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Flash-DSC provides valuable insights into glass relaxation and crystallization
被引:1
|作者:
Lancelotti, Ricardo F.
[1
]
Pereira, Luiz
[2
]
Hess, Kai-Uwe
[2
]
Dingwell, Donald B.
[2
]
Zanotto, Edgar D.
[1
]
机构:
[1] Univ Fed Sao Carlos, Grad Program Mat Sci & Engn, BR-13565905 Sao Carlos, SP, Brazil
[2] Ludwig Maximilians Univ Munchen, Dept Earth & Environm Sci, D-80333 Munich, Germany
基金:
欧洲研究理事会;
巴西圣保罗研究基金会;
关键词:
Fast scanning calorimetry;
Limiting fictive temperature;
Glass transition temperature;
Lead metasilicate;
Lithium disilicate;
Critical cooling rate;
FICTIVE TEMPERATURE;
TRANSITION;
VISCOSITY;
NUCLEATION;
DEPENDENCE;
ENTHALPY;
KINETICS;
LIQUIDS;
MODEL;
FLOW;
D O I:
10.1016/j.jnoncrysol.2024.123242
中图分类号:
TQ174 [陶瓷工业];
TB3 [工程材料学];
学科分类号:
0805 ;
080502 ;
摘要:
Conventional differential scanning calorimeters (DSC) are widely used to study thermal responses in glasses, such as crystallization, relaxation, and glass transition. However, their cooling (q(c)) and heating (q(h)) rates are limited, typically ranging from 0.01 to 2 K s(-1). Flash-DSC overcomes this limitation by achieving much higher rates (up to similar to 10(4) K s(-1)), allowing exploration of a wider range of experimental times, which is valuable for studying the glass transition phenomenon relevant to melts and glass industry. In this study, we utilized flash-DSC to investigate the thermal behavior of lithium disilicate (Li2Si2O5) and lead metasilicate (PbSiO3) glasses, employed here as examples of distinct fragility and glass-forming ability. We measured their limiting fictive temperatures (T'(f)), onset glass transition temperatures (T-g,T-onset), and the shift factors, which enable the retrieval of viscosity from DSC experiments. Our findings reveal that: i) the shift factor is composition-dependent; ii) when using a fixed heating rate for glass samples made with different cooling rates and the absolute values of q(h)>q(c), T-g,T-onset shifts to higher values as qc decreases, but when qh <= qc, T-g,T-onset shows no significant variation despite different T'(f) values due to relaxation on the heating path; iii) Li2Si2O5 glass exhibited non-overlapping heating curves in 8 repeated experiments after being cooled at the lowest rate, 50 K s(-1), suggesting partial crystallization during cooling, while PbSiO3 exhibited overlapping heating curves, indicating its superior glass forming ability. Therefore, the critical cooling rate for vitrification of Li2Si2O5 was estimated to be above 50 K s(-1). These findings indicate the power of flash-DSC to provide valuable insights into relaxation and crystallization phenomena.
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