热分析技术及其在高分子材料研究中的应用

简要介绍了热分析技术——热重法、差热分析、差示扫描量热法、热机械分析法和动态机械热分析法等及其在高分子材料领域的广泛应用。热分析技术的方法具有快速、方便等优点,在高分子材料的研究中发挥着重要作用。     

PMMA/SiO_2透明块体材料的制备及其热性能

以正硅酸乙酯为前驱体,采用无溶剂水解技术,制备出了均一、稳定、透明的SiO_2溶胶,通过透射电子显微镜分析,粒径在100 nm左右;在溶胶中加入甲基丙烯酸甲酯(MMA)和偶氮二异丁腈(AIBN),采用热固化制备了透明的块体PMMA/SiO_2杂化材料,通过差热(DSC)和热重分析(TGA)研究了杂化材料的热性能. DSC结果表明,当体系中的SiO_2质量分数超过20%时,杂化材料无明显的玻璃化转变现象. TGA结果表明,杂化材料的分解温度提高约110 ℃. 透射电子显微镜观察结果表明,无机相均匀分散在有机相中,两相之间没有明显的相分离现象.     

热重分析-傅里叶变换红外光谱法分析无机物填充高分子复合材料的组分

采用热重分析-傅里叶变换红外光谱(TGA-FTIR)联用技术分析无机物填充高分子复合材料的组分。将试样研磨至粒径为0.1~0.5mm,取样品13~15mg,均匀装填于TGA样品盘中,以15℃·min-1升温速率进行热重分析,同时采用50mL·min-1氮气吹扫流量将热分解后析出气体导入傅里叶变换红外光谱仪进行分析。通过解析红外光谱图,鉴别了样品中无机填充物及高分子基质的组分;分析热重曲线,测定了各组分含量,测定结果的相对标准偏差为2.92%;分析比对红外光谱的Gram-Schmidt正交重构图和热重分析的失重百分比-温度微分曲线,评价了热重-红外光谱的联用效果。     

微孔聚乳酸支架材料的热稳定性与动态热机械特性

采用无溶剂二氧化碳固态发泡技术,在2.5、3.5、4.0和5.0 MPa饱和压力下制备了泡孔孔径为350-20μm的聚乳酸支架材料.利用热重分析技术、动态热机械分析技术和扫描电子显微镜技术,测定了材料的起始分解温度、分解速率、储存/损耗模量和损耗因子等参数,并利用Kissinger、Ozawa-Doyle和Vyazovkin方程进行了热分解动力学计算,推算了氮气环境下材料的降解时间和使用寿命.结果表明,随着发泡压力的减小,支架材料的泡孔孔径增大,材料的柔韧性增强,表观活化能降低,降解时间缩短.     

热分析联用技术在高分子材料热性能研究中的应用

主要综述了热重-傅里叶变换红外(TG-FTIR)、裂解-色谱/质谱(Py-GC/MS)以及热重-质谱(TG-MS)三种常见的热分析联用技术的测试方法、原理,近几年这几种方法在高分子材料热性能研究中的应用进展和成果表明它们为材料的热分解过程和机理的探索提供了切实可行的研究方法,文章最后还展望了这些方法在热分析技术发展中的重要前景。     

聚苯乙烯纳米微球的合成及摩擦学行为的研究

用乳液聚合法合成了聚苯乙烯纳米微球 ,并对其进行透射电镜 (TEM)、热重 (TGA)、及差热 (DSC)等性能表征。在四球实验机上研究了其摩擦学行为 ,结果表明 ,高分子纳米粒子有良好的减摩、抗磨性能。     

二氢杨梅素对高分子材料的抗氧化作用

通过差示扫描量热仪(DSC)和热失重分析仪(TGA)测定了二氢杨梅素(DMY)的热稳定性。测定了添加DMY的不同高分子材料的氧化诱导温度(OIT*),并与添加相同质量分数工业抗氧剂Irganox B215的样品进行了比较。实验结果表明,DMY在230℃以下稳定性良好,可用于加工温度低于230℃的各种高分子材料的加工过程,添加DMY的各种高分子材料的抗氧化性能优于添加Irganox B215的样品。对其抗氧化作用机理分析表明,DMY的特殊结构,特别是分子中羟基的数量和位置是其具有强抗氧剂性的根本原因。DMY无毒、高效,有望作为新型天然抗氧剂得到广泛应用。     

