Influence of different percentages of N‐phenylaminopropyl—poss on the degradation kinetic of epoxy resin

In the present study, nanocomposites were prepared with different contents (1, 2, 5, 10% by weight) of polyhedral oligomeric silsesquioxane—POSS n‐phenylaminopropyl in an epoxy matrix. The samples were characterized by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and X‐ray diffraction (XRD). TGA analyses were performed at different heating rates to allow for the prediction of the kinetic parameters of degradation. XRD analyses were used to calculate the average molecular interchain spacing. TGA analysis showed that the presence of POSS increased the thermal stability of the nanocomposites. An increase in the activation energy on degradation was evidenced through the kinetic parameters, especially for the 10% POSS. Moreover, the addition of POSS changed the kinetic mechanism of the deceleratory mode (F_n) in favor of the diffusion (D_n) process. The diffusion mechanism is corroborated by the XRD analyses that showed the increase of distance between chains when was added POSS. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Polyhedral oligomeric silsesquioxanes nanoreinforced methacrylate/epoxy hybrids

The aim of this study was to design novel binary and ternary copolymers based on methacrylate and/or epoxy monomers reinforced with 10 wt % mono‐/octafunctional polyhedral oligomeric silsesquioxanes (POSS) compounds bearing one or eight epoxy or methacrylate moieties. The experimental parameters such as temperature and time of reaction, comonomer ratio and the incorporation of various types of POSS that strongly influences the curing behavior, polymerization kinetics, glass transition temperature (T_g), thermostability and morphological structure of the obtained copolymers were investigated through DSC, FTIR, DMA, TGA, and SEM techniques. The obtained results evidenced that the complex kinetic mechanisms of curing reactions for the binary and ternary copolymers ± POSS influence the thermomechanical and morphological properties of the materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42912.     

Preparation and thermal property of hybrid nanocomposites by free radical copolymerization of styrene with octavinyl polyhedral oligomeric silsesquioxane

The poly(styrene‐co‐octavinyl‐polyhedral oligomeric silsesquioxane) (PS–POSS) organic–inorganic hybrid nanocomposites containing various percent of POSS were prepared via one‐step free radical polymerization and characterized by FTIR, high‐resolution ¹H NMR, ²⁹Si NMR, GPC, DSC, and TGA technologies. The POSS contents in these nanocomposites were determined using FTIR calibration curve. The result shows that the POSS contents in nanocomposites can be tailored by varying the POSS feed ratios. On the basis of the POSS contents in the nanocomposites and the ¹H NMR spectra, the number of reacted vinyl groups of each octavinyl‐POSS macromonomer were calculated to be 6–8. DSC and TGA measurements indicate that the incorporation of POSS into PS homopolymer can apparently improve the thermal properties of the polymeric materials. The dramatic T_g and T_dec increases are mainly due to the formation of star and low cross‐linking structure of the nanocomposites, where POSS cores behave as the joint points and hinder the motion and degradation of the polymeric chains. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

The effect of POSS on the thermal properties of epoxy

Summary The thermal properties of a series of inorganic-organic diglycidyl ether of bisphenol A/octa(aminpropyl)silsesquioxane (EP/POSS-NH₂) composites of were systematically investigated. These thermal properties included dynamic mechanical properties, glass transition temperature and thermal degradation temperature. Dynamic mechanical analysis (DMA) and Thermogravimetric analysis (TGA) were adopted. Results showed that the incorporation of POSS into epoxy resin could improve the thermal stabilities of epoxy significantly.     

