Nd_9Fe_(85.5-x)Co_xB_(5.5)快淬薄带晶化动力学研究

采用真空再充Ar保护的DSC测量了Nd9Fe85.5-x Cox B5.5(x=3%,5%(原子分数))非晶薄带的升温曲线,计算了两种非晶薄带的晶化激活能E、频率因子Z、反应速率常数K、Avrami指数n。实验证实了Co从3%(原子分数)增大到5%(原子分数)时晶化过程从一步改变为两步晶化;计算结果表明晶化起始温度Tx及晶化峰值温度Tp的晶化激活能、晶化反应速率常数均随Co的增加而增大,其主要原因是增大的频率因子起了关键作用;分析计算结果认为Nd9Fe82.5Co3B5.5在升温速度10K/min时局域Avrami指数n随着晶化体积分数x的增加先急剧降低而后缓慢降低、90%之后又有所升高,表明晶化形核在x12%以三维形核方式为主,在x为12%~36%时晶化以二维形核方式为主,之后直到晶化结束以一维形核方式为主。     

FINEMET合金晶化行为的DSC研究

本文通过非等温DSC方法研究了Fe73.5CulNb3Si13.5B9合金的晶化行为.根据不同升温速率的DSC曲线,采用Kissinger方程计算了两个析晶峰的晶化表观激活能E1(406±14kJ/mol)和E2(455±37kJ/mol)及频率因子ν(ν1＝3.15839×1022,ν2＝5.24126×1021);根据表观激活能与晶化分数的关系图分析了合金的晶化过程;最后利用JMA模型计算出两个析晶峰的Avrami指数m1(1.44)和m2(3.5),并根据动力学参数分析了非晶Fe73.5CulNb3Si13.5B9合金的析晶机理.     

低频脉冲磁场处理非晶Fe78Si9B13合金纳米晶化的DSC研究

用低频脉冲磁场处理非晶Fe78Si9B13合金,采用差示扫描热分析(DSC)的方法测定了不同升温速率下非晶Fe78Si9B13合金的DSC曲线,利用Kissinger方程计算出了晶化过程的激活能.结果表明,晶化激活能由处理前的433.6kJ/mol降到200kJ/mol以下,提高了晶核形核速率,抑制了晶核长大速率,从而实现了非晶合金的低温纳米晶化.     

不同微观结构Zr_(55)Al_(10)Ni_5Cu_(30)块体非晶合金的晶化过程

用差示扫描量热仪分别对具有相似晶体体积分数和晶化激活能的Zr55Al10Ni5Cu30块体非晶合金铸态、轧制态试样进行等温和连续升温实验,研究了不同微观结构块体非晶合金的晶化过程。结果表明,在晶化初期(小于30 min),两个试样具有相似的晶化速率;晶化后期(大于30 min),轧制态试样表现出较快的晶化速率。这在一定程度上表明,用JMA公式和晶化开始温度Tx及峰值温度Tp计算出的晶化激活能不能全面反映非晶合金的热稳定性。另外,剪切带中原子之间相互联接的减弱以及短程有序的强化,使轧制态试样热稳定性降低和晶化过程变快。     

一种富钛NiTi薄膜的晶化动力学

本实验采用直流磁控溅射法制备了一种非晶的富TiNiTi薄膜，其成分为Ni46.34%（原子分数），Ti53.66％（原子分数）。采用变温方法研究了这种非晶薄膜的晶化动力学。测得非晶薄膜晶化的激活能为271kJ/mol，平均Avrami指数为1．17。采用以上获得的动力学参数计算了薄膜在773K的等温晶化动力学曲线。计算结果与实验结果吻合较好。在薄膜的晶化过程中伴随着Ti2Ni的析出。     

Mg65Cu25Gd10大块非晶合金热稳定性研究

Mg65 Cu25 Gd10非晶合金的热稳定性关系到其作为结构材料的实用性及发展前景.利用差示扫描量热法(DSC)研究了预先弛豫退火处理后Mg65 Cu25 Gd10非晶的特征转变温度和晶化激活能变化,分析了弛豫退火对其热稳定性的影响.通过kissinger方程计算其晶化激活能、频率因子、反应速率系数进一步说明此非晶的晶化过程,并通过X射线衍射分析退火非晶的析晶过程,结果表明低温弛豫提高了非晶的热稳定性.     

