常用醇类低温保护剂水溶液的DSC研究

利用差示扫描量热仪(Pyris-Diamond DSC),研究了乙二醇、丙三醇、1,3丙二醇、1,3丁二醇和2,3丁二醇水溶液的过冷行为、水合性质以及玻璃化转变温度,得出了这些性质与溶液浓度的关系.过冷度和未冻水含量在低浓度时没有明显的规律性;而在中高浓度则具有相同的变化规律:随着溶液浓度的增大而增大.各低温保护剂在水合性质上所表现出的差异性,体现了保护剂的官能团(羟基、甲基)所起到的重要作用.保护剂在玻璃化转变温度的明显差异,则反映它们在玻璃化能力方面的强与弱.     

纳米低温保护剂玻璃化过程中热学性质的研究

本文利用差示扫描量热仪(DSC)对含有羟基磷灰石(HA)纳米颗粒的丙三醇溶液玻璃化过程中的主要热学性质进行了测定。其中包括玻璃化与反玻璃化温度的测定,玻璃化过程中比热的测定。结果表明加入HA纳米颗粒后的丙三醇溶液的反玻璃化温度(Td)表现出明显的上升趋势,当溶液浓度高于50%时玻璃化温度(Tg)也稍有升高;加入纳米颗粒后溶液在整个玻璃化过程中比热明显减小,并且减小程度与HA颗粒浓度及粒径大小均表现出一定的非线性关系。     

DSC法研究不同邻对位比值酚醛树脂的固化行为

利用差示扫描量热(DSC)分析技术研究了不同邻对位比值(O/P值)的酚醛树脂的固化活化能及固化进程。采用Ozawa模型求解了不同O/P值酚醛树脂的固化活化能及固化动力学参数,结果表明,酚醛树脂的固化活化能随其O/P值的增加而降低,固化进程变得更加容易。固化反应过程中的Ozawa反应指数n0随着固化反应温度的升高而下降,并且随着树脂O/P值的增加,n0出现在更低的温度区间内。Ozawa反应速度常数k0在固化反应初期随温度的升高而增加,在反应后期则随着温度的升高而下降,并且随着树脂O/P值的增加,k0出现峰值对应的温度降低,表明固化先后经历了微凝胶增长与扩散反应控制两个阶段,树脂O/P值的增加加快了微凝胶的增长进程。     

差示扫描量热法研究改性双马来酰亚胺的固化过程

用差示扫描量热法(DSC) 研究了CDR-9418 双马来酰亚胺树脂的固化过程, 用动态和静态两种方法分析了其固化反应过程, 发现有两个固化反应放热峰, 并用T-Φ 外推法确定了凝胶温度、固化温度和后固化温度等固化工艺参数。      

非等温DSC法研究高韧性低收缩环氧体系固化动力学

采用非等温DSC法对一种高韧性低收缩环氧树脂体系(E-51/E-20/DAMI)固化动力学进行了研究。分别通过n级反应模型法和自催化模型法得到了固化反应动力学方程。结果表明,n级反应方程与实验值差别较大;而采用Malek判据判别该固化反应按自催化反应机理进行,并通过"单点非模型"拟合法求解动力学参数,模型计算曲线与DSC实验曲线基本吻合。但由于动力学控制和扩散控制竞争关系的改变,随升温速率的提高,实验曲线逐渐偏离模型曲线,体系的总放热焓变小。所确立的模型在5K/min～25K/min的升温速率下能较好地描述E-51/E-20/DAMI体系的固化反应过程。     

一种双组份液态环氧树脂材料的固化行为

将一种液态双酚A二缩水甘油醚环氧树脂用曼尼希改型胺进行等温固化,固化温度范围为5～60℃,采用差示扫描量热法（DSC）测试不同固化条件下固化后样品的玻璃化转变温度和剩余反应焓。结果表明,玻璃化转变温度Tg随固化时间的延长而上升,Tg与转化率之间存在着不依赖于固化温度的一一对应关系,将Tg与时间的关系曲线漂移叠合形成固化反应的总曲线,用时温漂移技术获得了体系唯一的表观活化能（52.65kJ/mol）,做出争含玻璃化曲线和iso-Tg曲线的时间-温度-转变（TTT）等温固化图。     

DSC 法研究聚醚胺 / 酚醛胺-环氧树脂体系的固化行为

采用示差扫描量热法(DSC),在 25 ~ 230 ℃范围内以不同的升温速率(5,10,15, 20 ℃ / min),研究了以聚醚胺 / 酚醛胺为固化剂的环氧树脂体系的固化行为,对其不同升温速率下的固化度进行了分析,采用 T-β 外推法得出了该体系的起始固化温度、峰顶固化温度和终止固化温度等固化工艺参数。     

