Experimental Investigation of the Glass Transition Temperature in Amorphous Selenium under High Pressures
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摘要: 针对熔体急冷法制备的非晶硒样品，开展了压力对非晶硒玻璃化转变温度和过冷液相区影响的实验研究。在活塞圆筒高压模具上开展差热分析，测得了0.1～1700 MPa压力范围内非晶硒的玻璃化转变温度
$ {T}_{\text{g}} $ 和晶化温度${T}_{x}$ ，拟合出玻璃化转变中点温度$ {T}_{1/2,\text{g}} $ 与外推起始晶化温度Tel,x随压力p的变化关系：${T}_{1/2,\text{g}}\left(p\right)=$ $322+0.046\,2p$ ，${T}_{\mathrm{e}\mathrm{l},x}\left(p\right)=398+0.030\,2p$ ，其中，$ {T}_{1/2,\text{g}} $ 和Tel,x的单位均为K，p的单位为MPa。$ {T}_{1/2,\text{g}} $ 和Tel,x均随压力的增加而升高。由于Tel,x(p)的斜率小于$ {T}_{1/2,\text{g}} $ (p)的斜率，导致过冷液相区的温度范围随着压力的增加而变窄。在六面顶压机上开展差热分析，测得了2000～4500 MPa压力范围内非晶硒的晶化温度。结合活塞圆筒实验结果，发现了非晶硒的晶化温度随压力的变化规律：在0.1～1700 MPa范围内，晶化温度随压力的增加而升高；在2000 MPa以上，晶化温度的上升速率随压力的增加明显降低。当压力引起非晶硒的微观结构变化时，Tg(p)与Tx(p)曲线的斜率变化发生在相近的压力下，结合实验结果—Tx(p)的斜率变化出现在2 GPa左右，因此，推测Tg(p)的斜率变化可能出现在2 GPa左右。大腔体高压装置实验获得的转变点压力与以往报道的金刚石压砧实验结果不一致，可能与这两类实验中玻璃化转变温度、晶化温度的测量方法不同及压力测量误差有关。Abstract: The effect of pressure on the glass transition temperature and the supercooled liquid region of amorphous selenium (a-Se), which was prepared through melting quenching, was investigated. The glass transition temperature$ {T}_{\text{g}} $ and crystallization temperature Tx were determined through the differential thermal analysis (DTA) during isobaric heating. The experimental results from piston-cylinder apparatus showed that both$ {T}_{\text{g}} $ and Tx increase with the increasing pressure in the pressure range of 0.1－1700 MPa. The glass transition middle temperatures$ {T}_{1/2,\text{g}} $ and extrapolated crystallization onset temperatures Tel,x were linearly fitted to pressure. The fitting results are${T}_{1/2,\text{g}}\left(p\right)=322+0.046\,2p$ and${T}_{\mathrm{e}\mathrm{l},x}\left(p\right)=398+0.030\,2p$ , where the unit of temperature is K, and the unit of pressure is MPa. The smaller slope of Tel,x(p), compared with that of$ {T}_{1/2,\text{g}} $ (p), induces the temperature range (Tel,x−$ {T}_{1/2,\text{g}} $ ) in the supercooled liquid region to be narrower with the increase of pressure. DTA data in the pressure range of 2000−4500 MPa was performed by using a cubic press. A slope change in Tx(p) curve is found. Tx increases with the increasing pressure within 0.1−1700 MPa, and the rate slows down when the pressure is above 2000 MPa. In the previous diamond anvil reports, a similar pressure dependence of Tx and Tg was observed, i.e., Tx and Tg both increase initially with the increasing pressure, and then become nearly constant above 1000 MPa. Since the slope changes in Tg(p) and Tx(p) curves occur nearly at the same pressure when the microstructure of a-Se changes, in view of the pressure of 2000 MPa corresponding to the inflection point of Tx(p) curve obtained in this study, it is speculated that the pressure of the inflection point of Tg(p) curve may be around 2000 MPa. The different pressures corresponding to the slope change obtained by the diamond anvil cell and the large-volume press may be related to the measurement method of Tg and Tx, as well as the pressure measurement error.-
Key words:
- glass transition /
- amorphous selenium /
- high pressure /
- differential thermal analysis
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图 1 活塞圆筒装置内样品的差热分析实验布局图（左）和装置实物（右）
Figure 1. Layout of differential thermal analysis of samples (left) and piston-cylinder device (right)
图 3 常压下a-Se在升温速率为13 K/min情况下的DSC和DTA曲线（内插图为初始样品的XRD谱）
Figure 3. DSC and DTA curves of a-Se with heating rate of 13 K/min under ambient pressure (Inset figure is the XRD pattern of the initial a-Se sample.)
图 4 有限元模拟方法的计算模型(a)和等效应力云图(b)
Figure 4. Calculation model used in finite element simulation (a) and equivalent stress nephogram (b)
图 5 活塞圆筒装置上测得的非晶硒在不同压力下(a)玻璃化转变过程中的DTA曲线和(b)晶化过程中的DTA曲线（内插图给出了T1/2,g, Tel,x 和 Tp,x的选取方法示意图）
Figure 5. Typical DTA curves of a-Se during glass transition process (a) and crystallization process (b) under different pressures measured by using piston-cylinder apparatus (Inset figure is the determination method diagram of T1/2,g, Tel,x and Tp,x)
图 6 非晶硒的玻璃化转变中点温度
$ {T}_{1/2,\text{g}} $ 、外推起始晶化温度Tel,x和晶化峰值温度Tp,x随压力的变化关系Figure 6. Pressure dependence of glass transition middle point temperature
$ {T}_{1/2,\text{g}} $ , the extrapolated crystallization onset temperature Tel,x and crystallization peak temperature Tp,x of a-Se
图 7 (a) 六面顶压机上测量的2000、2500和4500 MPa压力下非晶硒样品的DTA曲线和(b) 晶化峰值温度随压力的变化关系
Figure 7. (a) DTA curves of a-Se under the pressures of 2000 MPa, 2500 MPa and 4500 MPa generated by a cubic press and (b) pressure dependence of Tp,x
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