【摘要】：為了解玻璃化轉(zhuǎn)變過(guò)程中非線性特征參數(shù)的變化規(guī)律及與其它特征參數(shù)的關(guān)聯(lián),探討非線性參數(shù)與玻璃態(tài)材料熱穩(wěn)定性間的關(guān)聯(lián),本文利用差示掃描量熱儀對(duì)具有玻璃形成能力的單質(zhì)液體、不同混合模式的三種二元混合溶液(間甲基苯甲酸甲酯和鄰甲基苯甲酸甲酯、間甲基苯甲酸甲酯與鄰苯二甲酸二丁酯、1,2-丙二醇和2-乙基己胺)、三乙酰甘油酯和丙三醇玻璃態(tài)中的等溫結(jié)構(gòu)弛豫進(jìn)行了量熱學(xué)測(cè)量,結(jié)合Tool-Narayanaswamy-Moynihan-Hodge(TNMH)方程、Kohlrausch-Williams-Watts(KWW)方程和Richert方程對(duì)實(shí)驗(yàn)結(jié)果進(jìn)行了擬合分析。對(duì)具有不同液體強(qiáng)弱性參數(shù)、同分異構(gòu)體分子、具有不同官能團(tuán)物質(zhì)等單質(zhì)液體進(jìn)行焓弛豫研究,發(fā)現(xiàn)同種材料中,當(dāng)液體強(qiáng)弱性參數(shù)變化較大時(shí),非線性參數(shù)隨著液體強(qiáng)弱性參數(shù)的增加而降低。高聚物、無(wú)機(jī)物和離子液體、金屬玻璃等任一類玻璃體系中的結(jié)果也符合該規(guī)律。還發(fā)現(xiàn)通常情況下,材料的非線性參數(shù)值小于非指數(shù)性參數(shù)。利用焓弛豫對(duì)理想混合溶液、近似理想混合溶液和非理想混合溶液中的動(dòng)力學(xué)參數(shù)隨組分的變化進(jìn)行了分析,發(fā)現(xiàn)三種不同混合模式的玻璃形成體系中,非線性參數(shù)隨組分的偏離方向均與非指數(shù)性參數(shù)的偏離方向相同,偏離程度的大小受混合熱影響。對(duì)三乙酰甘油酯和丙三醇在玻璃態(tài)下的等溫結(jié)構(gòu)弛豫進(jìn)行焓弛豫研究,利用TNMH方程進(jìn)行擬合的研究結(jié)果表明,非線性參數(shù)值是溫度時(shí)間函數(shù),隨著等溫時(shí)間的延長(zhǎng)而變大。利用KWW方程和Richert方程分別進(jìn)行自由擬合和固定擬合得到的結(jié)果表明,利用Richert方程進(jìn)行固定擬合更加合理,非線性參數(shù)隨退火溫度的降低而變化,同時(shí)發(fā)現(xiàn)玻璃態(tài)下的非指數(shù)性參數(shù)值不等于玻璃化轉(zhuǎn)變溫度處的數(shù)值。研究結(jié)果有利于估測(cè)未知玻璃形成材料的非線性特征參數(shù),評(píng)判玻璃形成材料中特征參數(shù)計(jì)算的準(zhǔn)確性;利用二元混合溶液中參數(shù)的變化規(guī)律,可以外推某些具有低玻璃形成能力材料的動(dòng)力學(xué)特征參數(shù),加深對(duì)不易被單獨(dú)研究玻璃形成材料的認(rèn)識(shí),指導(dǎo)構(gòu)建具有特殊動(dòng)力學(xué)特征參數(shù)的結(jié)構(gòu)材料;玻璃態(tài)下材料等溫結(jié)構(gòu)弛豫的研究,有利于認(rèn)識(shí)非線性參數(shù)及非指數(shù)性參數(shù)在整個(gè)玻璃化轉(zhuǎn)變溫度區(qū)間隨時(shí)間和溫度的變化規(guī)律,有利于了解玻璃態(tài)材料在使用過(guò)程中的性能變化,有利于指導(dǎo)構(gòu)建非線性特征參數(shù)與玻璃態(tài)材料熱穩(wěn)定性間的關(guān)聯(lián)。
[Abstract]:In order to understand the variation of nonlinear characteristic parameters and their correlation with other characteristic parameters during glass transition, the relationship between nonlinear parameters and thermal stability of glass state materials is discussed. In this paper, differential scanning calorimeter (DSC) was used to treat three binary mixed solutions (methyl m-methylbenzoate and methyl o-methylbenzoate) with glass-forming ability and different mixing modes. The isothermal structural relaxation of methyl m-methylbenzoate, dibutyl phthalate, dibutylene phthalate and 2-ethylhexylamine), triacetylglycerol and glycerol in glass state was measured by calorimetry. The experimental results are fitted with Tool-Narayanaswamy-Moynihan-Hodge (TNMH) equation Kohlrausch-Williams-Watts (KWW) equation and Richert equation. The enthalpy relaxation of simple liquids with different liquid strength parameters, isomer molecules, and different functional groups is studied. It is found that in the same materials, when the liquid strength and weakness parameters change greatly, The nonlinear parameters decrease with the increase of liquid strength. The results in any kind of glass systems such as polymers, inorganic substances, ionic liquids and metallic glasses also accord with this rule. It is also found that, in general, the nonlinear parameter of the material is smaller than that of the non-exponential parameter. The variation of kinetic parameters with components in ideal mixed solution, approximate ideal mixed solution and non ideal mixed solution was analyzed by enthalpy relaxation. The deviation direction of nonlinear parameters with components is the same as that of non-exponential parameters, and the degree of deviation is affected by mixed heat. The isothermal structure relaxation of triacetylglycerol and glycerol in glass state was studied by enthalpy relaxation. The results of fitting by TNMH equation show that the nonlinear parameter value is a temperature time function and increases with the increase of isothermal time. The results of free fitting and fixed fitting with KWW equation and Richert equation show that it is more reasonable to use Richert equation for fixed fitting, and the nonlinear parameters vary with the decrease of annealing temperature. It is also found that the nonexponential parameter values in glass state are not equal to the values at the glass transition temperature. The results are helpful to estimate the nonlinear characteristic parameters of the unknown glass-forming materials, to evaluate the accuracy of the calculation of the characteristic parameters in the glass-forming materials, and to make use of the variation law of the parameters in binary mixed solution. It can extrapolate the kinetic characteristic parameters of some materials with low glass-forming ability, deepen the understanding of the glass-forming materials which are not easy to be studied separately, and guide the construction of structural materials with special dynamic characteristic parameters. The study of isothermal structure relaxation in glass state is beneficial to the understanding of the variation of nonlinear and nonexponential parameters with time and temperature in the whole glass transition temperature range. It is helpful to understand the change of properties of glass state materials in the process of application and to guide the construction of the correlation between nonlinear characteristic parameters and thermal stability of glass state materials.
【學(xué)位授予單位】：燕山大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類號(hào)】：TB30

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