Search Results (15)

In this study, two new nanohybrids (NH-A and NH-B) were synthesized through carbodiimide-assisted coupling. The reaction was performed between carboxymethyl-scleroglucans (CMS-A and CMS-B) with different degrees of substitution and commercial amino-functionalized silica nanoparticles using 4-(dimethylamino)-pyridine (DMAP) and N,N′-dicyclohexylcarbodiimide (DCC) as catalysts. The morphology and properties of the nanohybrids were investigated by using transmission (TEM) and scanning electron microscopy (SEM), electron-dispersive scanning (EDS), attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FT-IR), X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (XRD), inductively coupled plasma atomic emission spectroscopy (ICP-OES), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic light scattering (DLS). The nanohybrids exhibited differences in structure due to the incorporation of polyhedral oligomeric silsesquioxane (POSS) materials. The results reveal that hybrid nanomaterials exhibit similar thermal properties but differ in morphology, chemical structure, and crystallinity properties. Finally, a viscosity study was performed on the newly obtained nanohybrid materials; viscosities of nanohybrids increased significantly in comparison to the carboxymethyl-scleroglucans, with a viscosity difference of 7.2% for NH-A and up to 32.6% for NH-B. Full article

Nanocomposites of cyanate ester resin (CER) filled with three different reactive amino-functionalized polyhedral oligomeric silsesquioxane (POSS) were synthesized and characterized. The addition of a small quantity (0.1 wt.%) of amino-POSS chemically grafted to the CER network led to the increasing thermal stability of the CER matrix by 12–15 °C, depending on the type of amino-POSS. A significant increase of the glass transition temperature, T_g (DSC data), and the temperature of α relaxation, T_α (DMTA data), by 45–55 °C of the CER matrix with loading of nanofillers was evidenced. CER/POSS films exhibited a higher storage modulus than that of neat CER in the temperature range investigated. It was evidenced that CER/aminopropylisobutyl (APIB)-POSS, CER/N-phenylaminopropyl (NPAP)-POSS, and CER/aminoethyl aminopropylisobutyl (AEAPIB)-POSS nanocomposites induced a more homogenous α relaxation phenomenon with higher T_α values and an enhanced nanocomposite elastic behavior. The value of the storage modulus, E′, at 25 °C increased from 2.72 GPa for the pure CER matrix to 2.99–3.24 GPa for the nanocomposites with amino-functionalized POSS nanoparticles. Furthermore, CER/amino-POSS nanocomposites possessed a higher specific surface area, gas permeability (CO₂, He), and diffusion coefficients (CO₂) values than those for neat CER, due to an increasing free volume of the nanocomposites studied that is very important for their gas transport properties. Permeability grew by about 2 (He) and 3.5–4 times (CO₂), respectively, and the diffusion coefficient of CO₂ increased approximately twice for CER/amino-POSS nanocomposites in comparison with the neat CER network. The efficiency of amino-functionalized POSS in improving the thermal and transport properties of the CER/amino-POSS nanocomposites increased in a raw of reactive POSS containing one primary (APIB-POSS) < eight secondary (NPAP-POSS) < one secondary and one primary (AEAPIB-POSS) amino groups. APIB-POSS had the least strongly pronounced effect, since it could form covalent bonds with the CER network only by a reaction of one -NH₂ group, while AEAPIB-POSS displayed the most highly marked effect, since it could easily be incorporated into the CER network via a reaction of –NH₂ and –NH– groups with –O–C≡N groups from CER. Full article

Thermoplastic vulcanizates (TPVs) are multifunctional materials consisting of two or more phases with solid elastomeric properties at room temperatures and fluid-like properties above their melting point. They are produced through a reactive blending process known as dynamic vulcanization. The most widely produced TPV type is ethylene propylene diene monomer/polypropylene (EPDM/PP), which is the focus of this study. The peroxides are mainly selected to be used in crosslinking of EPDM/PP-based TPV. However, they still have some disadvantages, such as the side reactions resulting in the beta chain scission of the PP phase and undesired disproportionation reactions. To eliminate these disadvantages, coagents are used. In this study, for the first time, the use of vinyl functionalized polyhedral oligomeric silsesquioxane (OV-POSS) nanoparticles was investigated as a potential coagent in EPDM/PP-based TPV production via peroxide-initiated dynamic vulcanization. The properties of the TPVs having POSS were compared with the conventional TPVs containing conventional coagents, such as triallyl cyanurate (TAC). POSS content and EPDM/PP ratio were investigated as the material parameters. Mechanical properties of EPDM/PP TPVs exhibited higher values in the presence of OV-POSS, which resulted from the active participation of OV-POSS into the three-dimensional network structure of EPDM/PP during dynamic vulcanization. Full article

