Synergistic effect between POSS and fumed silica on thermal stabilities and mechanical properties of room temperature vulcanized (RTV) silicone rubbers

In this paper, both divinyl-hexa[(trimethoxysilyl)ethyl]-POSS (DVPS) and fumed silica were firstly introduced into polydimethylsiloxane (PDMS) system using as the cross-linker and the reinforcing filler respectively. And a series of novel RTV silicone rubbers synergistically enhanced by DVPS and fumed silica were prepared. The cross-linked networks in the novel RTV silicone rubbers have been studied by attenuated total reflection infrared spectroscopy, and the dispersions of POSS and fumed silica in these novel RTV silicone rubbers have been observed by means of scanning electron microscope (SEM). And thermal stabilities, thermo-oxidative stabilities and mechanical properties of these novel RTV silicone rubbers were studied by means of thermal gravimetric analysis and universal tensile testing machine, respectively. From the obtained results, it was found that synergistic effect between POSS-rich areas and fumed silica on thermal stability and mechanical property of RTV silicone rubber indeed existed. And the experimental results also exhibited that the thermal stabilities and mechanical properties of the novel RTV silicone rubbers were far better than those of the reference materials (DVPR and MTFR). The striking enhancements in thermal properties and improvements on mechanical properties of novel RTV silicone rubbers were likely attributed to the synergistic effect between POSS-rich domains and fumed silica. Meanwhile, it was found that the mechanical properties of RTV silicone rubbers prepared with a given amount of POSS cross-linker were enhanced with the increment of the loading amount of fumed silica.     

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.     

Effects of organo-montmorillonite dispersion on thermal stability of epoxy resin nanocomposites

Montmorillonite (MMT) was modified with the acidified cocamidopropyl betaine (CAB) and the resulting organo-montmorillonite (O-MMT) was dispersed in an epoxy/methyl tetrahydrophthalic anhydride system to form epoxy nanocomposites. The dispersion state of the MMT in the matrix was investigated by X-ray diffraction and scanning electronic microscopy. The thermal stability of the epoxy nanocomposites was examined by TGA. Thermal stability of the epoxy nanocomposite is dependent upon the dispersion state of the OMMT in the epoxy matrix although all the epoxy nanocomposites had enhanced thermal stability compared with the neat epoxy resin. The thermal stability of the epoxy resin nanocomposites was correlated with the dispersion state of the MMT in the epoxy resin matrix.     

Preparation, characterization and biodegradation of biopolymer nanocomposites based on fumed silica

PLA and PCL based nanocomposites prepared by adding three different types of fumed silica were obtained by melt blending. Materials were characterized by means of Scanning Electron Microscopy (SEM), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA) and Dynamic–Mechanical Thermal Analysis (DMTA).A good distribution of the fumed silica into both polymer matrices was observed. The highest thermo-mechanical improvements were reached by addition of the fumed silica with higher surface area. PLA and its nanocomposites were degraded in compost at 58 °C; at this temperature all samples presented a significant level of polymer degradation, but a certain protection action of silica towards PLA degradation was observed, whereas the addition of fumed silica did not show considerable influence on the degradation trend of PCL. These dissimilarities were attributed to the different degradation mechanism of the two polymers.     

Influences of template concentration and epoxy functionality on porous epoxy systems: Characteristics of thermal stability, optical, dielectric, and mechanical properties

Two different multi-porous epoxy thermosets (MPETs), bi-functionality of DGEBA and tri-functionality of TGTPM, were prepared foremost for the interaction of template concentration and epoxy functionality under several physical properties. By performing an automated mercury porosimeter test, we found out template concentration was critical to the amount of voids/pores. Meanwhile, epoxy functionality decided the formation of porous structure through SEM. Comparing with TGTPM MPETs system, the DGEBA MPETs system with 20 wt% template displayed appreciable T_g and tan δ properties while the phenomenon exhibited higher thermal stability property. Additionally, thermal conductivity patterns show the DGEBA MPETs system is a remarkable material of thermal resistance. However, it reduces optical clarity, dielectric permittivity and mechanical strength according to the UV-visible spectroscopy, LCR meter, and DMA, normally. Therefore, we can understand that template concentration and epoxy functionality are key factors of physical degradation and stability in porous epoxy materials.     

