The phase transition, hygroscopicity, and thermal expansion properties of Yb_(2-x)Al_xMo_3O_(12)

Materials with the formula Yb2-xAlxMo3O12 （x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.7, 0.9, 1.0, 1.1, 1.3, 1.5, and 1.8） were synthesized and their structures, phase transitions, and hygroscopicity investigated using X-ray powder diffraction, Raman spectroscopy, and thermal analysis. It is shown that Yb2-xAlxMo3012 solid solutions crystallize in a single monoclinic phase for 1.7 〈 x 〈 2.0 and in a single orthorhombic phase for 0.0 〈 x 〈 0,4, and exhibit the characteristics of both monoclinic and orthorhombic structures outside these compositional ranges. The monoclinic to orthorhonlbic phase transition temperature of A12Mo3012 can be reduced by partial substitution of A13＋ by Yb3＋, and the Yb2-zAlxMo3012 （0.0 〈 x 〈 2.0） materials are hydrated at room temperature and contain two kinds of water species. One of these interacts strongly with and hinders the motions of the polyhedra, while the other does not. The partial substitution of A13＋ for Yb3＋ in Yb2Mo3012 decreases its hygroscopicity, and the linear thermal expansion coefficients after complete removal of water species are measured to be -9.1 x 10-6/K, -5.5 x 10-6/K, 5.74 x 10-6/K, and 9.5 x 10 6/K for Ybl.sAlo.2（MoO4）3, Yb1.6Alo.4（MoO4）3, Ybo.4All.6（Mo04）3, and Ybo.2Al1.8（MoO4）3, respectively.

Near-zero thermal expansion inβ-CuZnV_(2)O_(7)in a large temperature range

We report a new type of near-zero thermal expansion materialβ-CuZnV_(2)O_(7)in a large temperature range from 173 K to 673 K.It belongs to a monoclinic structure(C2/c space group)in the whole temperature range.No structural phase transition is observed at atmospheric pressure based on the x-ray diffraction and Raman experiment.The high-pressure Raman experiment demonstrates that two structural phase transitions exist at 0.94 GPa and 6.53 GPa,respectively.The mechanism of negative thermal expansion inβ-CuZnV_(2)O_(7)is interpreted by the variations of the angles between atoms intuitively and the phonon anharmonicity intrinsically resorting to the negative Grüneisen parameter.

Phase transition and thermal expansion property of Cr_(2-x)Zr_(0.5x)Mg_(0.5x)Mo_3O_(12) solid solution

Compounds with the formula Cr2-xZr0.5xMg0.5xMo3O12（x = 0.0, 0.3, 0.5, 0.9, 1.3, 1.5, 1.7, 1.9） are synthesized, and the effects of Zr4＋ and Mg2＋ co-incorporation on the phase transition, thermal expansion, and Raman mode are investigated. It is found that Cr2-xZr0.5xMg0.5xMo3O12 crystallize into monoclinic structures for x 〈 1.3 and orthorhombic structures for x _〉 1.5 at room temperature. The phase transition temperature from a monoclinic to an orthorhombic structure of Cr2Mo3O12 can be reduced by the partial substitution of （ZrMg）6＋ for Cr3＋. The overall linear thermal expansion coefficient decreases with the increase of the （ZrMg）6＋ content in an orthorhombic structure sample. The co-incorporation of Zr4＋ and Mg2＋ in the lattice results in the occurrence of new Raman modes and the hardening of the symmetric vibrational modes, which are attributed to the MoO4 tetrahedra sharing comers with ZrO6/MgO6 octahedra and to the strengthening of Mo-O bonds due to less electronegativities of Zr4＋ and Mg2＋ than Cr3＋, respectively.

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.

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.