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.     

Calorimetry and thermogravimetry as tools for the assessment of the thermal stability of polyoxide-based nonionic surfactants

Differential scanning calorimetry (DSC) and thermogravimetry (TGA) have been used to evaluate the thermal stability of nonionic surfactants. We have studied monofunctional diblock copolymers of poly(ethylene oxide-propylene oxide) (R-PEO–PPO–OH, where R length is linear C₄ or C_12–14) as nonionic surfactants. It was observed that the thermal stability was dependent on the copolymer structure. Moreover, the higher the EO/PO ratio in the copolymers the higher the oxidative thermal stability. The autoxidation exhibits exothermic behaviour and the enthalpy related to the process depends on the EO/PO ratio. The initial temperatures of degradation obtained from DSC and TGA were in agreement.     

Novel methacrylate copolymers with fluorine containing: Synthesis, characterization, reactivity ratios, thermal properties and biological activity

New methacrylate based monomers 2-(4-benzoylphenoxy)-2-oxoethyl-2-methylacrylate (BOEMA), 2-(4-acetylphenoxy)-2-oxoethyl-2-methylacrylate (AOEMA), and 2-[(4-fluorophenyl)amino]-2-oxoethyl-2-methylacrylate (FPAMA), were synthesized first time. The free-radical-initiated copolymerization of AOEMA and BOEMA with FPAMA were carried out in 1,4-dioxane solution at 65 °C using 2,2′-azobisisobutyronitrile (AIBN) as an initiator with different monomer-to-monomer ratios in the feed. The monomers and copolymers were characterized by FTIR, ¹H NMR and ¹³C NMR spectral studies. The copolymer compositions were evaluated by nitrogen content in polymers. The reactivity ratios of the monomers were determined by the application of Fineman-Ross and Kelen-Tudos methods. The analysis of reactivity ratios revealed that BOEMA and AOEMA are less reactive than FPAMA, and copolymers formed are statistically in nature. The molecular weights ( and ) and polydispersity index of the polymers were determined using gel permeation chromatography. Thermogravimetric analysis of the polymers reveals that the thermal stability of the copolymers increases with an increase in the mole fraction of FPAMA in the copolymers. Glass transition temperatures of the copolymers were found to decrease with an increase in the mole fraction of FPAMA in the copolymers. The prepared homo and copolymers were tested for their antimicrobial activity against bacteria, fungi and yeast.     

Tailored crystallization behavior,thermal stability,and biodegradability of poly(ethylene adipate): Effects of a biocompatible diamide nucleating agent

An eco-friendly linear organic diamide derivative (EBH) acting as a nucleating agent (NA) was incorporated into the biodegradable poly(ethylene adipate) (PEA) polyester to prepare a kind of new biocompatible composite. The differential scanning calorimetry (DSC) measurement of PEA showed that crystallization temperature (T_c) and crystallization rate increased significantly and crystallization time (t) reduced markedly upon incorporation of EBH. The hydrogen bond interaction existed between PEA and EBH, resulting in the uniform dispersion of EBH in the PEA matrix. In the in situ FTIR test, PEA showed a higher crystallization rate during isothermal crystallization in the presence of EBH. The adjustment rate of the PEA –CO group in the presence of EBH was lower than that of the –C-O-C and –CH₂ groups, also caused by the hydrogen bond interaction between PEA and EBH. In the TG analysis, EBH enhanced the thermal degradation temperature of PEA. Enzymatic degradation of PEA slowed down upon incorporation of EBH. Mechanisms on the nucleation, increased thermal stability, and decreased enzymatic degradation rate of PEA in the presence of EBH have also been proposed and discussed.     

Thermal stability of polyurethanes

Summary The combined application of thermogravimetry reactiongas chromatography and gel-permeation chromatography permits to follow the heat degradation of polyurethane polymers in inert gas, air and water-saturated environment. The examinations give information on the rate of thermal degradation, the individual volatile degradation components, the critical points of the polymer chains and on the change of their molecular-weight distribution. Gas chromatographic examinations also permit the identification of the chain-extending components of different types of polyurethanes.     