Reactivity, viscoelastic behaviour and mechanical performances of hybrid systems based on epoxy resins and reactive polyhedral oligosilsesquioxanes

An epoxy formulation was modified by adding various amounts of an epoxy functionalized polyhedral oligomeric silsesquioxane (POSS). The obtained networks were characterized in terms of reactivity, viscoelastic behaviour and mechanical properties. Spectroscopy measurements by FT-NIR demonstrated that the epoxy groups of POSS were almost as reactive as those of the DGEBA in the curing stage, while in the post-curing a lower reactivity of the latter was found, possibly due to steric hindrance effects. The dynamic-mechanical analysis showed an increase in the storage modulus in both glassy and rubbery regions. On the other hand, T_g and T_β decreased with POSS content. The viscoelastic analysis showed that the addition of POSS enhanced the free volume and the tendency of the network to undergo thermal expansion. In particular, the β transition was made increasingly localized by increasing the POSS content. With respect to mechanical performances, the yield process was facilitated by incorporation of the POSS nanocages within the network, possibly due to an enhancement of the chain mobility. Fracture measurements showed an improvement of the parameters K_c and G_c up to 5 wt% of POSS, after which a decrease of toughness was observed. These results were supported by a fractographic analysis.     

Isothermal crystallization of HDPE/octamethyl polyhedral oligomeric silsesquioxane nanocomposites: Role of POSS as a nanofiller

The isothermal crystallization of HDPE/POSS (polyhedral oligomeric silsesquioxane) nanocomposites (POSS content varying from 0.25 to 10 wt %) was studied using differential scanning calorimetry (DSC) technique. The Avrami model could successfully describe the isothermal crystallization behavior of the nanocomposites. The value of Avrami exponent (n) varies between 2 and 2.5 for all the compositions studied. For a given composition, the values vary with crystallization temperature and in general increased with POSS content up to 1 wt % POSS content and decreased thereafter. The presence of POSS was found to increase the rate of crystallization, which manifested itself in the increased value of the Avrami rate constant (K) and reduced value of crystallization half‐time (t_1/2). The rate of crystallization peaked at 1 wt % POSS content and was almost constant at higher POSS loadings. X‐ray diffraction studies revealed that POSS exists as nanocrystals in HDPE matrix while some POSS gets dispersed at molecular level too. It is observed that only the POSS dispersed at molecular level acts as a nucleating agent while the POSS nanocrystals do not affect the crystallization process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Epoxy‐functionalized polyhedral oligomeric silsesquioxane/cyanate ester resin organic–inorganic hybrids with enhanced mechanical and thermal properties

A series of cyanate ester resin (CE) based organic–inorganic hybrids containing different contents (0, 5, 10, 15 and 20 wt%) of epoxy‐functionalized polyhedral oligomeric silsesquioxane (POSS‐Ep) were prepared by casting and curing. The hybrid resin systems were studied by the gel time test to evaluate the effect of POSS‐Ep on the curing reactivity of CE. The impact and flexural strengths of the hybrids were investigated. The micromorphological, dynamic mechanical and thermal properties of the hybrids were studied by SEM, dynamic mechanical analysis (DMA) and TGA, respectively. Results showed that POSS‐Ep prolonged the gel time of CE. CE10 containing 10 wt% POSS‐Ep displayed not only the optimum impact strength but the optimum flexural strength. SEM results revealed that the improvement of mechanical properties was attributed to the large amount of tough whirls and fiber‐like pull‐outs observed on the fracture surfaces of CE10. DMA results indicated that POSS‐CE tended to decrease E′ of the hybrids in the glassy state but to increase E′ of the hybrids in the rubbery state. TGA results showed that CE10 also possesses the best thermal stability. The initial temperature of decomposition (T_i) of CE10 is 426 °C, 44 °C higher than that of pristine CE. © 2013 Society of Chemical Industry     

Mechanical,thermal, and viscoelastic response of novel in situ CTBN/POSS/epoxy hybrid composite system