溶液浇铸聚甲基丙烯酸甲酯薄膜的DSC研究

用ＤＳＣ观测了溶液浇涛ＰＭＭＡ薄膜的热焓松弛行为,对物理老化,溶液浓度以及溶剂极性对其热焓松弛行为的影响进行了详细的讨论,其特征用凝聚缠结的观点予以解释。     

酚醛树脂-双马来酰亚胺体系的固化动力学

采用非等温DSC法探讨了酚醛树脂与双马来酰亚胺体系的固化反应,在30 ℃～400 ℃范围内以不同升温速率(5 ℃/min、10 ℃/min、15 ℃/min、20 ℃/min)进行动态固化行为分析.应用Kissinger、Crane和Ozawa法求得了固化反应的表观活化能、固化反应级数、凝胶温度和固化温度等动力学参数.结果表明,固化体系的平均表观活化能为109 kJ/mol,反应级数为0.94,凝胶温度Tgel为79.68 ℃,固化温度Tcure为121.93 ℃,表观活化能E是固化度α的增函数.     

非等温DSC研究超支化聚醚/PEG/IPDI体系的固化反应动力学

采用非等温差示扫描量热法(DSC)研究了超支化聚醚对聚乙二醇/异佛尔酮二异氰酸酯体系(PEG/IPDI)固化反应动力学的影响。结果表明,PEG/IPDI体系的固化反应表观活化能约为53.278 kJ/mol,反应级数为0.914,指前因子为1.500×105min-1;加入6%的超支化聚醚后,体系的固化峰温升高,表观活化能、反应级数和指前因子分别提高至87.577 kJ/mol、0.960、1.201×1010min-1,机理函数仍遵循Avrami-Erofeev方程G(α)=[-ln(1-α)]n,只是方程中的指数n有所变化。超支化聚醚对PEG/IPDI体系的固化反应有一定的延缓作用,但不改变固化机理。浅析了超支化聚醚影响PEG/IPDI体系固化的原因。     

Recrystallization and grain growth of nanocomposite Ti–B–N coatings

Nanocomposite Ti–B–N coatings with different chemical composition were prepared by non-reactive co-sputtering of a segmented TiN–TiB₂ target. The coatings investigated are primarily composed of nanocrystalline TiN and TiB₂ phases. Increasing boron content results in a decreasing grain size from approximately 6 to 2 nm. During a thermal treatment of such coatings solely recovery and recrystallization with subsequent grain growth would appear, since the two phases are in thermodynamic equilibrium. Differential scanning calorimetry (DSC) and X-ray diffraction analysis were used to investigate the recrystallization behavior and subsequent grain growth of the nanocomposite Ti–B–N coatings. On heating the coating samples, which were removed chemically from their low alloyed steel substrates, an exothermal peak appeared during the DSC measurements indicating grain growth. From the onset temperature of this peak the recrystallization temperature was found which increases with increasing boron content from 1032 to 1070 °C. Activation energies for grain growth are obtained from Kissinger plots and yield values decreasing from 7.9 to 4.4 eV with increasing boron content. After heat treatment up to 1400 °C during the DSC measurements the coatings showed grain sizes within the range of 15–30 nm. It was found that the highest recrystallization temperature does not imply the highest activation energy for grain growth.     

Crystallization kinetics and densification of YAG nanoparticles from various chelating agents

Yttrium aluminium garnet (YAG, Y₃Al₅O₁₂) nanoparticles were prepared using sonochemical sol-gel method with three different chelating agents and the effect of crystallization kinetics was investigated with differential scanning calorimetry-thermogravimetry (DSC-TG). The activation energy values of crystallization for the as-synthesized YAG nanoparticles using citric acid (CA), glycine (G) or a mixture of citric acid-glycine (CA-G), as chelating agents were found to be 160.5, 142.2 and 140.4 kJ mol⁻¹ and the corresponding Avarami constants were 2.2, 2.1 and 1.9, respectively. Samples produced with the mixed chelating agent under sonification, could be crystallized to single phase YAG nanoparticles (10-65 nm) after annealing at 1100 °C. Pellets made from the annealed YAG particles could be sintered to a relative density greater than 99% at 1500 °C with a grain size of 4.5 μm, made up of secondary particles formed from primary nano-crystals within the grains. Grain size and relative density increased with different chelating agents from CA to G and CA-G in the increasing order when YAG samples were sintered. Grain growth and densification occurred at a relatively low temperature of 1500 °C as compared to over 1800 °C in solid-state reactions.     

用DSC测定兔主动脉血管冻结相变区间的表观比热容及其影响因素

利用差示扫描量热仪(DSC)测定了兔主动脉血管在相变温区比热容的变化;定量研究了不同浓度低温保护剂(CPA)的水合作用对主动脉血管比热容的影响.研究结果表明,二甲基亚砜(DMSO)浓度越大,主动脉血管的比热峰值越小,当浓度达到15%时,其峰值只有0%时的1/2左右;无DMSO时的结合水含量为0.119g/g水,而含15%DMSO时的结合水含量达到0.411 g/g水,使得冻结完成后的表观比热反而更大.根据实验数据,修正了已有相变区间表观比热容的关系式,该关系式可应用于对血管进行低温保存时的传热以及热应力模型分析求解.     