激光3D打印非晶合金晶化体积分数的理论预测

采用一种有效的方法预测激光3D打印块状非晶合金的晶化程度,对于激光3D工艺参数的选择与优化至关重要。本工作从非晶合金的晶化动力学入手,通过测试不同加热速率下非晶合金的特征温度,获得非晶合金发生晶化所要克服的晶化激活能和Arrhenius指前因子,并结合有限元模拟技术,提出了一种预测激光3D打印非晶合金晶化体积分数的方法。以Zr_(50)Ti_5Cu_(27)Ni_(10)Al_8(Zr50)非晶合金为模型体系,验证了该方法的有效性。结果表明:利用该方法获得的激光3D打印单道Zr50非晶合金晶化相体积分数为1.23%,与实验得到的晶化相体积分数1.65%较接近,这有力地证明了提出的激光3D打印非晶合金晶化体积分数的理论预测方法是可行的。     

非晶Pr8Fe86B6合金的晶化动力学

用差热分析（DTA），结合X射线衍射（XRD）研究了非晶Pr8Fe86B6合金的晶化动力学。结果表明：该非晶Pr8Fe86B6合金的晶化相为α-Fe固溶体、Pr2Fe23B3和Pr2Fe14B金属间化合物，通过对三相晶化激活能的分析得出：α－Fe相的激活能在晶化初期变化不大，当其体积分数大于8％时，其晶化激活能开始减小；而Pr2Fe23B3和Pr2Fe14B相的激活能随其体积分数的增加而减小，且α－Fe相较Pr2Fe23B3和Pr2Fe14B相容易晶化析出。     

非晶Sm5Fe74.3Nb1.5Si11.7B4.5C2.5Cu0.5合金经预退火后的晶化动力学的DTA研究

研究了非晶Sm5Fe74.3Nb1.5Si11.7B4.5C2.5Cu0.5合金经400℃，保温10min预退火后的晶化动力学。结果表明；该合金的晶化相为α-Fe固溶体和Sm2Fe17Cx金属间化合物，两相的晶化表观激活能分别为557KJ/mol和514KJ/mol，当晶化体积分数为60%时，α-Fe相的晶化激活能达极大值；Sm2Fe17Cx相晶化激活能则随其晶化体积分数的增加而逐渐减小。     

低温弛豫对Mg65Cu25Gd10大块非晶合金热稳定性及力学行为影响

Mg65Cu25Gd10非晶合金的热稳定性关系到其作为结构材料的实用性及发展前景.利用差示扫描量热法(DSC)研究了预先低温弛豫处理后Mg65Cu25Gd10非晶的特征转变温度和晶化激活能,分析了低温弛豫对其热稳定性的影响,通过Kissinger方程计算其晶化激活能、频率因子、反应速率系数进一步说明此非晶的晶化过程.同时,通过比较其力学性能的变化,发现非晶压缩性能受非晶稳定性影响不大,抗压强度下降很小.但其断裂方式及断面微观特征有明显变化.     

环氧树脂固化动力学研究进展

差示扫描量热仪(DSC)是研究环氧树脂固化动力学的有效手段,获得动力学参数的方法分为模型拟合法和非模型拟合法2类.模型拟合法的关键在于确定动力学三因子,即反应模型、指前因子和活化能;其拟合过程需要事先选择模型及模型参数,并且等温和非等温条件下拟合得到的动力学参数差别较大,无法通过非等温条件下的数据预测等温固化行为.非模型拟合法则通过计算活化能与固化度的对应关系研究固化行为,可以避免模型及模型参数选择不当造成的误差,并且等温和非等温条件下拟合得到的动力学参数基本一致,可由非等温数据预测等温固化行为.准确的动力学方程可为优化固化工艺、提高固化产物性能提供理论基础.     