The present study focuses on the preparation of a novel hybrid epoxy nanocomposite with glycidyl polyhedral oligomeric silsesquioxane (POSS) as nanofiller, carboxyl terminated poly(acrylonitrile‐co‐butadiene) (CTBN) as modifying agent and diglycidyl ether of bisphenol A (DGEBA) as matrix polymer. The reaction between DGEBA, CTBN, and glycidyl POSS was carefully monitored and interpreted by using Fourier transform infrared (FTIR) and differential scanning calorimetry (DSC). An exclusive mechanism of the reaction between the modifier, nanofiller, and the matrix is proposed herein, which attempts to explains the chemistry behind the formation of an intricate network between POSS, CTBN, and DGEBA. The mechanical properties, such as tensile strength, and fracture toughness, were also carefully examined. The fracture toughness increases for epoxy/CTBN, epoxy/POSS, and epoxy/CTBN/POSS hybrid systems with respect to neat epoxy, but for hybrid composites toughening capability of soft rubber particles is lost by the presence of POSS. Field emission scanning electron micrographs (FESEM) of fractured surfaces were examined to understand the toughening mechanism. The viscoelastic properties of epoxy/CTBN, epoxy/POSS, and epoxy/CTBN/POSS hybrid systems were analyzed using dynamic mechanical thermal analysis (DMTA). The storage modulus shows a complex behavior for the epoxy/POSS composites due to the existence of lower and higher crosslink density sites. However, the storage modulus of the epoxy phase decreases with the addition of soft CTBN phase. The T_g corresponding to epoxy‐rich phase was evident from the dynamic mechanical spectrum. For hybrid systems, the T_g is intermediate between the epoxy/rubber and epoxy/POSS systems. Finally, TGA (thermo gravimetric analysis) studies were employed to evaluate the thermal stability of prepared blends and composites. POLYM. COMPOS., 37:2109–2120, 2016. © 2015 Society of Plastics Engineers     

Poly(vinyl pyrrolidone‐co‐octavinyl polyhedral oligomeric silsesquioxane) hybrid nanocomposites: Preparation,thermal properties,and Tg improvement mechanism

A series of poly(vinyl pyrrolidone‐co‐octavinyl polyhedral oligomeric silsesquioxanes) (PVP‐POSS) organic–inorganic hybrid nanocomposites containing different percentages of POSS were prepared via free radical polymerization and characterized by FTIR, high‐resolution ¹H‐NMR, solid‐state ²⁹Si‐NMR, GPC, DSC, and TGA. POSS contents in these nanocomposites can be effectively controlled by varying the POSS feed ratios which can be accurately quantified by FTIR curve calibration. On the basis of ²⁹Si‐NMR spectra, average numbers of reacted vinyl groups of each octavinyl‐POSS macromer are calculated to be 5–7, which depends on POSS feed ratios. Both GPC and DSC results indicate that these nanocomposites display network structure and the degree of crosslinking increases with the increase of the POSS content. The incorporation of POSS into PVP significantly improves their thermal properties (T_g and T_dec) primarily due to crosslinking structure and dipole–dipole interaction between POSS cores and PVP carbonyl groups. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of EP‐POSS mixture and the properties of EP‐POSS/epoxy,SiO2/epoxy,and SiO2/EP‐POSS/epoxy nanocomposite

The hybrid material of EP‐POSS mixture was synthesized by the hydrolysis and condensation of (γ‐glycidoxypropyl) trimethoxysilane. A series of binary systems of EP‐POSS/epoxy blends, epoxy resin modified by silica nanoparticles (SiO₂/epoxy), and ternary system of SiO₂/EP‐POSS/epoxy nanocomposite were prepared. The dispersion of SiO₂ in the matrices was evidenced by transmission electron micrograph, and the mechanical properties, that is, flexural strength, flexural modulus, and impact strength were examined for EP‐POSS/epoxy blends, SiO₂/epoxy, and SiO₂/EP‐POSS/epoxy, respectively. The fractured surface of the impact samples was observed by scanning electron micrograph. Thermogravimetry analysis were applied to investigate the different thermal stabilities of the binary system and ternary system by introducing EP‐POSS and SiO₂ to epoxy resin. The results showed that the impact strength, flexural strength, and modulus of the SiO₂/EP‐POSS/epoxy system increased around by 57.9, 14.1, and 44.0% compared with the pure epoxy resin, T_i, T_max and the residues of the ternary system were 387°C, 426°C, and 25.2%, increased remarkably by 20°C, 11°C and 101.6% in contrast to the pure epoxy resin, which was also higher than the binary systems. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 810‐819, 2013     