Characteristics of kenaf fibre/epoxy composites subjected to thermal degradation

Kenaf fibres are receiving much attention in the natural fibre composite industry due to its potential as polymer reinforcements. However, like all natural fibres, kenaf fibres have lower thermal resistance as compared to synthetic fibres. In this current work, the characteristics of kenaf fibre/epoxy composites, both treated and untreated using alkalization process, exposed to high temperature were studied. Thermogravimetric analysis (TGA) was used to study the thermal decomposition behaviour of treated and untreated kenaf/epoxy composites as well as their components, kenaf fibre and neat epoxy from room temperature up to 600 °C. The weight loss and physical changes of these samples were observed through furnace pyrolysis. Surface morphology of the composites after degradation was observed using scanning electron microscopy (SEM). The results from the TGA showed that the addition of kenaf fibres into the epoxy slightly improves both the charring and thermal stability of the samples. However, it was observed that alkalization causes reduction in these behaviours for the kenaf/epoxy composite. Generally, increased exposure time causes higher weight loss of the composites only up to 150 °C. At higher temperature, duration of exposure has little influence on the weight loss. Fibre-matrix debondings were observed on degraded samples implying mechanical degradation of the composites had occurred.     

Influence of iron content on thermal stability of magnetic polyurethane foams

Magnetorheological (MR) materials are a group of smart materials which have the controllable magnetic properties with an external magnetic field. Magnetic foams, a specific type of MR solids, were synthesized from flexible polyurethane (PU) foams and carbonyl iron particles. Effects of the carbonyl iron particles on the thermal stability of the magnetic foams have been studied. Thermogravimetric analysis (TGA) was applied to characterize the thermal degradation process of the magnetic foams and then the apparent activation energy of degradation was calculated by using Ozawa's method [Ozawa T. A new method of analyzing thermogravimetric data. Bulletin of the Chemical Society of Japan 1965; 38: 1881-1886.]. The carbonyl iron particles were found to improve the thermal stability of magnetic foams in nitrogen by showing higher 10 wt% loss temperature, slower weight loss rate and higher apparent activation energy than pure PU foams. But the magnetic foams were observed to have slightly worse thermal stability in air than pure PU foams at the earlier degradation stage. At the later degradation stage, the magnetic foams exhibited the higher activation energy than pure PU foams in air.     

Enhanced thermal stability and structural characteristics of different MMT-Clay/epoxy-nanocomposite materials

Epoxy-clay nanocomposites, HDTMA-BDGE, HDTMA-BPDG, HDTMA-BBDG, HDTMA-TGDDM and HDTPP-BDGE were synthesized using hexadecylammonium clay and hexadecylphosphonium clay, respectively. The Montmorillonite (MMT) clay was modified with quaternary ammonium salt and with triphenylphosphonium salt which was intercalated into the interlayer region of MMT-Clay. The epoxy-clay systems were cured by using diaminodiphenylsulphone as a curing agent. The X-ray diffraction patterns obtained for the systems confirmed the nanodispersion of MMT-Clay in the epoxy networks. The ammonium clay-modified systems displayed appreciable mechanical and glass-transition temperature properties while, the phosphonium clay-modified system exhibited highest thermal resistance properties compared with unmodified epoxy systems. The T_g decrease observed in all the clay-modified epoxy systems, may be compromised with their advantage of requiring the filler content very low (5wt%), when compared to the conventional epoxy systems whose filler quantity is normally required from 25 to 30 wt%.     

