitrides with micron-scale, submicron-scale and nanometer-scale microstructures, respectively, were investigated using the Mn3Cu0.5Ge0.5N composition as an example. It was discovered that the NTE start temperature, NTE operation temperature range and coefficient of NTE change obviously in a wide range with decreasing the grain size level of the microstructure. The mechanisms for the broadening of the NTE operation temperature range and the decrease in the absolute value of NTE coefficient were proposed based on the grain-size-dependence of the frustrated magnetic interactions and magnetic ordering. The present study indicates that the NTE properties of the antiperovskite manganese nitrides can be tailored by the control of the microstructure scale.

The enhanced negative thermal expansion in less-oxygen-vacancies copper pyrophosphate

For oxides,controlling the concentration of oxygen vacancy is a useful way to optimize their functional properties.However,when it comes to the field of negative thermal expansion(NTE),much less attention has been paid to the effect of oxygen vacancy on NTE,though oxide-typed NTE materials account for more than 40%of the total NTE materials.Here,we report that the linear coefficient of thermal expansion at 250–350 K of copper pyrophosphate(i.e.,Cu_(2)P_(2)O_(7))can be significantly improved from–13.88 to–36.60 ppm/K when the synthesis temperature is raised from 1073 to 1373 K.The combined study including X-ray absorption near edge structure,neutron powder diffraction,and X-ray diffraction has confirmed the selective vacancies in the O1 site for low-temperature synthesized samples,which suppress both the phase-transition and framework-structure driven NTE simultaneously.Our result proposes a new approach for optimizing the NTE effect of oxides.

o-ZrW_(1.6)Mo_(0.4)O_8:A Novel Orthorhombic Intermediate Phase Formed During the Synthesis of the Negative Thermal Expansion Cubic ZrW_(1.6)Mo_(0.4)O_8 Material by the Precursor Dehydration Route

The mechanism of the precursor dehydration route was revealed for the synthesis of NTE c-ZrW_ 1.6 Mo_ 0.4 O_8. The hydrate precursor was dehydrated at 473 K and transformed to a NTE cubic compound above 800 K. A novel intermediate phase o-ZrW_ 1.6 Mo_ 0.4 O_8 occurs between the temperature range of 573—800 K. The XRD pattern of novel intermediate was refined with the structural model of LT-ZrMo_2O_8 by using Rietveld method. The residuals are R_ wp =7.80% and R_p=5.79%. The space group is Pmn2_1 and the lattice parameters are a=0.5917(4) nm, b=0.7273(4) nm, c=0.9148(6) nm, and Z=2.

A new isotropic negative thermal expansion material of CaSnF_(6)with facile and low-cost synthesis

Double ReO_(3)-type fluorides have a great interest in the field of negative thermal expansion(NTE)and luminescent materials.However,their application is limited by the scarcity of quantity,expensive raw materials,and harsh preparation conditions.In this work we have found a new NTE material,CaSnF_(6),by applying the concept of the average atomic volume.More importantly,different from the previous solid-phase sintering and direct fluorination methods,the nano CaSnF6 has been synthesized for the first time by solvothermal method.The results of X-ray diffraction(XRD)and Raman spectroscopy show that a phase transition occurs from rhombohedral(R3)to cubic(Fm3m)structure at about 200 K,and a strong isotropic NTE(αv=−15.78×10^(−6)K^(−1))appears in the cubic phase.Lattice dynamics calculations from first-principles illustrate that the NTE is due to the transverse vibration of fluorine atoms excited by low-frequency phonons.This work not only broadens the NTE family of fluorides,but also provides a new facile and low-cost fabricati on method for the preparation of NTE fluorides.

Large anisotropic negative thermal expansion in Cu-TDPAT metalorganic framework:A combined in situ X-ray diffraction and DRIFTS study

Cu-TDPAT(H_(6)TDPAT=2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine),a stable nanoporous metal-organic framework with rht topology,has sparked broad interest as an adsorbent for several chemical separation processes.In this work,in situ synchrotron diffraction experiments followed by sequential LeBail refinements reveal that Cu-TDPAT shows unusually large anisotropic negative thermal expansion(NTE).The PASCal crystallography tool,used to analyze the magnitude of the NTE,reveals an average volumetric thermal expansion coefficientαv=-20.3 MK^(-1).This value is significantly higher than the one reported for Cu-BTC(also known as HKUST-1),which contains the same Cu-paddlewheel building unit,αv=-12 MK^(-1).In situ synchrotron single crystal X-ray diffraction and in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)were employed to shed light on the NTE mechanism.Using these two methods,we were able to elucidate the three main structural motions that are responsible for the NTE effect.The more pronounced NTE behavior of Cu-TDPAT is attributed to the lower symmetry combined with the more complex ligand structure when compared to Cu-BTC.The knowledge obtained in this work is important for understanding the behavior of the adsorbent under transient variable temperature conditions in fixed adsorption beds.