Nonisothermal crystallization kinetics of poly(ethylene terephthalate) nanocomposites

This article reports the nonisothermal crystallization kinetics of poly(ethylene terephthalate) (PET) nanocomposites. The non-isothermal crystallization behaviors of PET and the nanocomposite samples are studied by differential scanning calorimetry (DSC). Various models, namely the Avrami method, the Ozawa method, and the combined Avrami-Ozawa method, are applied to describe the kinetics of the non-isothermal crystallization. The combined Avrami and Ozawa models proposed by Liu and Mo also fit with the experimental data. Different kinetic parameters determined from these models prove that in nanocomposite samples intercalated silicate particles are efficient to start crystallization earlier by nucleation, however, the crystal growth decrease in nanocomposites due to the intercalation of polymer chains in the silicate galleries. Polarized optical microscopy (POM) observations also support the DSC results. The activation energies for crystallization has been estimated on the basis of three models such as Augis-Bennett, Kissinger and Takhor methods follow the trend PET/2C20A < PET/1.3C20A < PET, indicating incorporation of organoclay enhance the crystallization by offering large surface area.     

Application of non-isothermal dilatometry for evaluation of kinetic parameters in non-reversing reactions

The applicability of the non-isothermal dilatometric technique for the investigation of rate processes is discussed. Equations have been derived for a non-reversing reaction, which may be used to calculate the kinetic parameters from non-isothermal dilatometric curves. The main advantages of the approach are considerable economies in experimental procedure and the avoidance of experimental errors associated with the onset of reaction before isothermal conditions are attained. The position of the inflection point on the dilatometric curve and the slope at that point give the activation energy and frequency factor of the reaction. The usefulness of the new approach is demonstrated by the good agreement between values of activation energy obtained by the new equations and reported literature values for the second and third stages in the tempering reaction of a plain carbon steel.     

A macrokinetic approach to crystallization modelling of semicrystalline thermoplastic matrices for advanced composites

A theoretical macrokinetic model for the crystallization of polyphenylene sulphide (PPS) matrix for high performance composites is presented. The model, accounting for the induction time due to nucleation, is able to predict crystallization changes in isothermal and non-isothermal conditions, including cold and melt crystallization, and quenching effects. Moreover, a simple expression is proposed for the temperature dependence of the kinetic constant allowing a straightforward calculation of model parameters. Theoretical results are in good agreement with calorimetric experimental data obtained in a wide range of thermal conditions. Time temperature transformation plots, constructed from the model developed for isothermal (TTT) and non-isothermal (CCT) conditions, are presented providing a fundamental tool for understanding the crystallization behaviour of semicrystalline matrices and to determine the most appropriate processing conditions.     

苯乙炔基封端聚酰亚胺树脂的固化动力学研究

采用非等温差示扫描量热法(DSC)研究了两种苯乙炔基封端型聚酰亚胺树脂固化动力学过程,分析了不同升温速率下,两体系的特征固化温度,反应热及反应速率与温度的关系。运用Kissinger法和Melak法进行数据处理。结果表明:(1)苯乙炔封端型聚酰亚胺树脂的固化过程符合n级固化反应方程,建立的固化反应方程较好地描述了其固化过程,且与实验数据拟合结果较好。(2)两树脂体系相比,分子链柔性较大的聚酰亚胺树脂特征固化温度较低,固化温区较宽,固化反应活化能较低,且反应级数较大。     

Evaluation of crystallization kinetics of glasses by non-isothermal analysis

Based on Johnson-Mehl-Avrami transition equation, this paper proposes a new non-isothermal method for evaluating the crystallization kinetics of glasses. An equation relating the kinetic parameters of the crystallization activation energy, E, and the frequency factor, v, to the inflection-point temperature, T _f, and the heating rate, , of differential thermal analysis (DTA) experiment is established. The inflection-point temperature, T _f, can be easily determined from the derivative differential thermal analysis (DDTA) curves. The validity of the proposed method is ascertained by applying it to Li₂O·2SiO₂ glass. The acquired values of the crystallization kinetic parameters by this method are excellent agreement with the isothermal analysis results. In contrast, the traditional non-isothermal methods give much higher values.     

