Effect of preparation conditions on the thermal stability of an epoxy-functional inorganic-organic hybrid material system with phenyl side group

A hybrid material system consisting of (3-glycidyloxypropyl)trimethoxysilane and dimethyldimethoxysilane as matrix materials and diphenyldimethoxysilane (DPDMS) as both a matrix material and a potential thermal stabiliser by the sol-gel method. A detailed thermogravimetric analysis study of the influence of processing parameters, including DPDMS content, UV irradiation and sol ageing, on the thermal stability of the resultant thin films was presented. FT-IR spectroscopy was used to monitor the changes in the relative amount of epoxy rings in the system during processing. It was demonstrated that the crosslinking of epoxy groups in the structure is the primary reason for changes in the thermal stability of the system. It was also shown that the thermal stability, in terms of 10% mass loss, of the material system could be improved up to 280 °C, by adjusting the preparation conditions, compatible with several subsequent high temperature optoelectronic integration processes.     

Effect of preparation conditions on the thermal stability of an epoxy-functional inorganic-organic hybrid material system doped with Zr

An inorganic-organic hybrid material system consisting of (3-glycidyloxypropyl)trimethoxysilane, dimethyldimethoxysilane and zirconium(IV) n-propoxide was prepared by the sol-gel method. The influence of processing parameters including Zr content, UV irradiation and sol ageing on the thermal stability of the resultant thin films was characterised by thermogravimetry. It was demonstrated that the crosslinking of epoxy groups in the structure was the primary reason for variation in the thermal stability of the system. As Zr and/or UV irradiation may be employed to crosslink the epoxy groups in the structure, the thermal stability of the system can be tuned by the optimal combination of these two crosslinking methods.     

Improving thermal stability of biodegradable aliphatic polycarbonate by metal ion coordination

Poly(propylene carbonate) (PPC), a typical aliphatic polycarbonate, has attracted much attention during the last two decades due to its biodegradability and commercializing perspective. However, the application of this material as thermoplastics has been limited by its poor thermal stability. Metal soaps, such as calcium stearate (CaSt₂), are important processing additives in plastics industry. In the present work, PPC-CaSt₂ complexes were prepared, the thermal stability of which was investigated by thermogravimetric analysis (TGA). The results show that the complexes are more thermal stable than pure PPC material. Supramolecular lamellar mesomorphous structures of the complexes were corroborated by the combination of small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM) and polarizing optical microscopy (POM). Metal ion coordination of CaSt₂ to flexible PPC chains was determined by Fourier transform infrared spectroscopy (FT-IR). This coordination interaction plays the key role in improving the thermal property of PPC and constructing the self-organized structure of the complexes.     

Effect of thermomechanical processing on the thermal stability of amorphous Fe-B alloys

Results from investigating the effect of thermomechanical processing on the thermal stability of amorphous Fe-B alloys are presented. It is shown that the combined thermomechanical processing of amorphous alloys raises the temperature of intense crystallization onset by 80 K for binary alloys; by 20–50 K, for multicomponent alloys. The greater expansion of the thermal stability interval of binary alloys relative to multicomponent alloys is explained by the presence of alloying dopants such as molybdenum, nickel, and silicon that inhibit the diffusion of boron and thus hinders nucleation and the growth of the crystalline phase. The enhanced thermal stability of amorphous alloys induced by thermomechanical processing is explained by the reduction in size of amorphous-phase frozen crystallization centers and by the formation of a nanostructured state.     

Evaluation of a glycerol derived biofuel by thermal analysis

This work describes thermal analysis evaluation of a glycerol derived compound (fatty acid esters of (2,2-dimethyl-1,3-dioxolan-4-yl) methanol) developed to work as a biofuel. Mixtures of these ketal–glyceryl esters with fatty acid methyl esters typical of soybean biodiesel were prepared and evaluated in relation to biodiesel critical thermal properties such as temperature of crystallization, thermal stability and volatilization measured by differential scanning calorimetry and thermogravimetric analysis. The volatility of the products containing fatty acid methyl esters and (2,2-dimethyl-1,3-dioxolan-4-yl) methyl esters could be predicted by thermogravimetric analyses conducted in nitrogen that avoided time consuming distillation and greatly reduced material expenditure.     