高分子结晶和熔融行为的Flash DSC研究进展

近年来,作为常规示差扫描量热仪(DSC)技术的发展,商业化的快速扫描芯片量热技术(fast-scan chip-calorimeter,FSC)对推动高分子结晶学研究进展发挥了重要的作用.本文首先介绍了闪速示差扫描量热仪Flash DSC的研发历程及其对高分子结晶样品的测试技术,然后举例介绍了其在高分子结晶和熔融行为研究中的一些应用,包括总结晶动力学、晶体成核动力学、成核剂和填料对结晶的影响、共聚单元对结晶的影响、多重熔融峰的鉴定、折叠链片晶的不可逆和可逆熔化、以及极性大分子晶体的熔融等.Flash DSC极大地扩展了扫描温度速率范围,使得其研究的时间窗口能与实际高分子材料加工过程和计算机分子模拟的时间窗口相互匹配,所提供的综合信息有助于我们更好地理解高分子结晶、退火和熔融行为的微观机理.     

新颖表面结构的脲醛树脂-聚丙烯酰胺复合微球的制备研究

将高分子微凝胶模板法应用于制备脲醛树脂[Urea-formaldehyde resin (UF Resin)]-聚丙烯酰胺[Polyacrylamide (PAM)]有机-有机复合微球材料. 以PAM高分子微凝胶为模板, 通过控制甲醛和尿素的缩聚反应在反相悬浮体系中进行, 制备得到了具有新颖表面形貌的脲醛树脂-聚丙烯酰胺[UF Resin/PAM]有机-有机复合微球, 利用扫描电子显微镜(SEM)、热重分析(TGA)、红外(FT-IR)等手段对复合微球进行了表征. 实验结果表明, 复合微球的表面形貌与甲醛和尿素溶液的pH值、甲醛和尿素溶液的浓度、甲醛和尿素的摩尔比、模板的组成等因素有关. 可以预期, 本研究方法将为制备具有特异表面形貌的有机-有机复合微球材料提供了一条有效的途径.     

单体结构对全息聚合物分散液晶光栅稳定性的影响

使用3种不同化学结构的单体材料制备了全息聚合物分散液晶光栅,并从光栅形貌、衍射能力、驱动特性、聚合物热稳定性4个方面评价了光栅的热稳定性.研究发现,含有刚性结构单体材料体系的光栅形貌、衍射能力等方面在200℃的温度下没有明显变化.表明光栅的热稳定性与单体材料的化学结构密切相关,单体材料中含有刚性结构有助于光栅热稳定性的提高.利用热重分析(TGA)对光栅中聚合物材料热分解温度进行了测定,并结合Freeman-Carroll微商法计算出了上述聚合物的分解活化能和分解反应级数.结果发现,含有刚性结构的聚合物材料的热分解温度、分解活化能和分解反应级数都高于柔性链结构材料,进一步验证了材料体系中刚性结构的添加有助于提高光栅的热稳定性.     

Effect of thermal annealing on synthetic sodium oxalate crystals

The thermal stability of sodium oxalate (Na₂C₂O₄) has been analyzed in the range of room temperature and 900 °C by different techniques. All of them, namely (i) environmental scanning electron microscopy (ESEM); (ii) differential-thermal analysis with simultaneous thermo-gravimetry (DTA-TG); (iii) temperature programmed decomposition mass spectrometry (TDP-MS); (iv) X-ray diffraction with heating stage (HS-XRD); (v) temperature programmed Raman spectroscopy (TP-Raman); and (vi) thermoluminescence (TL), provide information about the changes induced by thermal treatments. Thus, dehydration, decomposition, phase transition, decarbonylation, dissociation or lattice stress are some of the processes here described.     