The aim of the study was to examine the applicability of bioactive and antibacterial nanoparticles to an experimental adhesive. The adhesive (60 wt% BisGMA, 15 wt% TEGDMA, 25 wt% HEMA) was mixed with combinations of 5 wt% methacryl-functionalized polyhedral oligomeric silsesquioxane (MA-POSS) and one kind of bioactive/antibacterial nanoparticles: 1 wt% core-shell silica-silver nanoparticle (SiO₂@Ag), 1 wt% bioactive glass with bismuth (BAG-Bi) or 1 wt% calcium phosphate (CAP). Pure adhesive served as control. The physicochemical (degree of conversion (DC), linear shrinkage (LS), shear and complex viscosity, water sorption (WS), sol fraction (SF)), biological (antimicrobial effect) and bioactive (mineral precipitation) properties were investigated. DC and LS remained unchanged. The combination of BAG-Bi/MA-POSS resulted in a significantly increased WS and SF compared to control. In addition, the combination of CAP/MA-POSS slightly increased the shear viscosity of the adhesive. The addition of the nanoparticles did not influence the antimicrobial effects compared to the pure adhesive. Improved mineral inducing capacity could be detected in all nanoparticle combinations. The combination of bioactive and/or antibacterial nanoparticles showed improved mineral inducing capacity, but no antibacterial properties. The material properties were not or only slightly affected. Full article

Rapid advancements in materials that offer the appropriate mechanical strength, barrier, and antimicrobial activity for food packaging are still confronted with significant challenges. In this study, a modest, environmentally friendly method was used to synthesize functionalized octakis(3-chloropropyl)octasilsesquioxane [fn-POSS] nanofiller. Composite films compared to the neat thermoplastic starch (TS) film, show improved thermal and mechanical properties. Tensile strength results improved from 7.8 MPa to 28.1 MPa (TS + 5.0 wt.% fn-POSS) with fn-POSS loading (neat TS). The barrier characteristics of TS/fn-POSS composites were increased by fn-POSS by offering penetrant molecules with a twisting pathway. Also, the rates of O₂ and H₂O transmission were decreased by 50.0 cc/m²/day and 48.1 g/m²/day in TS/fn-POSS composites. Based on an examination of its antimicrobial activity, the fn-POSS blended TS (TSP-5.0) film exhibits a favorable zone of inhibition against the bacterial pathogenic Staphylococcus aureus and Escherichia coli. The TS/fn-POSS (TSP-5.0) film lost 78.4% of its weight after 28 days in natural soil. New plastic materials used for packaging, especially food packaging, are typically not biodegradable, so the TS composite with 5.0 wt.% fn-POSS is therefore of definite interest. The incorporation of fn-POSS with TS composites can improve their characteristics, boost the use of nanoparticles in food packaging, and promote studies on biodegradable composites. Full article

Honeycomb films pore-filled with metal (Au, Ag, and Cu) nanoparticles were successfully prepared by combining the breath figure method and an in situ reduction reaction. First, a polyhedral oligomeric silsesquioxane (POSS)-based star-shaped polymer solution containing metal salt was cast under humid conditions for the formation of honeycomb films pore-filled with metal salt through the breath figure method. The morphology of the honeycomb films was mainly affected by the polymer molecular structure and the metal salt. Interestingly, the promoting effect of the metal salt in the breath figure process was also observed. Then, honeycomb films pore-filled with metal nanoparticles were obtained by in situ reduction of the honeycomb films pore-filled with metal salt using NaBH₄. Notably, the metal nanoparticles can be selectively functionalized in the pores or on the surface of the honeycomb films by controlling the concentration of the NaBH₄. Metal-nanoparticle-functionalized honeycomb films can prospectively be used in catalysis, flexible electrodes, surface-enhanced Raman spectroscopy (SERS), and wettability patterned surfaces. Full article

In this study, we investigated the influence of methacryl-functionalized polyhedral oligomeric silsesquioxane (MA-POSS) nanoparticles as a plasticizer and thermal stabilizer for a poly(vinyl chloride) (PVC) homopolymer and for a poly(vinyl chloride)/dissononyl cyclohexane-1,2-dicarboxylate (PVC/DINCH) binary blend system. The PVC and the PVC/DINCH blend both became flexible, with decreases in their glass transition temperatures and increases in their thermal decomposition temperatures, upon an increase in MA-POSS content, the result of hydrogen bonding between the C=O groups of MA-POSS and the H–CCl units of the PVC, as determined using infrared spectroscopy. Furthermore, the first thermal decomposition temperature of the pure PVC, due to the emission of HCl, increased from 290 to 306 °C, that is, the MA-POSS nanoparticles had a retarding effect on the decomposition of the PVC matrix. In tensile tests, all the PVC/DINCH/MA-POSS ternary blends were transparent and displayed flexibility, but their modulus and tensile strength both decreased, while their elongation properties increased, upon an increase in MA-POSS concentration, both before and after thermal annealing. In contrast, the elongation decreased, but the modulus and tensile strength increased, after thermal annealing at 100 °C for 7 days. Full article