A review on the thermal stability of calcium apatites

High temperature processing is essential for the preparation of apatites for biomaterials, lighting, waste removal and other applications. This requires a good understanding of the thermal stability and transitions upon heating. The most widely used is hydroxyapatite (HAp), but increasing interest is being directed to fluorapatite (FAp) and chlorapatite (ClAp). The structural modifications for substitutions are discussed to understand the temperature processing range for the different apatites. This is based on a review of the literature from the past few decades, together with recent research results. Apatite thermal stability is mainly determined by the stoichiometry (Ca/P ratio and structural substitutions) and the gas composition during heating. Thermal stability is lowered the most by a substitution of calcium and phosphate, leading to loss in phase stability at temperatures less than 900?°C. The anions in the hexagonal axis, OH in HAp, F in FAp and Cl in ClAp are the last to leave upon heating, and prevention of the loss of these groups ensures high temperature stability. The information discussed here will assist in understanding the changes of apatites during heating in calcination, sintering, hydrothermal processing, plasma spraying, flame pyrolysis, and other high-temperature processes.     

Unexpected selective enhancement of the thermal stability of aromatic polyimide materials by cerium dioxide nanoparticles

The unusual effect of selective enhancement of the thermal stability of aromatic polyimide materials was established through the introduction of cerium dioxide nanoparticles into these polymers as nanofiller. Depending on the chemical structure of the polymers, a marked increase or a substantial decrease in the thermal stability of the nanocomposite material was registered by thermal analysis, as compared with that of unfilled polymer material. The positive effect was registered only for the composite materials based on the matrix polyimides containing the sulfur atoms located in the sulfonic groups arranged in the elementary units. The results of the thermogravimetric examination are compared with the data obtained during the mechanical tests of the same samples. The possible reasons for the alteration of the thermal stability of polymers by ceria nanoparticles are discussed. The effect above can be of substantial practical interest providing new options for the design of polyimide nanocomposite materials with enhanced thermal stability.     

Dramatic thermal stability of virus-polymer conjugates in hydrophobic solvents

We have developed a method for integrating the self-assembling tobacco mosaic virus capsid into hydrophobic solvents and hydrophobic polymers. The capsid was modified at tyrosine residues to display an array of linear poly(ethylene glycol) chains, allowing it to be transferred into chloroform. In a subsequent step, the capsids could be transferred to a variety of hydrophobic solvents, including benzyl alcohol, o-dichlorobenzene, and diglyme. The thermal stability of the material against denaturation increased from 70 °C in water to at least 160 °C in hydrophobic solvents. With a view toward material fabrication, the polymer-coated TMV rods were also incorporated into solid polystyrene and thermally cast at 110 °C. Overall, this process significantly expands the range of processing conditions for TMV-based materials, with the goal of incorporating these templated nanoscale systems into conductive polymer matrices.     

苯并三呋咱氧化物中主要杂质对其热安定性的影响

根据苯并三呋咱氧化物（BTF）中主要杂质的种类，分别选择了三叠氮三硝基苯（TNTAB）、三氯三硝基苯（TCTNB）和叠氮化钠（NaN3)作为杂质研究对象，采用机械混合的方法制备了一系列不同配比的BTF混合物，再通过差热（DTA）、差示扫描量热（DSC）、真空安定性试验（VST）、布氏压力法、热失重、5s爆发点等热分析方法进行测试，结果表明TCTNB和NaN3对BTF热安定性影响较小，而TNTAB是影响BTF热安定性的主要因素。     

Chlorinated thermal stabilizer for optically clear PMMA

Optically clear poly(methyl methacrylate) (PMMA) blends with HET‐EG oligoester (synthesized by condensation of chlorendic acid with ethylene glycol) at six different compositions were prepared by bulk polymerization. The effect of HET‐EG in the PMMA matrix on the optical clarity of PMMA blend was measured using ultraviolet‐visible spectroscopic study. The thermal stability of PMMA blends was investigated using differential scanning calorimetric (DSC) and thermogravimetric (TG) analyses. The parameters to deduce the thermal stability of pure PMMA and PMMA blends were calculated from DSC and TG results. The thermal stability of PMMA was found to increase effectively by loading 5% of HET‐EG oligoester without marring optical clarity. The probable physical and chemical actions of HET‐EG oligoester on the thermal stability of PMMA are discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

Evaluation of thermal stability,an overview

A systematic application of thermal analytical techniques for the assessment of the thermal stability of a material is emphasized. This approach employs ASTM E-27.02 (Methods of Test) and is illustrated using a sulfur—nitrogen heterocyclic compound model.     

