Unveiling the dependence of glass transitions on mixing thermodynamics in miscible systems.

Unveiling the dependence of glass transitions on mixing thermodynamics in miscible systems.
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揭示混溶系统中玻璃化转变对混合热力学的依赖性

DOI:
10.1038/srep08500
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发表时间:
2015-02-17
期刊:
影响因子:
4.6
通讯作者:
Wang LM
Wang LM
中科院分区:
综合性期刊3区
文献类型:
--
作者:
Tu W;Wang Y;Li X;Zhang P;Tian Y;Jin S;Wang LM

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混合物中的玻璃化转变对混合热力学的依赖性通过关注混合焓、ΔHmix与符号(正与负)和大小(小与大)的变化来检查。以绝对ΔHmix很小的邻-间-甲氧基甲苯(MMB)和邻-间-二溴苯(DBB)两个同分异构体体系为例,论证了正Δ Hmix和负ΔHmix的影响.两个相反的组合物的玻璃化转变温度,Tg的依赖性,观察与MMB的混合物显示出明显的负偏差从理想的混合规则和DBB的混合物具有轻微的正偏差。将具有大的和负的ΔHmix的1,2-丙二胺(12 PDA)与丙二醇(PG)的体系与具有小的ΔHmix的体系进行比较,并且观察到相当正的Tg偏移。涉及纯组分性质的模型,如Tg、玻璃化转变热容增量ΔCp和密度ρ,不能解释系统中观察到的Tg变化。相反,ΔHmix和最大Tg位移之间显示出线性相关性。
The dependence of the glass transition in mixtures on mixing thermodynamics is examined by focusing on enthalpy of mixing, ΔHmix with the change in sign (positive vs. negative) and magnitude (small vs. large). The effects of positive and negative ΔHmix are demonstrated based on two isomeric systems of o- vs. m- methoxymethylbenzene (MMB) and o- vs. m- dibromobenzene (DBB) with comparably small absolute ΔHmix. Two opposite composition dependences of the glass transition temperature, Tg, are observed with the MMB mixtures showing a distinct negative deviation from the ideal mixing rule and the DBB mixtures having a marginally positive deviation. The system of 1, 2- propanediamine (12PDA) vs. propylene glycol (PG) with large and negative ΔHmix is compared with the systems of small ΔHmix, and a considerably positive Tg shift is seen. Models involving the properties of pure components such as Tg, glass transition heat capacity increment, ΔCp, and density, ρ, do not interpret the observed Tg shifts in the systems. In contrast, a linear correlation is revealed between ΔHmix and maximum Tg shifts.
DOI: 10.1002/jctb.5010020901
发表时间: 1952-01-01
期刊: JOURNAL OF APPLIED CHEMISTRY
影响因子: --
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GORDON, M;TAYLOR, JS
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发表时间: 1998-07-09
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DOI: 10.1051/jcp/1973701355
发表时间: 1973-01-01
期刊: JOURNAL DE CHIMIE PHYSIQUE ET DE PHYSICO-CHIMIE BIOLOGIQUE
影响因子: --
作者:
ABELLO, L
通讯作者: ABELLO, L