Effect of fluorine functional groups on surface and mechanical interfacial properties of epoxy resins

To improve the surface and mechanical interfacial properties of epoxy resins, fluorine-containing epoxy resin (FEP) was prepared and blended with a commercially available tetrafunctional epoxy resin (TGDDM). As a result, when the fluorine content increased, the total surface energy of TGDDM/FEP blends was gradually decreased, while the water repellency of the blends was increased. The glass transition temperature and thermal stability factors of the blends showed maximum values at 20-40 wt% FEP compared with neat TGDDM epoxy resins. And the mechanical interfacial properties of the blend specimens were significantly increased with increasing the FEP content, which could be attributed to the intermacromolecular interactions in the cured TGDDM/FEP blends. These results indicate that the water repellency and toughness improvements have been achieved without significantly deterioration of the thermal properties in the TGDDM/FEP blends.     

Thermogravimetric study of some crosslinked copolymers based on poly(acrylonitrile-co-divinylbenzene)

Copolymer networks based on acrylonitrile (AN)/divinylbenzene (DVB) have been investigated by thermogravimetric analysis (TG) to evaluate their thermal stability in nitrogen atmosphere. Thermal stability was determined from TG-DTG curves to investigate the influence of AN and DVB in the synthesis of copolymers on the copolymer thermal properties. The TG and DTG curves of copolymers clearly show two thermodegradation stages. The solid residues produced after thermodegradation stages were analyzed by FTIR and elemental analysis (CHN). The decomposition temperatures were dependent on amount of AN and DVB used as the crosslinking agent. The degradation temperatures of copolymers were influenced by the diluent system during their synthesis. FTIR analyses indicate that the cyclization of the polymer proceeds before any mass loss.     

Improved thermal stability of polybenzoxazines by transition metals

The incorporation of various transition metal salts increases the char formation of polybenzoxazines. It is shown that the effect of the transition metal salt is not simply additive and is independent of the amine and phenol structures. While the metal salts have an insignificant effect on the polymerization, their presence in benzoxazine favors the formation of carbonyl functional groups. It is proposed that reduced flammability of polybenzoxazines is achieved through the evolution of CO₂ during thermal degradation.     

The comparison of thermal stability of some hydrofluoroethers and hydrofluoropolyethers

The thermal stability of representative hydrofluoropolyether (HFPE) and hydrofluoroether (HFE) compounds has been evaluated. The observed stability order appears to be correlated with the nature of the hydrogenated chain ends; in particular, molecules having fully hydrogenated chain ends (OCH₃ and OC₂H₅) show a significantly lower stability compared with the OCF₂H terminated compounds. The main degradation products suggest, however, that the same primary reaction is responsible for the decomposition of all the compounds examined; this reaction involves the fragmentation of the R_fOC_xH_yF_z bond with fluorine transfer between the two carbon atoms close to the oxygen, leading to the formation of a hydrofluorocarbon C_xH_yF_(z+1) and an acyl fluoride or a ketone.     

Thermal stability of polybenzoxazines with lanthanum chloride and their crosslinked structures

Lanthanum chloride (LaCl₃) was incorporated into five kinds of benzoxazines by different preparation methods. The thermal stability and the structures of polybenzoxazines were characterized by thermogravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy. The evolved gases from the degradation process of polybenzoxazines were analyzed by FTIR. The results showed that the thermal stability and char yields of three kinds of polybenzoxazines containing LaCl₃ can be improved obviously. LaCl₃ has an important effect on the polymerization reactions of benzoxazines. More stable arylamine Mannich bridges were observed in the chemical structures of the polybenzoxazines. It is these structures that can effectively retard the volatilization of aniline derivatives and result in the improvement of the thermal stability of the polybenzoxazines.     

Thermal stability of boron subphthalocyanines as a function of the axial and peripheral substitution

In this work, we have carried out the synthesis and thermogravimetric study of 10 different axially and peripherally substituted boron subphthalocyanines, in order to compare their thermal stabilities under non-oxidizing conditions. We demonstrate that, in general, these compounds enjoy a relatively high thermal stability, a property that is fundamental for future potential applications. The loss of the axial group is usually the first thermal degradation process to occur, and the temperature at which it takes place increases as a function of the nature of this substituent in the order: Br < OH ? OPh ∼ Cl. Peripheral substituents also have an influence on the thermal properties of subphthalocyanines, though their role is somewhat less notable.     