Evaluation of the thermal stability of some nonlinear optical chromophores

Optical data storage is poised to benefit from a new class of advanced polymeric materials engineered to exhibit photorefractivity. Likewise, the transmission and processing of data will also benefit from a related class of materials with electro-optic activity. Organic chromophores are critical constituents of these materials which function due to a change of index of refraction in response to an electric field. However, a number of materials and processing problems remain to be solved before devices incorporating these optically nonlinear chromophores are practical. For example, for electrooptical applications the NLO waveguide should be able to withstand short duration processing temperatures in excess of 300°C and long duration use temperatures of at least 80°C. The requirement for thermochemical stability follows from the need to implement highT _g matrices to provide stability of the orientational or polar order required for long-term device performance and reliability. As a result, the thermal stability of chromophores is now more closely evaluated in addition to their transparency and optical nonlinearity properties. Some chromophore classes, such as the azo dyes studied here, have attractive properties for these applications but further enhancements in overall properties are needed. Identification of the fundamental chemical processes in thermal decomposition of these dyes should lead to introduction of structural changes which provide better stability. Here thermogravimetric analysis (TGA) coupled with mass spectrometry (TGA/MS) is used to provide an assay of thermochemical stability with an added benefit that insight into the mechanisms of thermal decomposition may by identified. In this initial study diaryl substitution of the amine in derivatives of 4-amino-4-nitroazobenzene was observed to greatly enhance thermal stability relative to dialkyl substitution. Substitution of phenyl for alkyl eliminates structural features involved in the most facile degradation mechanism available to the alkyl derivative.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthdayThe authors acknowledge contributions by colleagues at IBM including H. Truong and R. Siemens for the thermal analysis. This work was supported by the Air Force Office of Scientific Research and the National Institute of Science and Technology Advanced Technology Program.     

Review on the chemical and thermal stability of stationary phases for reversed-phase liquid chromatography

At present, in high-performance liquid chromatography (HPLC) for the majority of analyses, reversed-phase liquid chromatography (RPLC) is the separation mode of choice. Faster method development procedures using aggressive eluents under elevated temperature conditions, the need for improved selectivities, efficiencies and resolution, the reduction of solvent consumption and also the decrease of analysis times require reversed-phase (RP) columns of high chemical and thermal stability. Until now, the majority of columns for RPLC separations are manufactured from silica substrates. Silica has many favorable properties making this material nearly ideal as a support for RP columns. However, its solubility, that increases considerably in eluents of pH above +/-7, is a drawback preventing its widespread use over the entire pH range. In addition, also the thermal stability of silica is limited. Recently, however, substantial progress has been made in the synthesis of RPLC silica-based stationary phases showing satisfactory thermal and chemical stability under many different experimental conditions. Also, new substrates mainly based on other inorganic substrates like, e.g. alumina and zirconia have been developed now as a starting material for the preparation of RPLC stationary phases of improved chemical and thermal stability. In addition, for the same reasons, many efforts have also been made to synthesize polymer and also polymer-coated phases. These latter phases, more particularly those based on zirconia, but also polymer phases show a high degree of chemical and thermal stability compared to silica counterparts. In this paper, an overview will be given of the state-of-the-art of the thermal and chemical stability of the different available stationary phases for RPLC.     

Effect of stearate preheating on the thermal stability of plasticized PVC compounds

Effect of preheating of stearates on the processing and post-processing thermal stability of poly(vinyl chloride) compounds, plasticized with di(2-ethylhexyl) phthalate (DEHP) and epoxidized soybean oil (ESO), using several ratios of calcium/zinc stearates and DEHP/ESO is reported. The compounds were prepared as follows: (1) dry-blending the compound components, (2) pelletizing the dry-blend and (3) extruding the pellets to obtain a ribbon geometry. Processing stability was determined by: (a) mechanical characterization and (b) visual color comparison of extruded samples. Post-processing thermal stability was followed by: (a) measurement of HCl release from heated pellets and (b) color changes in heated ribbon samples. From a practical point of view, the preheating has a negligible effect on the initial color of formulations; except for the case of formulations without both ESO and CaSt₂. However, the effect of the preheating on the post-processing thermal stability is strongly determined by the composition formulation.     