Phosphorus based epoxy terminated structural adhesive 2. Curing, adhesive strength and thermal stability

The curing behavior of phosphorus based epoxy terminated polymers was studied using diaminodiphenyl ether, diaminodiphenyl sulfone, benzophenone tetracarboxylic dianhydride and the commercial hardener of Ciba-Geigy's two-pack araldite, as curing agent. The adhesive strength of these adhesives was measured by various ASTM methods like lap-shear, peel, and cohesive tests on metal-metal, wood-wood and wood-metal interfaces. All these results were compared with the synthesized epoxy resins prepared from bisphenol-A and epichlorohydrin having the epoxy equivalent value of 0.519. The thermal stability of both the virgin resin and its cured form was also studied by thermogravimetric analysis.     

Effect of P/Si polymeric silsesquioxane and the monomer compound on thermal properties of epoxy nanocomposite

The unique polymeric silsesquioxane/4,4′-diglycidyether bisphenol A (DGEBA) epoxy nanocomposites have been prepared by sol-gel method. The structure of nanocomposites was characterized by attenuated total reflectance (ATR) and solid state ²⁹Si NMR. The characteristic intensity of trisubstituted (T) structure was higher than that of tetrasubstituted (Q) structure from solid state ²⁹Si NMR spectra of 3-isocyanatopropyltriethoxysilane (IPTS) modified epoxy. The activation energies of curing reaction of epoxy system and IPTS modified epoxy system are 28-66 kJ/mol and 57-75 kJ/mol, respectively, by Ozawa’s and Kissinger’s methods. The triethyoxysilane side chain of IPTS modified epoxy might interfere the curing reaction of epoxy/amine and increase the activation energy of curing. The thermal degradation of nanocomposites was investigated by Thermogravimetric analysis (TGA). The char yield of nanocomposites was proportional to the 2-(diphenylphosphino)ethyltriethoxysilane (DPPETES) moiety content at high temperature. A higher char content could inhibit thermal decomposition dramatically and enhance the thermal stability. Moreover, the nanocomposites possess high optical transparency.     

Determining the effect of Ru substitution on the thermal stability of CeFe4−xRuxSb12

The ternary, rare-earth filled (RE) Skutterudites (REM₄Pn₁₂; M = Fe–Os; Pn = P–Sb) have been proposed for use in high-temperature thermoelectric devices to convert waste heat to useful power. CeFe₄Sb₁₂ has been one of the most popular materials proposed for this application; however, it oxidizes at relatively low temperatures. The thermal stability of Skutterudites can be enhanced by selective substitution of the constituent elements and Eu(Fe,Ru)₄Sb₁₂ variants have been found to oxidize at temperatures above that of CeFe₄Sb₁₂. Unfortunately, these materials have poor thermoelectric properties. In this study, the thermal stability of CeFe_4−xRu_xSb₁₂ was examined depending on the value of x. (These compounds have similar thermoelectric properties to those of CeFe₄Sb₁₂.) It has been found by use of TGA and XANES that the temperature at which point CeFe_4−xRu_xSb₁₂ oxidizes increases with greater Ru substitution. XANES was also used to confirm the general charge assignment of Ce³⁺Fe_4−x²⁺Ru_x²⁺Sb₁₂¹⁻.     

Modification of fumed silica surface with different sulfonamides via a postsynthesis method and their application as antibacterial agents

The surface of nanosized fumed silica (FSi) was modified with different amine groups by the use of silylating agents. The obtained propylamine, propylpiperazine, and propyl-p-phenylenediamine–modified FSi were treated with different sulfonyl chlorides to gain sulfonamide-modified FSi compounds. These compounds were characterized by various techniques including Fourier transform infrared spectroscopy, thermogravimetric analysis, differential thermal analysis, scanning electron microscopy, and energy-dispersive X-ray spectroscopy (EDX), confirming the grafted sulfonamides on the FSi surface. Sulfonamide-modified surfaces are efficient catalysts for the Michael addition-based syntheses and coupling reactions. Furthermore, the antibacterial tests showed that these modified FSi compounds have antibacterial activities and thus are useful materials for preparing antibacterial silicone-based compounds such as silicone glue and oil.     