Giant surfactants refer to a new kind of amphiphile by incorporating functional molecular nanoparticles with polymer tails. As a size-amplified counterpart of small-molecule surfactants, they serve to bridge the gap between small-molecule surfactants and amphiphilic block copolymers. This work reports the design and synthesis of single-tailed giant surfactants carrying a hydrophobic poly(ε-caprolactone) (PCL) as the tail and a hydrophilic cage-like polyhedral oligomeric silsesquioxane (POSS) nanoparticle as the head. The modular synthetic strategy features an efficient “growing-from” and “click-modification” approach. Starting from a monohydroxyl and heptavinyl substituted POSS (VPOSS-OH), a PCL chain with controlled molecular weight and narrow polydispersity was first grown by the ring-opening polymerization (ROP) of ε-CL under the catalysis of stannous octoate, leading to a PCL chain end-capped with heptavinyl substituted POSS (VPOSS-PCL). To endow the POSS head with adjustable polarity and functionality, three kinds of hydrophilic groups, including hydroxyl groups, carboxylic acids, and amine groups, were installed to the periphery of POSS molecule by a high-efficiency thiol-ene “click” reaction. The compounds were fully characterized by NMR, gel permeation chromatography (GPC), MALDI-TOF mass spectrometry, and TGA analysis. In addition, the preliminary self-assembly study of these giant surfactants was also investigated by TEM and dynamic laser light scattering (DLS), which indicated that they can form spherical nanoparticles with different diameters in aqueous solution. This work affords a straightforward and versatile way for synthesizing single-tailed giant surfactants with diverse head surface functionalities. Full article

The present study reports on the use of three types of polyhedral oligomeric silsesquioxanes (POSS) nanoparticles with various organic substituents as fillers in a fluoroelastomer (FKM). A series of/POSS elastomer composite thin films is prepared. Microstructural SEM/TEM (scanning electron microscopy/transmission electron microscopy) imaging reveals a dispersion state allowing the presence of micron-sized domains. The influence of POSS content is studied in order to optimize thermal stability and mechanical properties of the composite thin films. Both POSS-A (with an acryloyl functional group and seven isobutyl substituents) and POSS-P (with eight phenyl substituents) lead to higher thermal stability and modulus of the composites, with respect to the unfilled FKM terpolymer matrix. covalent grafting of POSS-A onto the FKM network is found to play a critical role. Enhanced storage modulus in the rubbery plateau region (+210% at 200 °C for 20 phr) suggests that POSS-A is particularly suitable for high temperature applications. Full article

In this article, we studied two different types of polyhedral oligomeric silsesquioxanes (POSS^®) functionalized nanoparticles as additives for nanocomposite membranes for CO₂ separation. One with amidine functionalization (Amidino POSS^®) and the second with amine and lactamide groups functionalization (Lactamide POSS^®). Composite membranes were produced by casting a polyvinyl alcohol (PVA) layer, containing either amidine or lactamide functionalized POSS^® nanoparticles, on a polysulfone (PSf) porous support. FTIR characterization shows a good compatibility between the nanoparticles and the polymer. Differential scanning calorimetry (DSC) and the dynamic mechanical analysis (DMA) show an increment of the crystalline regions. Both the degree of crystallinity ($X_c$) and the alpha star transition, associated with the slippage between crystallites, increase with the content of nanoparticles in the PVA selective layer. These crystalline regions were affected by the conformation of the polymer chains, decreasing the gas separation performance. Moreover, lactamide POSS^® shows a higher interaction with PVA, inducing lower values in the CO₂ flux. We have concluded that the interaction of the POSS^® nanoparticles increased the crystallinity of the composite membranes, thereby playing an important role in the gas separation performance. Moreover, these nanocomposite membranes did not show separation according to a facilitated transport mechanism as expected, based on their functionalized amino-groups, thus, solution-diffusion was the main mechanism responsible for the transport phenomena. Full article