Study of crystallization kinetics and structural relaxation behavior in phase separated Ag33Ge17Se50 glassy alloys

We report on the crystallization processes and structure (crystal phases) of Ag₃₃Ge₁₇Se₅₀ glassy alloy using differential scanning calorimetry and x-ray diffraction techniques, respectively. The devitrification that gives rise to the first exothermic peak results in the crystallization of Ag₂Se and Ag₈GeSe₆ phases, while the growth of GeSe₂ accompanied by the transformation of Ag₈GeSe₆ to Ag₂Se phase occurs during the second crystallization process. Different theoretical models are used to elucidate various kinetic parameters for the crystallization transformation process in this phase separated system. With annealing below the glass transition temperature, an inverse behavior between the variation of the optical gap and the band tailing parameter is observed for the thermally evaporated films. These results are explained as the mixing of different clusters/species in the amorphous state and/or changes caused by structural relaxation of the glassy network for the thermally evaporated films.     

Structure and properties of mixtures based on long chain polyacrylate and 1-alcohol composites

A series of phase change materials (PCMs) based on long chain polyacrylate and 1-alcohol, i.e., poly (stearyl methacrylate) and 1-tetradecanol (PSMA/C14OH) were prepared through the solution-mixing method. Thermal energy storage capacity, thermal stability and morphology of PSMA/C14OH PCMs were characterized by Fourier transform infrared spectroscopy (FTIR), polarized optical microscopy (POM), field emission scanning electron microscopy (FE-SEM), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). DSC results demonstrated that the heat of fusion of PSMA/C14OH PCMs increased from 85.9 to 172.3 J g⁻¹ with the weight fraction of C14OH increasing from 20 to 80 wt%. And, the thermal stability also enhanced with PSMA weight. The spherulite (ca. 250 μm) in PSMA/C14OH composites containing 60 wt% C14OH proved the compatibility between PSMA and C14OH, indicating the cocrystallization behavior of alkyl side groups appeared. The cocrystallization behavior contributes the enhanced thermal stability of PSMA/C14OH PCMs, and it is suitable as the thermal energy storage materials in the future.     

Coupling of conductivity to the relaxation process in polymer electrolytes

Conductivity relaxation using modulus formalism has been used to explore the coupling of ionic conductivity to dielectric relaxation in polymer electrolyte based on polyethylene oxide complexed with various content of LiAsF₆. The temperature dependence of conductivity followed the VTF behavior suggesting close correlation between conductivity and the segmental relaxation process in polymer electrolytes. The coupling of conductivity to the segmental process has been discussed in terms of coupling index. For all compositions studied, the coupling index was within the range of 1–11 in the temperature range of investigation, which was in agreement with the coupled systems.     

Experimental protocol to determine the ability of PET to crystallise

PET [poly(ethylene terephtalate)] is a semi-crystalline thermoplastic that is very suitable for forming processes and is widely used in various technologies. For specific applications, it is necessary to avoid the crystallization of the material by quenching from the melting state while for other applications this crystallization is required. It follows that the ability of PET to crystallize could be a crucial industrial problem, particularly because of the large range of PET proposed by plastic suppliers. This work deals with a calorimetric method able to discriminate this aptitude between various PET rapidly and to give a criterion of crystallizability.     

Prediction of the self-accelerating decomposition temperature (SADT) for liquid organic peroxides from differential scanning calorimetry (DSC) measurements

We present a prediction (estimation, calculation, screening) method for the estimation of the self-accelerating decomposition temperature (SADT) for liquid organic peroxides from differential scanning calorimetry (DSC) measurements based on the concepts of thermal explosion theory originally introduced by Semonov which are adopted to our problem assuming nth-order reaction kinetics. For the peroxides under investigation, we demonstrate good agreement with the experimental SADT. This method can be used as a quick and easy applicable method for the estimation of the critical temperatures.     

Synthesis,characterization, thermal and dielectric properties of pure and cadmium doped calcium hydrogen phosphate

The synthesis of pure and cadmium doped calcium hydrogen phosphate as single crystal has been accomplished by a room temperature solution growth technique viz., silica gel technique. Silica gel obtained from sodium metasilicate with a strongly acidic cation exchanger in the H-form, was used for crystal growth experiments. The nature of the grown material was established by powder X-ray diffraction (PXRD) studies, whereas from single crystal X-ray diffraction (SXRD) the crystal system comes out to be monoclinic. The stoichiometry of the grown composition was established by energy dispersive X-ray analysis (EDAX). Fourier transform infrared spectroscopic (FTIR) studies signifies the presence of phosphate (PO₄)²⁻ group and water of crystallization. Thermo gravimetrical analysis and investigations of dielectric properties were undertaken to study the thermal stability, dielectric constant and transition temperature of the grown material. Dielectric studies suggest that there is a shift in the value of transition temperature (T_c) thereby indicating relaxor behaviour of the material.