Thermal stability of microencapsulated epoxy resins with poly(urea-formaldehyde)

A series of microcapsules filled with epoxy resins with poly(urea-formaldehyde) (PUF) shell were synthesized by in situ polymerization, and they were heat-treated for 2 h at 100 °C, 120 °C, 140 °C, 160 °C, 180 °C and 200 °C. The effects of surface morphology, wall shell thickness and diameter on the thermal stability of microcapsules were investigated. The chemical structure and surface morphology of microcapsules were investigated using Fourier-transform infrared spectroscope (FTIR) and scanning electron microscope (SEM), respectively. The thermal properties of microcapsules were investigated by thermogravimetric analysis (TGA and DTA) and by differential scanning calorimetry (DSC). The thermal damage mechanisms of microcapsules at lower temperature (<251 °C) are the diffusion of the core material out of the wall shell or the breakage of the wall shell owing to the mismatch of the thermal expansion of core and shell materials of microcapsules. The thermal damage mechanisms of microcapsules at higher temperature (>251 °C) are the decomposition of shell material and core materials. Increasing the wall shell thickness and surface compactness can enhance significantly the weight loss temperatures (T_d) of microcapsules. The microcapsules with mean wall shell thickness of 30 ± 5 μm and smoother surface exhibit higher thermal stability and can maintain quite intact up to approximately 180 °C.     

Effects of TriSilanolIsobutyl-POSS on thermal stability of methylsilicone resin

Methylsilicone resin/polyhedral oligomeric silsesquioxane (POSS) composites with various proportions of POSS monomer were synthesized by the reaction of functionalized TriSilanolIsobutyl-POSS macromonomer with hydroxyl-terminated methylsilicone resin. The structures of the obtained hybrid polymers were characterized with Fourier-transformed infrared (FT-IR) and transmission electron microscopy (TEM). The FT-IR spectra suggested successful bonding of TriSilanolIsobutyl-POSS and methylsilicone resin. TEM analysis showed that POSS can dissolve in methylsilicone resin at the molecular level. The influences of TriSilanolIsobutyl-POSS on the thermal stability and degradation behavior of methylsilicone resin were studied by thermogravimetric analysis (TGA), solid-state ²⁹Si NMR and X-ray photoelectron spectroscopy (XPS). All these techniques showed that TriSilanolIsobutyl-POSS incorporation results in increased decomposition temperatures and oxidation resistance, primarily by reducing the effect of silanol end groups on the thermolysis through condensation reaction of Si-OH groups and partial loss of isobutyl followed by the formation of an inorganic SiO₂ layer to prevent methylsilicone from further degradation.     

Interfacial phenomena in starch/fumed silica at varied hydration levels

Hydrated powders of non-gelatinised starch and hydrogels of gelatinised starch alone or with addition of modified nanosilica (with grafted aminopropylmethylsilyl groups substituting one-third of surface silanols) were studied using broadband dielectric relaxation spectroscopy (DRS), thermally stimulated depolarisation current (TSDC) method and ¹H NMR spectroscopy with layer-by-layer freezing-out of bulk and interfacial waters. The ¹H NMR and TSDC techniques with the use of Gibbs–Thomson relation for the freezing point depression allow us to calculate: (i) the thermodynamic parameters of interfacial water weakly and strongly bound to polymer molecules and nanoparticles; (ii) size distributions of pores filled by structured water; (iii) surface area and volume of micro-, meso- and macropores. The DRS and TSDC results for hydrogels and hydrated powders with starch/modified fumed silica show that the β- and γ-relaxations of starch are strongly affected by water and functionalised silica nanoparticles which slow down both low- and high-frequency and low- and high-temperature relaxations.     

