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[Abstract]:The study of the structure of Ga under extreme conditions is a long-term important base study. As an elementary element with a rich multi-form phase, Ga shows a rare physical characteristic in the form of a special bond in which the covalent bond and the metal bond coexist. The stable Ga-I phase is a special case of the rare excimer metal, and the high-voltage solid phase Ga-II and the Ga-III phase have the characteristics of the common metal. The other interesting point of this element is the study of the liquid structure of the system, Ga not only can form the subcooled liquid at normal pressure, and the liquid density is 3% higher than the stable Ga-I density, and the abnormal melting curve is shown. In addition, liquid phase change may be present in that liquid Ga, but there is still a great deal of dispute in the related study. Although a large number of experimental and theoretical studies have been conducted on liquid Ga, the understanding of its characteristics and structure is still very limited, for example, direct experimental measurements of the density under high pressure conditions have been challenging due to the lack of long-range order of the liquid Ga system, There is a need for further research. In this paper, we study the local structure, density and liquid-liquid phase change of the liquid Ga system under the condition of liquid Ga pressure, and the following results are obtained. (1) The relative volume change of liquid and solid Ga at different temperature was studied by using in-situ high-voltage synchrotron radiation X-ray 3D imaging technique in combination with energy dispersive X-ray diffraction. The P-V relation curve of liquid Ga is obtained directly by 3D imaging pattern data reconstruction, and the isothermal volume modulus of the liquid Ga is 23.6 (0.5) GPa and 24.6 (0.4) GPa, respectively, by using the equation of state to obtain the compression conditions of 300 K-3.02 GPa and 330 K-3.63 GPa, respectively. The liquid phase change of liquid Ga under the condition of 330 K-2.44 GPa was found through abnormal compression. (2) The local structure of liquid Ga under the pressure of 1.9 GPa is studied by in-situ high-energy X-ray scattering experiment, and the two-body distribution function of the system is simulated by using the measurement density as the basic input parameter. The pressure interval applied in the experiment covers the range of the Ga-I to Ga-II solid phase transition in the Ga system. Previous studies are based on the known crystal structure, and the local structure of the liquid Ga displayed in the region is composed of the local clusters of Ga-I and Ga-II, but the accuracy of such a fitting method has always been large. Our studies show a distinct result, that is, the local structure of liquid Ga is similar to that of the high-voltage crystalline phase Ga-II and Ga-III. The melting model of Ga is set up according to the free-volume theory, and it is pointed out that the atomic rearrangement of Ga-I phase quickly breaks the original structure in the melting of the system, and a sufficient free volume is obtained to form a liquid state. (3) The distribution function and the system density of the atomic distance of the liquid Ga are determined by the above experiments, and the fractal characteristics of the system are studied by the power law. the only non-integer power exponent d _ f can be used to characterize the fractal characteristics of the metal glass according to the power law, but for the same long-range disordered liquid ga system, The result of the power law shows that the system has a multiple power index and the power exponent values of the four adjacent ligands are greater than the Euclidean dimension 3. The results show that the power law is unable to determine the unique fractal dimension of the liquid Ga. In fact, the phenomenon that the nearest neighbor coordination number of the liquid Ga increases with the pressure leads to the absence of geometric self-similarity of the nearest neighbor coordination ball under different pressures, that is, the fractal dimension of the liquid Ga will change under the pressure. Based on the percolation model, the multi-exponential behavior of the system is limited to 11.65-11.38 with the pressure increase. Within the range of the associated length. The liquid Ga system which is out of this range presents a uniform state, and the fractal dimension D _ f = 3. (4) The structure of Ga 330 K under the condition of 3.7 GPa is studied by X-ray scattering, and the P-T range covers the liquid and solid state of the Ga system. Under the action of temperature and pressure, the liquid Ga is crystallized in the pressure region of 3.4-3.7 GPa, and the mixed twinning composed of Ga-II and Ga-III is presented. The crystallization phase and the phase diagram show a large deviation from the Ga-III phase, indicating that the temperature and pressure range is the metastable region. The results show that Ga melt, Ga-II and Ga-III have similar structural modules, resulting in the formation of Ga-II phase and Ga-III phase in the liquid Ga. At the same time, according to the classical nucleation theory, the metastable behavior of Ga is related to the nucleation probability of Ga-II and Ga-III. In addition, a rare 2.4-3.4 GPa liquid metastable zone was also found under the condition of 330 K. In the two experiments, different Ga-phases are observed under different temperature and pressure paths under the same temperature and pressure conditions, indicating that the metastable behavior of the liquid and solid state of the Ga system is closely related to the temperature and pressure path. In conclusion, for the first time, the density of liquid Ga under high pressure is directly measured by X-ray imaging experiment, and the liquid phase change of potential pressure is found at the temperature of 330 K. The high-voltage local structure of liquid Ga is studied. In this paper, a Ga melting model is established according to the free volume theory, and the relation of the multiple power index in the different scale range of the liquid Ga system is pointed out, and the solid state and the liquid metastable zone exist at the same time of the Ga at the temperature of 330 K. The research results of this paper further promote the study of the high-voltage structure and physical characteristics of Ga, and help to understand this particular element more deeply.
【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TG146.43

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