Novel nitrogen‐containing epoxy resin. II. Cure kinetics by differential scanning calorimetry

The isothermal and nonisothermal cure behaviors of a novel nitrogen‐containing epoxy resin (XT resin) were studied by differential scanning calorimetry (DSC). Various kinetic parameters and details of cure process were obtained based on the Avrami theory. The results indicated that Avrami method is suitable for calculating the kinetic parameters up to the gel point at least. The apparent activation energy (E_a) for isothermal cure process was in agreement with that for nonisothermal cure process. E_a value in the early stage (78.5–81.0 KJ mol^?1) was about three times than that in the later stage (23.3–26.5 KJ mol^?1). The kinetic results from Avrami theory may present a combined effect of all factors, and which is helpful to understand the cure technique for XT–DDS system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3483–3489, 2006     

Epoxy nanocomposites with octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane

The POSS-containing nanocomposites of epoxy resin were prepared via the co-curing reaction between octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane (OpePOSS) and the precursors of epoxy resin. The curing reactions were started from the initially homogeneous ternary solution of diglycidyl ether of bisphenol A (DGEBA), 4,4′-Diaminodiphenylmethane (DDM) and OpePOSS. The nanocomposites containing up to 40 wt% of POSS were obtained. The homogeneous dispersion of POSS cages in the epoxy matrices was evidenced by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM) and atomic force microscopy (AFM). Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) showed that at the lower POSS concentrations (<30 wt%) the glass transition temperatures (T_gs) of the nanocomposites almost remained invariant whereas the nanocomposites containing POSS more than 40 wt% displayed the lower T_gs than the control epoxy. The DMA results show that the moduli of the nanocomposites in glass and rubbery states are significantly higher than those of the control epoxy, indicating the nanoreinforcement effect of POSS cages. Thermogravimetric analysis (TGA) indicates that the thermal stability of the polymer matrix was not sacrificed by introducing a small amount of POSS, whereas the properties of oxidation resistance of the materials were significantly enhanced. The improved thermal stability could be ascribed to the nanoscaled dispersion of POSS cages and the formation of tether structure of POSS cages with epoxy matrix.     

Epoxy nanocomposites containing mercaptopropyl polyhedral oligomeric silsesquioxane: Morphology,thermal properties,and toughening mechanism

A novel polyhedral oligomeric silsesquioxane (POSS) containing a mercaptopropyl group [mercaptopropyl polyhedral oligomeric silsesquioxane (MPOSS)] was synthesized via the hydrolytic condensation of γ-mercaptopropyl triethoxysilane in an ethanol solution catalyzed by concentrated hydrochloric acid and was used to modify epoxy–amine networks by a cocuring reaction with diglycidyl ether of bisphenol A (DGEBA). The structure, morphology, and thermal and mechanical properties of these MPOSS/DGEBA epoxy nanocomposites were studied and investigated with thermogravimetric analysis/differential thermal analysis (TGA–DTA), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). From SEM analysis, we observed that the miscibility between epoxy and POSS occurred at a relatively high POSS content, which characterized this mixture as a polymer nanocomposite system. The impact test showed that MPOSS reinforced the epoxy effectively, and the SEM study of the impact fracture surface showed that the fibrous yielding phenomenon observed was an indication of the transition of the brittle stage to a ductile stage and correlated well with the large increases in the impact strength; this was in agreement with the in situ reinforcing and toughening mechanism. The TGA–DTA analysis indicated that the MPOSS/DGEBA epoxy hybrids exhibited lower thermostability at a lower temperature but higher thermostability and higher efficiency in char formation at an elevated temperature. Differential scanning calorimetry showed that the glass transition temperature (T_g) of the MPOSS/epoxy hybrids were lower than that of the neat epoxy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of poly(methyl methacrylate) nanocomposites containing octavinyl polyhedral oligomeric silsesquioxane