Structural characterization and thermal decomposition of layered double hydroxide/poly(p-dioxanone) nanocomposites

Nanocomposites based on layered double hydroxides (LDH) and poly(p-dioxanone) (PPDO) were prepared by melt processing using dodecylbenzene sulfonate (DBS) and 4-hydroxybenzene sulfonate (HBS) as organic modifiers. The incorporation of organic anions in LDH was demonstrated by wide-angle X-ray scattering (WAXS) and Fourier transform infrared (FTIR). The dispersion degree of the organically modified LDHs in the PPDO matrix was analyzed by WAXS, indicating that only the LDH modified with HBS was exfoliated. The effect of the organically modified LDHs on the thermal stability of PPDO was studied using thermogravimetric analysis (TGA). The thermal stability of PPDO matrix was enhanced by the incorporation of the LDH modified with HBS due to the shielding effect of the exfoliated layers. In contrast, the LDH modified with DBS produced a decrease of the thermal stability of PPDO, probably due to hydrolytic decomposition of ester group. The thermogravimetric analysis also showed that the organo-modified LDH did not modify the thermal decomposition mechanism of the polymer, but had an effect on the thermal stability.     

Solid-state processing of phb-powders

Poly(3-hydroxybutyrate) (PHB) is a completely biodegradable polyester, produced by bacterial fermentation. Because of poor thermal stability, melt processing of the material is accompanied by thermal degradation and poor mechanical properties. To prevent thermal degradation, a solid-state processing technology has been applied. The extrusion of PHB-powder at temperatures far below the melting point leads to products of improved mechanical properties. In particular, the ductility of the material increases considerably compared to traditional melt processed PHB. The improved mechanical properties have been attributed to structural differences on the molecular and supermolecular level.     

Catalytic thermal oxidation of phenolic antioxidants by hindered piperidine compounds

The interactions of two hindered piperidine compounds, bis(2,2,6,6,-tetramethyl-4-piperidinyl) sebacate and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxy, with various phenolic antioxidants, during the thermal processing of polypropylene have been examined using ultraviolet-visible absorption, infra-red and ESR techniques. Evidence is presented to show that the stable N-oxy radical generated during thermal processing catalytically oxidises phenolic antioxidants to their corresponding quinone forms. The implications of this interaction, particularly with regard to its effect on light stability, are discussed.     

Cross-property interaction between stiffness,damage and thermal conductivity in particulate nanocomposite

A nanocomposite made from epoxy and nano silica particles was subjected to compressive fatigue loading and the resulting interaction between stiffness, damage and thermal conductivity investigated. First, the thermal conductivity (K) and the elastic modulus (E) of the as-fabricated materials were measured prior to any fatigue loading. Then, the samples were subjected to cyclic loading, and the thermal conductivity and the modulus of elasticity of the specimens were measured after every 5 to 10 thousand cycle intervals until a significant change in the response of the material was observed. In addition, a semi-analytical model is proposed to quantify damage in the material by taking the modulus of elasticity and thermal conductivity data obtained from the experiment. Finally, the cross-property relation between the modulus of elasticity, the thermal conductivity and the damage density in the material at any state of the fatigue cycle is investigated.     

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.     

Measurement of oxidation stability of polyolefins by thermal analysis

Isothermal differential thermal analysis has been used to study the thermal stability of polybutene and crosslinked polyethylene in the temperature range from 120°C to 240°C. Oxidation induction times were measured from 2 min up to 7250 h. The Arrhenius-plots of DTA results showed curvature at 150°C, so straight line extrapolations from short-term experiments at elevated temperatures to low temperatures and long times are not possible. Oxidation induction time and mechanical failure in oven ageing experiments coincided over the measured temperature range. Decrease in the molecular weight of polybutene accelerated after the end of the induction period.Thermoanalytically measurable residual thermal stability decreased linearly with ageing time and is a more sensitive indicator of the beginning of thermal degradation than measurement of tensile properties. Finally, the extraction of stabilizer by hot water was measured by isothermal DTA.