Effects of silphenylene units on the thermal stability of silicone resins

A series of silicone resins containing silphenylene units were synthesized by a hydrolysis-polycondensation method, with methyltriethoxysilane, dimethyldiethoxysilane and 1,4-bis(ethoxydimethylsilyl)benzene. Their thermal degradation behaviours were studied by thermogravimetric analysis (TGA), differential thermogravimetry (DTG) and Fourier-transform infrared (FTIR) spectroscopy, and the effect of silphenylene units on the thermal stability of silicone resins was also investigated. Results showed that the thermal stability of silicone resins was improved by the introduction of silphenylene units into the backbone. Under nitrogen atmosphere, the temperature for maximum degradation rate of silicone resins with silphenylene units was lower compared to the pure methylsilicone resin. With the increase of silphenylene units, the amount of degradation residues increased under nitrogen atmosphere while it decreased under air atmosphere. Additionally, the short-term and long-term stability of silicone resins were also improved by the introduction of silphenylene units.     

Structure and thermal stability of microencapsulated phase-change materials

A series of microcapsules containing n-octadecane with a urea-melamine-formaldehyde copolymer shell were synthesized by in-situ polymerization. The surface morphology, diameter, melting and crystallization properties, and thermal stability of the microcapsules were investigated by using FTIR, SEM, DSC, TGA and DTA. The diameters of the microcapsules are in the range of 0.2–5.6 m. The n-octadecane contents in the microcapsules are in the range of 65–78wt%. The mole ratio of urea-melamine has been found to have no effect on the melting temperature of the microcapsules. Two crystallization peaks on the DSC cooling curve have been observed. The thermal damage mechanisms are the liquefied n-octadecane leaking from the microcapsule and breakage of the shell due to the mismatch of thermal expansion of the core and shell materials at high temperatures. The thermal stability of materials can be enhanced up to 10 °C by the copolymerization of urea, melamine and formaldehyde in a mole ratio 0.2:0.8:3. The thermal stability of 160 °C heat-treated microcapsules containing 8.8% cyclohexane can be further enhanced up to approximately 37 °C.     

Entrainment of cold gas into thermal plasma jets

There is increasing evidence that the entrainment of cold gas surrounding a turbulent plasma jet is more of an engulfment type process rather than simple diffusion. A variety of diagnostic techniques have been employed to determine the development of turbulence in a plasma jet and to measure concentration and temperatures of the cold gas entrained into atmospheric-pressure argon plasma jets in ambient argon or air. The results indicate that the transition to turbulence causes a rapid drop of the axial jet velocity due to entrainment of the cold gas surrounding the plasma jet. Dissipation of the cold engulfed gas bubbles by molecular diffusion is relatively slow if molecular gases (for example air) are entrained, as indicated by conditional sampling and CARS measurements. Temperature measurements using emission spectroscopy and enthalpy probes show strong discrepancies in the jet fringes.     

Synthesis,characterization and thermal stability of novel carborane-containing epoxy novolacs

Carborane bisphenol novolacs(3 and 4) were synthesized in the presence of acid catalyst from carborane bisphenols(5 and 6) and formaldehyde. Further epoxidization of carborane bisphenol novolacs with epichlorohydrin gave carborane bisphenol epoxy novolacs(1 and 2). The molecular weight and epoxy value of obtained resins were determined using the molecular weight of their precursors. The epoxy values of 1 and 2 were 0.48 and 0.52 respectively, higher than the maximum theoretical epoxy value(0.45) of difunctional carborane bisphenol epoxy resins. FTIR and NMR were utilized to characterize 1 and 2. The curing behaviors were also studied by DSC and the optimized curing conditions were obtained.TGA analysis indicated that carborane moiety could shield its adjacent organic structures against initial decomposition. On the other hand, B―H on carborane cage could react with oxygen to form a three-dimensional network linked by B―O―B and B―C bonds, which further blocked the movement of formed radicals and thus the degradation process was inhibited.     

The influence of hematite nano-crystals on the thermal stability of polystyrene

A synthetic procedure based on thermal hydrolysis of iron(III) chloride solutions for the preparation of hematite (α-Fe₂O₃) sol consisting of nano-crystals (NCs) is described. The α-Fe₂O₃ NCs were characterized by transmission electron microscopy and X-ray diffraction measurements. Incorporation of α-Fe₂O₃ NCs into polystyrene (PS) was based on the transfer of α-Fe₂O₃ NCs from the aqueous phase to the organic solvent. A significant shift in the glass transition temperature of PS by 17 °C towards higher temperatures was observed after incorporation of α-Fe₂O₃ NCs. Also, the thermal stability of PS was improved by about 100 °C in the presence of 3.6 wt% of α-Fe₂O₃ NCs.     