The organic/inorganic hybrid materials from polyhedral oligomeric silsesquioxane (POSS, inorganic nanoparticles) and polybenzoxazine (PBZ) have received much interesting recently due to their excellent thermal and mechanical properties, flame retardance, low dielectric constant, well-defined inorganic framework at nanosized scale level, and higher performance relative to those of non-hybrid PBZs. This review describes the synthesis, dielectric constants, and thermal, rheological, and mechanical properties of covalently bonded mono- and multifunctionalized benzoxazine POSS hybrids, other functionalized benzoxazine POSS derivatives, and non-covalently (hydrogen) bonded benzoxazine POSS composites. Full article

In this study, we prepared a mesoporous carbon with hexagonally packed mesopores through evaporation-induced self-assembly (EISA)—with the diblock copolymer poly(ethylene oxide-b-ε-caprolactone) (PEO-b-PCL) as the template (EO₁₁₄CL₈₄), phenolic resin as the carbon precursor, hexamethylenetetramine (HMTA) as the curing agent, and star octakis-PEO-functionalized polyhedral oligomeric silsesquioxane (PEO–POSS) as the structure modifier—and subsequent carbonization. We then took the cylindrical mesoporous carbon as a loading matrix, with AgNO₃ and Pd(NO₃)₂ as metal precursors, to fabricate Ag nanowire/mesoporous carbon and Pd nanoparticle/mesoporous carbon nanocomposites, respectively, through an incipient wetness impregnation method and subsequent reduction under H₂. We used transmission electron microscopy, electron diffraction, small-angle X-ray scattering, N₂ isotherm sorption experiment, Raman spectroscopy, and power X-ray diffraction to investigate the textural properties of these nanometal/carbon nanocomposites. Most notably, the Raman spectra of the cylindrical mesoporous carbon, Ag/mesoporous carbon, and Pd/mesoporous carbon revealed interesting phenomena in terms of the ratios of the intensities of the D and G bands (I_D/I_G), the absolute scattering intensities, and the positions of the D bands. Full article

The covalent incorporation of inorganic building blocks into a polymer matrix to obtain stable and robust materials is a widely used concept in the field of organic-inorganic hybrid materials, and encompasses the use of different inorganic systems including (but not limited to) nanoparticles, mono- and polynuclear metal complexes and clusters, polyhedral oligomeric silsesquioxanes (POSS), polyoxometalates (POM), layered inorganic systems, inorganic fibers, and whiskers. In this paper, we will review the use of two particular kinds of structurally well-defined inorganic building blocks, namely transition metals oxoclusters (TMO) and polyoxometalates (POM), to obtain hybrid materials with enhanced functional (e.g., optical, dielectric, magnetic, catalytic) properties. Full article

Hybrid materials with superior structural and functional properties can be obtained by incorporating nanofillers into polymer matrices. Polyhedral oligomeric silsesquioxane (POSS) nanoparticles have attracted much attention recently due to their nanometer size, the ease of which these particles can be incorporated into polymeric materials and the unique capability to reinforce polymers. We review here the state of POSS-containing polymer nanocomposites. We discuss the influence of the incorporation of POSS into polymer matrices via chemical cross-linking or physical blending on the structure of nanocomposites, as affected by surface functional groups, and the POSS concentration. Full article

Our continuing quest to improve the performance of polymer composites under moist and saltwater environments has gained momentum in recent years with the reinforcement of inorganic nanoparticles into the polymer. The key to mitigate degradation of composites under such environments is to maintain the integrity of the fiber/matrix (F/M) interface. In this study, the F/M interface of carbon/vinyl ester composites has been modified by coating the carbon fiber with polyhedral oligomeric silsesquioxane (POSS). POSS is a nanostructured inorganic-organic hybrid particle with a cubic structure having silicon atoms at the core and linked to oxygen atoms. The advantage of using POSS is that the silicon atoms can be linked to a substituent that can be almost any chemical group known in organic chemistry. Cubic silica cores are ‘hard particles’ and are about 0.53 nm in diameter. The peripheral organic unit is a sphere of about 1–3 nm in diameter. Further, cubic structure of POSS remains intact during the polymerization process and therefore with appropriate functional groups, if installed on the fiber surface, would provide a stable and strong F/M interface. Two POSS systems with two different functional groups; namely, octaisobutyl and trisilanolphenyl have been investigated. A set of chemical and mechanical procedures has been developed to coat carbon fibers with POSS, and to fabricate layered composites with vinyl ester resin. Interlaminar shear and low velocity impact tests have indicated around 17–38% improvement in mechanical properties with respect to control samples made without the POSS coating. Saltwater and hygrothermal tests at various environmental conditions have revealed that coating with POSS reduces water absorption by 20–30% and retains the composite properties. Full article