A series of poly(methyl methacrylate) (PMMA) containing octavinyl-polyhedral oligomeric silsesquioxane (OV-POSS) nanocomposites were synthesized by solution polymerization. The products were characterized by FTIR, ¹H NMR, GPC, TEM, DSC and TGA. The actual contents of OV-POSS in the obtained products and the reaction degree of the vinyl groups in the POSS were calculated on the basis of FTIR, TGA and ¹H NMR data respectively. The DSC and TGA results indicate that the incorporation of POSS molecules could improve the thermal properties of PMMA nanocomposites significantly. The glass transition temperature (T_g) and thermal decomposition temperature (T_dec1) of the nanocomposite with 12.27 wt % of OV-POSS were increased by 23 °C and 93 °C correspondingly. In our experiment, the improved thermal properties were largely attributed to the nanoreinforcement effect of POSS cages and the formation of star-shaped structures with cubic silsesquioxane core.     

The effect of hybrid nanoparticle additives on epoxy‐nanocomposite behavior and morphology

Amine modified polyhedral oligomeric silsesquioxane (POSS‐NH₂) was used to modify sodium montmorillonite (MMT) nanoclays for improved dispersion in epoxy resin. The dispersion of the clay particles was inspected using scanning electron microscopy, energy dispersive spectroscopy (EDS) and X‐Ray diffraction and the thermal properties compared using differential scanning calorimetry (DSC) and thermogravametric analysis. The introduction of the amine‐POSS was found to have a positive effect on the dispersion of the MMT clays and prevented agglomeration. The absence of clay agglomerates lead to an increase in glass transition temperature (T_g) from 44°C in the samples with the untreated clay up to 54°C in the samples with 10% additional POSS‐NH₂. The addition of POSS‐NH₂ initial increase of the weight loss (T_{d 5%}) but slowed down the rate of degradation due to the formation of an inert silica layer and eventually leading to an increased charyield. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Low dielectric and high thermal conductivity epoxy nanocomposites filled with NH2‐POSS/n‐BN hybrid fillers

Hybrid fillers of mono‐amine polyhedral oligomeric silsesquioxane/nanosized boron nitride (NH₂‐POSS/n‐BN) were performed to fabricate NH₂‐POSS/n‐BN/epoxy nanocomposites. Results revealed that the dielectric constant and dielectric loss values were decreased with the increasing addition of NH₂‐POSS obviously, but increased with the increasing addition of BN fillers. For a given loading of NH₂‐POSS (5 wt %), the thermal conductivities of NH₂‐POSS/n‐BN/epoxy nanocomposites were improved with the increasing addition of n‐BN fillers, and the thermal conductivity of the nanocomposites was 1.28 W/mK with 20 wt % n‐BN fillers. Meantime, the thermal stability of the NH₂‐POSS/n‐BN/epoxy nanocomposites was also increased with the increasing addition of n‐BN fillers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41951.     

Influence of polyhedral oligomeric silsesquioxanes on thermal and mechanical properties of polycarbonate/POSS hybrid composites

Two types of silsesquioxanes were synthesized by hydrolytic condensation reaction, and then were incorporated into polycarbonate (PC) matrix by melt blending to prepare PC/POSS hybrid composites. The study of morphology of the composites showed that octaphenylsilsesquioxane (PH‐POSS) exhibited partial compatibility with PC matrix, while 3‐glycidyloxypropylsilsesquioxane (EP‐POSS) could react with phenolic hydroxyl groups of matrix. Thermal and mechanical properties were studied by DSC, TGA, and DMA. The result showed that the incorporation of POSS not only improved thermal stabilities of PC composites, but also retarded their thermal degradation. Si O fractions left during POSS degradations were the key factor governing the formation of a gel network layer on the exterior surface. This layer possessed more compact structures, higher thermal stabilities, and some thermal insulation. In addition, percentage residues at 700°C (C₇₀₀) significantly increased from 10.8 to 15.5–22.8% in air. The storage modulus of two series of composites was slightly improved up to 90°C; furthermore, the temperature range of the rubbery state of them shifted to high temperature. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Thermal degradation analysis of the isocyanate polyhedral oligomeric silsequioxanes (POSS)/sulfone epoxy nanocomposite