Polymer/montmorillonite nanocomposites with improved thermal properties: Part I. Factors influencing thermal stability and mechanisms of thermal stability improvement

The results of recent research indicate that the introduction of layered silicate - montmorillonite - into polymer matrix results in increase of thermal stability of a number of polymer nanocomposites. Due to characteristic structure of layers in polymer matrix and nanoscopic dimensions of filler particles, several effects have been observed that can explain the changes in thermal properties. The level of surface activity may be directly influenced by the mechanical interfacial adhesion or thermal stability of organic compound used to modify montmorillonite. Thus, increasing the thermal stability of montmorillonite and resultant nanocomposites is one of the key points in the successful technical application of polymer-clay nanocomposites on the industrial scale. Basing on most recent research, this work presents a detailed examination of factors influencing thermal stability, including the role of chemical constitution of organic modifier, composition and structure of nanocomposites, and mechanisms of improvement of thermal stability in polymer/montmorillonite nanocomposites.     

Rheology and thermal stability of polylactide/clay nanocomposites

Polylactide/clay nanocomposites (PLACNs) were prepared by melt intercalation. The intercalated structure of PLACNs was investigated using XRD and TEM. Both the linear and nonlinear rheological properties of PLACNs were measured by parallel plate rheometer. The results reveal that percolation threshold of the PLACNs is about 4 wt%, and the network structure is very sensitive to both the quiescent and the large amplitude oscillatory shear (LAOS) deformation. The stress overshoots in the reverse flow experiments were strongly dependent on the rest time and shear rate but shows a strain-scaling response to the startup of steady shear flow, indicating that the formation of the long-range structure in PLACNs may be the major driving force for the reorganization of the clay network. The thermal behavior of PLACNs was also characterized. However, the results show that with the addition of clay, the thermal stability of PLACNs decreases in contrast to that of pure PLA.     

Thermal stability of solid and aqueous solutions of humic acid

The effects of temperature on the stability of a soil humic acid were studied in the present work. Solid samples of Gohy-573 humic acid (HA) and dissolved ones in aqueous solution (pH 6.0, 0.1 mol L⁻¹ NaClO₄) were investigated in order to understand the impact of temperature on the chemical properties of the material. The methods applied to solid samples in the present investigation were thermogravimetric analysis (TGA), temperature-programmed desorption coupled with mass spectrometry (TPD-MS), and in situ diffuse reflectance infrared Fourier transformed spectroscopy (in situ DRIFTS). Humic acid samples were studied in the 25-800 °C range, with focus on thermal/chemical processes up to 250 °C. The reversibility of the changes observed was investigated by cyclic changes to specified temperature ranges (40-110 °C). All measurements were conducted under inert-gas atmosphere in order to avoid samples combustion at increased temperatures. Aqueous solutions were analyzed by UV-vis absorption spectroscopy after storage at temperatures up to 95 °C, and storage times up to 1 week. For temperatures below 100 °C experiments on solid and aqueous samples have shown results which were consistent to each other. The amount of water desorbed is temperature dependent and up to 70 °C this process was totally reversible. Above 70 °C an irreversible loss of water was also observed, which according to UV-vis spectroscopy corresponds to water produced by condensation leading to more condensed polyaromatic structures. The water released up to 110 °C was about 7 wt% of the total mass of the dried humic acid, where less than 50% corresponded to reversibly adsorbed water. At higher temperatures (>110 °C), gradual decomposition resulting in the formation of carbon dioxide (110-240 °C), and carbon monoxide (140-240 °C) takes place. Hence, thermal treatment of Gohy-573 humic acid above 70 °C results in irreversible structural changes, that could affect chemical properties (e.g., complex formation) of the material.     

Effects on the thermal expansion coefficient and dielectric properties of CLST/PTFE filled with modified glass fiber as microwave material

The CLST/PTFE/5%GF composite sharply decreases the CTE in both X&Y and Z directions, obtained a promising microwave dielectric material for microwave communication.