RESUMEN
Negative thermal expansion (NTE) alloys possess great practical merit as thermal offsets for positive thermal expansion due to its metallic properties. However, achieving a large NTE with a wide temperature range remains a great challenge. Herein, a metallic framework-like material FeZr2 is found to exhibit a giant uniaxial (1D) NTE with a wide temperature range (93-1078 K, [Formula: see text]). Such uniaxial NTE is the strongest in all metal-based NTE materials. The direct experimental evidence and DFT calculations reveal that the origin of giant NTE is the couple with phonons, flexible framework-like structure, and soft bonds. Interestingly, the present metallic FeZr2 excites giant 1D NTE mainly driven by high-frequency optical branches. It is unlike the NTE in traditional framework materials, which are generally dominated by low energy acoustic branches. In the present study, a giant uniaxial NTE alloy is reported, and the complex mechanism has been revealed. It is of great significance for understanding the nature of thermal expansion and guiding the regulation of thermal expansion.
RESUMEN
Understanding the role of guest molecules in the lattice void of open-framework structures is vital for tailoring thermal expansion. Here, we take a new negative thermal expansion (NTE) compound, TiCo(CN)6, as a case study from the local structure perspective to investigate the effect of H2O molecules on thermal expansion. The in situ synchrotron X-ray diffraction results showed that the as-prepared TiCo(CN)6·2H2O has near-zero thermal expansion behavior (100-300 K), while TiCo(CN)6 without water in the lattice void exhibits a linear NTE (αl = -4.05 × 10-6 K-1, 100-475 K). Combined with the results of extended X-ray absorption fine structure, it was found that the intercalation of H2O molecules has the clear effect of inhibiting transverse thermal vibrations of Ti-N bonds, while the effect on the Co-C bonds is negligible. The present work displays the inhibition mechanism of H2O molecules on thermal expansion of TiCo(CN)6, which also provides insight into the thermal expansion control of other NTE compounds with open-framework structures.
RESUMEN
Negative or zero thermal expansion (NTE or ZTE) of materials is intriguing for controllable thermal expansion. We report a series of orthorhombic α-Cu2-xZnxV2O7 (x = 0, 0.1, 0.2), in which the volumetric coefficients of thermal expansion are successfully tuned from -10.19 × 10-6 K-1 to -1.58 × 10-6 K-1 in the temperature range of 100-475 K by increasing the content of Zn2+. It has been revealed that the transverse vibrations of oxygen bonded with vanadium are dominant in the contraction of the bc plane, leading to the overall volume NTE in α-Cu2V2O7. The introduction of Zn2+ densifies the crystal structure, which is presumed to suppress the space of transverse vibrations and results in the ZTE in α-Cu1.8Zn0.2V2O7. This work presents an effective method to realize ZTE in anisotropic framework systems.