Hyphenated techniques of thermal analysis for characterisation of soil humic substances

Our aim was to investigate the thermal behaviour of humic substances extracted from temperate and tropical soils by means of hyphenated techniques of thermal analysis (e. g. simultaneous thermal analysis DSC/TG coupled with mass spectrometry, MS, for the analysis of evolved gas, EGA) in order (i) to verify whether the chemical composition of isolated humic substances also reflected the differences in microbial parameters previously measured in related soil samples and (ii) to identify suitable indices of thermal stability. Our results show that the investigation of humic substances by thermal methods can provide information on soil organic matter dynamics. Differences in thermal behaviour between the two groups of soils were found. The indices of thermal stability here proposed, IR (index of thermal recalcitrance), and ID (index of thermal decomposability) clearly showed that in humic substances from tropical soils the thermally recalcitrant organic fraction dominated, whilst in temperate humic substances the opposite held. This agrees with previous results on the microbial dynamics and organic matter turnover of the respective soils and indicates that these indices of thermal stability could represent a useful tool in soil environmental quality investigations.     

Rh(III), Pd(II), Pt(IV) and Au(III) complexes of 2-thiopyrimidine derivatives

Some news thiopyrimidine derivatives and complexes [4-amino-5-nitroso-6-oxo-1,2,3,6-tetrahydro-2-thio-pyrimidine (TANH), its 2-methylthio derivative (MTH), the ammonium salt ofTANH (sTANH) and six new complexes of formulas: Rh(MT)₂Cl · 2H₂O, Pd(MTH)₂Cl₂, Pt(MTH)₂Cl₄, Au(MTH)Cl₃ Pd(TANH)₂Cl₂ and Au(TAN ^–)Cl] have been synthesized and characterized by elemental analysis, IR and¹H-NMR spectroscopy techniques. The thermal behaviour of all compounds has also been studied.

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Rh(III), Pd(II), Pt(IV) und Au(III) Komplexe von 2-Thiopyrimidin Derivaten

Zusammenfassung Es wurden einige neue Thiopyrimidinderivate und deren Komplexe synthetisiert und mittels Elementaranalyse, IR und¹H-NMR charakterisiert: 4-Amino-5-nitroso-6-oxo-1,2,3,6-tetrahydro-2-thio-pyrimidin (TANH), dessen 2-Methylthio-Derivat (MTH), das Ammoniumsalz vonTANH (sTANH) und sechs neue Komplexe der Formeln Rh(MT)₂Cl · 2H₂O, Pd(MTH)₂Cl₂, Pt(MTH)₂Cl₄, Au(MTH)Cl₃, Pd(TANH)₂Cl₂ und Au(TAN ^–)Cl. Das thermische Verhalten der Verbindungen wurde ebenfalls untersucht.

     

Thermal decomposition process of silver behenate

The thermal decomposition processes of silver behenate have been studied by infrared spectroscopy (IR), X-ray diffraction (XRD), combined thermogravimetry-differential thermal analysis-mass spectrometry (TG-DTA-MS), transmission electron microscopy (TEM) and UV-vis spectroscopy. The TG-DTA and the higher temperature IR and XRD measurements indicated that complicated structural changes took place while heating silver behenate, but there were two distinct thermal transitions. During the first transition at 138 °C, the alkyl chains of silver behenate were transformed from an ordered into a disordered state. During the second transition at about 231 °C, a structural change took place for silver behenate, which was the decomposition of silver behenate. The major products of the thermal decomposition of silver behenate were metallic silver and behenic acid. Upon heating up to 500 °C, the final product of the thermal decomposition was metallic silver. The combined TG-MS analysis showed that the gas products of the thermal decomposition of silver behenate were carbon dioxide, water, hydrogen, acetylene and some small molecule alkenes. TEM and UV-vis spectroscopy were used to investigate the process of the formation and growth of metallic silver nanoparticles.     