The sulfone epoxy (SEP)/polyhedral oligomeric silsesquioxane (POSS) nanocomposite contains bulky POSS side chains was studied in this research. Its glass transition temperature (T_g) decreases with the bulky POSS content, indicating that the bulky POSS side chains could not only generate the oligomers but also interrupt the network architectures of SEP. Homogeneous and uniform dispersion of POSS in SEP matrix can be obtained through the carbamate/oxazolidon covalent linkage, which is evidenced by scanning electron microscopy. The increasing concentration of POSS into SEP exhibits an increase of char yield in the nanocomposites, indicating that the POSS segments provide the antithermal‐oxidation effect for SEP/POSS, thereby inhibiting thermal degradation under open air at high temperatures. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Star‐shaped POSS–methacrylate copolymers with phenyl–triazole as terminal groups,synthesis, and the pyrolysis analysis

Star‐shaped polyhedral oligomeric silsesquioxane (POSS)–methacrylate hybrid copolymers with phenyl–triazole as terminal groups had been designed and synthesized via sequential atom transfer radical polymerization (ATRP), azidation, and phenylacetylene‐terminated procedures, and the hybrid copolymers here could be denoted as POSS–(PXMA‐Pytl)₈, where X can be M, B, L, and S, represented four different methacrylate monomers, such as methacrylate (MMA), butyl methacrylate (BMA), lauryl methacrylate (LMA), and stearyl methacrylate (SMA), respectively. Thermal gravimetric analysis (TGA) and in situ Fourier transform infrared spectroscopy (FTIR) were applied for studying the thermal stability and degradation mechanism, and it was found that all of the POSS–(PXMA‐Cl)₈ and POSS–(PXMA‐Pytl)₈ copolymers exhibited excellent thermal stabilities, which had great potential in heat‐resistant material application. Different tendencies of decomposition temperatures at 5% and 10% weight loss (T₅ and T₁₀) dependent on the side‐chain length and terminal group species were investigated respectively. The longer alkyl side chains of the monomers, the lower thermal stabilities, and enhanced T₅ and T₁₀ were also shown with the introduction of phenyl–triazole groups instead of chlorine groups. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40652.     

Effect of POSS‐grafted titanium dioxide on the electrical and thermal properties of LDPE/TiO2 polymer nanocomposite

Two types of nanocomposites have been fabricated by a ball‐milling technique. The first type consists of untreated titanium dioxide (TiO₂) incorporated into low‐density polyethylene (LDPE). For the second one, TiO₂ filler chemically treated with trisilanol phenyl–polyhedral oligomeric silsesquioxane (TP–POSS) as compatibilizing agent was ball‐milled with LDPE. All specimens were tested by microstructure analysis and thermal, dielectric characterization techniques. Microstructure analysis by atomic force microscopy and scanning electron microscopy show clearly an increased dispersion in presence of POSS. Scanning electron microscopy even shows the formation of a particular structure due possibly to interactions between functionalization. It was observed that the modification of the surface of TiO₂ by the POSS decreased the dielectric loss. All nanocomposites containing treated TiO₂ revealed an improvement in thermal conductivity, with the most distinct value of 19% in case of LDPE containing 5 wt % treated TiO₂. The incorporation of TiO₂ fillers seems to reduce the dielectric breakdown strength of the nanocomposites. However, nanocomposites containing 3 and 5 wt % treated TiO₂ have exhibited a slightly enhancement in dielectric breakdown strength up to 5%. The improvement in surface resistance to partial discharge was found in all nanocomposites specimens, especially for both types of composite containing 7 wt % untreated and treated TiO₂. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46095.