Performance improvement of EPDM and EPDM/Silicone rubber composites using modified fumed silica,titanium dioxide and graphene additives

In this work, a polymeric composite was prepared from ethylene propylene diene monomer (EPDM) and silicone rubber (S) with additives of modified fumed silica (MFS), titanium dioxide (TiO₂) and graphene. The dielectric and thermal performances of the EPDM-based composites were studied. An increase in the dielectric constant and AC dielectric breakdown strength was observed for the EPDM rubber composites containing MFS, TiO_2, and graphene additives. In addition, the incorporation of the additives resulted7in a significant increase in the thermal stability (~30–50 °C) and thermal conductivity (~7–35%) of the composites. The combination of these various improvements gives suitable performance advantage to the polymeric composite for use in insulating applications.     

Cure behavior and thermal stability of an epoxy: new bismaleimide blends for composite matrices

A new bismaleimide (BMI) resin was synthesized to formulate epoxy(tetraglycidyl diaminodiphenyl methane; TGDDM) – bismaleimide thermoset blends for composite matrix applications. 4,4′-diaminodiphenyl methane (DDM) was used as an amine curing agent for the TGDDM. A Fourier transform infrared (FTIR) spectroscopy was employed to characterize the new BMI resin. Cure behavior of the epoxy–BMI blends was studied using a differential scanning calorimeter (DSC). DSC thermograms of the thermoset blends indicated two exothermic peaks. The glass transition temperature of the thermoset blends decreased with BMI content. Thermogravimetric analysis (TGA) was carried out to investigate thermal degradation behavior of the cured epoxy–BMI thermoset blends. The new BMI resin reacted partially with the DDM and weak intercrosslinking polymer networks were formed during cure of the thermoset blends.     

Functionalized reduced graphene oxide/epoxy composites with enhanced mechanical properties and thermal stability

One-pot hydrothermal reduction of graphene oxide (GO) in N-methyl-2-pyrrolidone (NMP) suspension was performed, wherein GO surface were functionalized by free radicals generated from NMP molecules. The NMP functionalized reduced GO (NMPG) nanosheets were then incorporated into epoxy matrix to prepare epoxy composites. The significant improvement of 100 and 240% in fracture toughness (critical intensity factor, K_IC) and fracture energy (critical strain energy release rate, G_IC) achieved from single edge notched bending (SENB) test revealed the excellent toughening ability of NMPG. The improved compatibility and interfacial interaction between the epoxy matrix and NMPG yielded∼28, 19 and 51% improvement in tensile strength, Young's and storage modulus, respectively. Thermal stability of pure epoxy and its composites was determined at 5, 10 and 50% weight loss, which showed 30, 27.5 and 29 °C improvement with 0.2 wt% NMPG loading. The work provides a simple method to prepare graphene-based epoxy composites with improved performance.     

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.     

Thermal stability and lifetime estimates of a high temperature epoxy by Tg reduction

Thermal degradation of a high temperature epoxy network is studied in terms glass transition temperature (T_g) reduction over a temperature window encompassing the T_g of the network. The T_g is shown to decrease as the network is thermally aged at elevated temperatures in air and in argon. The duration of the aging experiments is extended to long time such that the absolute T_g reduction approaches a long time reduction plateau. Degradation is dominated by non-oxidative pyrolysis with a small contribution from diffusion limited thermal oxidative degradation at the surface. A time–temperature superposition is constructed from the extent of T_g reduction of samples aged in air and the thermal shift factors are shown to have Arrhenius scaling behavior. An activation energy is extracted that agrees with previous activation energy measurements derived from other property measurements of the same network aged under similar conditions. The agreement of the activation energy with past results shows that T_g reduction is controlled by the same degradation mechanism and may be used as an observable for lifetime estimates when thermal degradation is pyrolytic in nature. The extent of T_g reduction is modeled with an autocatalytic rate expression and compared to previous property measurements to show the difference in sensitivity of observable material properties on degradation.