钼钒砷杂多酸有机铵盐的合成及热稳定性研究

合成了4个系列（14种）钼钒砷有机铵盐,用红外光谱、pH电位滴定、DAT－TG对其进行表征,确认其分子式为[RnNH4-N]4[HPA](R=Me、Et、Pr、Bu基;n＝1、2、3、4）;并采用DTA－TG、IR进行系列盐分步切断的热性质研究。发现其稳定性随烷基增大、取代基数目增多而增加;且盐的分解是分步进行的,最终产物为杂多阴离子的组成氧化物。     

Crystallization properties and thermal stability of polypropylene composites filled with wollastonite

The influence of wollastonite (CaSiO₃) content on the crystallization properties and thermal stability of polypropylene (PP) composites was investigated. The results showed that the crystallization temperature, crystallization end temperature and crystallization temperature interval, as well as the degree of crystallinity of the composites, were higher than those of the unfilled PP resin, while the crystallization onset temperature was little changed from that of the unfilled PP resin. The increase of degree of crystallinity for the composites could be attributed to the heterogeneous nucleation of the CaSiO₃ in the PP matrix. The thermal stability increased with increasing filler weight fraction (ϕ_f); the thermal decomposition rate decreased nonlinearly with increasingϕ_f. Finally, the dispersion of the filler particles in the matrix was observed, and the mechanisms of thermal stability and crystallizing behavior were discussed.     

热分析-傅里叶变换红外光谱-气相色谱-质谱联用测定葡萄糖的热分解产物

应用热分析-傅里叶变换红外光谱-气相色谱-质谱联用测定葡萄糖的热分解产物。葡萄糖样品在同步热分析条件下,分别在氮气和氮氧混合气氛围中进行热解,同时进行红外扫描,根据样品的热重曲线和红外谱图进行判定和选择GC-MS温度点,裂解产物进入GC-MS进行分离和鉴定。结果表明:葡萄糖在220℃,300℃,350℃和470℃下的热分解产物中共检出44种化合物;葡萄糖在高温下的热裂解产物中共检出76种化合物。分析结果对葡萄糖在不同温度下的应用有较好的理论指导。     

Thermal degradation of polymethylsilsesquioxane and microstructure of the derived glasses

The present work aims to elucidate the physicochemical factors determining the microstructure of Si-O-C glasses derived from a polymethylsilsesquioxane powder pyrolyzed at 200-1300 °C in helium atmosphere. The pyrolysis behavior of the powder was studied by thermogravimetry coupled with mass spectrometry. The chemical composition of the glasses was determined by elemental analysis while the microstructure was studied by optical microscopy combined with scanning and transmission electron microscopy. The degradation of the polymer proceeds by a three-stage decomposition characterized by different mass losses as well as by different amount and type of evolved gaseous species. The derived glasses contain networks of pores and bubbles with diameters more than 0.1 mm. The increasing thermal treatment of the polymer above 200 °C does not lead to the disappearance of macropores. Micrometer-sized amorphous filaments are observed in porous interiors. A formation mechanism of pores and filaments is proposed. Polymer swelling accompanied by pore coagulation and gas release is believed to be responsible for the spatial separation of oligomers forming filaments.     

Spektroskopisches und thermisches Verhalten von K4H2[S2I2O14]

The infrared andRaman spectra of the tittle compound have been recorded and an assignment for the internal vibrations of the H₂S₂I₂O ₁₄ ^4– polyanion is proposed. The thermal behaviour was investigated using TG-, DTA-, IR- and X-ray methods; it is shown that the polyanion breaks down after the release of one mole of H₂O, generating a mixture of -K₂SO₄ and I₂O₅.

     

Quantification of hindered phenols in polyamide 11 during thermal aging

Polyamide 11 films stabilized by Irganox^® 1098, Irganox^® 1010 or Irganox^® 245 were subjected to thermal oxidation at 110 °C. The residual phenol content was assessed by comparing three analytical methods: high performance liquid chromatography (HPLC), determination of the Oxidation Induction Time (OIT) and Onset Oxidation Temperature (OOT) by thermal analyses. Both OIT and OOT are reliable for virgin PA11 after a relevant calibration by HPLC measurement. In the case of oxidized samples, OOT measurements have the benefits of being more easily interpretable than OIT and less time-consuming than HPLC measurements.