PET-PEE/ATO纳米复合材料的非等温结晶动力学

采用无机纳米锑掺杂二氧化锡(ATO)和有机聚醚酯(PEE)协同提高聚对苯二甲酸乙二酯(PET)的抗静电性能,合成了聚对苯二甲酸乙二酯-聚醚酯/锑掺杂二氧化锡纳米复合材料(PET-PEE/ATO)。使用Ozawa方程和Liu-Mo方程研究了PET-PEE/ATO纳米复合材料的非等温结晶过程。Ozawa方程研究发现,在非等温结晶过程中,PET、PET-PEE、PET/ATO、PET-PEE/ATO的成核性能依次提高。Liu-Mo方程发现,ATO和PEE的加入分别促进了异相成核作用和加快了结晶生长,PET-PEE/ATO结晶成核性能最好,结晶速率最快。     

Non-isothermal Crystallization Kinetics of Polyamide 6/Diamine-modified MWNTs Nanocomposite

The non-isothermal crystallization kinetics of polyamide 6/diamine-modified multi-walled carbon nanotube (PA6/D-MWNT) nanocomposite was investigated by differential scanning calorimetry (DSC). The modified Avrami equation, the Ozawa equation and the combined Avrami/Ozawa equation were employed to analyze the non-isothermal crystallization data. The crystallization activation energies were also evaluated by the Kissinger method. It was found that the combined Avrami/Ozawa equation could successfully describe the non-isothermal crystallization process. The results showed that D-MWNTs not only acted as effective heterogeneous nucleating agents for PA6 and noticeably increased the crystallization temperature of PA6, but also influenced the mechanism of nucleation and crystal growth of PA6 and then reduced the overall crystallization rate of the neat PA6 matrix. The crystallization activation energy for the nanocomposite sample was greater than that of the neat PA6, which indicated that the addition of D-MWNTs hindered the mobility of PA6 chain segments.     

Autocatalytic decomposition reactions,hazards and detection

In the chemical industry, estimation methods based on dynamic Differential Scanning Calorimetry (DSC) measurements have been developed for a preliminary screening of the risk associated to a chemical operation. An important point for the assessment of thermal risk is the identification of autocatalytic reactions. These types of reactions require our special attention and should be clearly distinguished from nth order reactions. Until today, the most reliable tool for the identification of autocatalytic decompositions was an isothermal DSC measurement. A new screening method based on dynamic DSC measurements for the identification of autocatalytic decompositions has been developed. The method consists of fitting a first order kinetic model to the measured heat release rate curve (from dynamic DSC measurement) and determining the apparent activation energy. If the apparent activation energy is higher than 220 kJ/mol, the decomposition is autocatalytic. By taking into account the cases with the border value of the apparent activation energy (180-220 kJ/mol), as well as the exception to this method, it should be possible to apply our new screening tool to about 80% of the cases.     

On the crystallization behavior of amorphous Fe-Cr-Mo-B-P-Si-C powder prepared by mechanical alloying

The crystallization behavior and thermal stability of Fe-Cr-Mo-B-P-Si-C amorphous alloy, prepared by mechanical alloying (MA), were investigated by using differential scanning calorimetry (DSC). One exothermic peak was observed on DSC traces, implying that the crystallization process undergoes only one stage. The crystallization kinetic parameters, including activation energy (E_a), Avrami exponent (n) were determined with non-isothermal analysis method based on the DSC data. The results suggest that the crystallization mechanism is governed dominantly by a three-dimensional diffusion-controlled growth. In addition a relatively high value of activation energy of crystallization (386.04 ± 10 kJ/mol) was found, indicating that this amorphous alloy has high thermal stability.