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The present paper studies the effect of polyaniline grafting on magnetite functionalized with aminopropyltrimethoxysilane. All the compounds were characterized by analytical techniques (X-ray fluorescence, X-ray diffraction, Fourier transform infrared spectroscopy, thermal analysis, Transmission electron microscopy), as well as by determining their magnetic properties. The electron microscopy analysis of the hybrids shows similar morphologies for all the samples. The presence of the iron atoms on the surface of the final product supports the idea of the existence of an inverted core-shell type structure, the more polar ferrite orienting itself towards water. The correlation between the maximum grafting probability and the maximum magnetization is evidenced, demonstrating the importance of the polymer grafting method on the magnetic properties.

Sol-gel derived organic-inorganic hybrid systems were obtained by applying alkaline-catalyzed co-hydrolysis and copolycondensation reactions of tetraethoxysilane (TEOS), methyltriethoxysilane (MTES), isobutyltriethoxysilane (IBTES), diethoxydimethylsilane (DMDES), and vinyltriethoxysilane (VTES), respectively, into a polymer latex functionalized with vinyltriethoxysilane (VTES). The properties of the latex hybrid materials were analyzed by FTIR, water contact angle, environmental scanning electron microscopy (ESEM), TEM and AFM analysis, respectively. FT-IR spectra confirmed that the chemical structures of the sol-gel derived organic-inorganic materials are changed as function of inorganic precursor and Si O Si networks are formed during the co-hydrolysis and copolycondensation reactions. The water contact angle on the sol-gel latex film containing TEOS + VTES increased to 135° ± 2 compared to 65° ± 5 for the blank latex, due VTES incorporation into latex material. TGA curves of hybrid sample modifies against neat polymer, the thermal stability being influenced by the presence of the inorganic partner. ESEM analysis showed that the latex hybrid films prepared with different inorganic precursors were formed and the Si-based polymers were distributed on the surface of the dried sol-gel hybrid films. TEM and AFM photos revealed that the latex emulsion morphology was modified due to the VTES incorporation into system.

This paper debates the effect of the stabilizer (vinyl benzyl trimethyl ammonium chloride—VBTAC or cetyl trimethyl ammonium chloride—CTAC) and the structure (typical SiO2 matrix or inorganic–organic interpenetrated matrix) influence in molecular imprinting of gallic acid-polyphenol class of templates. For this purpose, gallic acid-imprinted particles were obtained via typical polycondensation sol–gel reactions and via sol–gel/radical polymerization concurrent reactions of tetraethoxy silane (TEOS) and aminopropyl ethoxy silane (APTES) or vinyl triethoxy silane (VTES), respectively. The influence of the mesophase formation and stabilizer nature upon the re-binding of gallic acid was investigated using thermal, infrared and morphology measurements. Adsorption assays of organosilica particles were well correlated with their physical properties. Unlike the polycondensation of TEOS with APTES in the presence of CTAC, concurrent radical polymerization of VBTAC consumed the vinyl functionalities of VTES, decreasing the capacity of VBTAC to mediate the mesophase formation and the capacity of VTES to coordinate template molecules; hence, both the binding capacity and the “memory” effect of the interpenetrated organosilica structure were significantly affected.

The radical polymerization of aniline hydrochloride (ANIHCl) in the presence of ammonium persulfate was studied. 1D-Polyaniline (PANI) with fibrillar morphologies was obtained in the presence of anionic surfactants. The changes of the PANI-template structures in aqueous solution were studied using static fluorescence measurements. The dispersed PANI nanoparticles were characterized using dynamic light scattering, scanning electron microscopy (SEM), and Raman and Fourier transform infrared spectroscopies. The thermal analysis and the electrical conductivity of the dried samples were also performed. The fluorescence measurements indicated that nanocrystals of ANIHCl form in water complexes with the anionic surfactants at smaller concentrations than the critical micellar concentration. The same method revealed that other organic complexes with sulfonate groups do not induce an increase of the hydrophobic region due to short hydrocarbon tails. The SEM micrographs and Raman spectra revealed that the PANI nanofibers are compact and different compared to the nanoparticles prepared without surfactants.

Thermogravimetric analysis (TG), derivative thermogravimetry (DTG), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis, simultaneous differential thermogravimetry (SDT) coupled with mass spectrometry (MS), and pyrolysis coupled with gas chromatography/mass spectrometry (Py-GC/MS) were used to characterize molecularly imprinted polymers (MIPs) obtained with two anti-cancerous template molecules, diosgenin and sclareol, imprinted in acrylonitrile–acrylic acid copolymer matrices. First of all, TG analyses revealed a specific mass loss in the temperature range 220–300 °C characteristic to diosgenin-MIPs, while for the sclareol-MIPs, the specific interval was 100–240 °C. Further, the DSC analyses evidenced two major aspects: first, that the copolymer matrices have a single glass transition temperature (T g), which confirms the random statistic copolymer structure, an essential characteristic of a homogenous MIP matrix; secondly, both templates influence the T g values of the MIPs, fact that is an additional proof of molecular imprinting. The SDT results confirmed the TG and DSC results and, additionally, proved that the system with higher acrylic acid content generates stronger template–matrix interactions via hydrogen, van der Waals, and other non-covalent forces, fact that appears as an increased thermal stability on the TG curve and a higher maximum for template decomposition on the DTG curve. The MS results evidenced that a single mass fragment, 139 ± 1 m/z, characteristic for the class of steroid sapogenines of which diosgenin belongs, is enough to prove, qualitatively and quantitatively, the molecular imprinting and the template elution. As global conclusion, the applied thermal analyses proved to be exceptional tools for analyzing these molecularly imprinted polymers.

In this research, both commercially available (Cloisite 93A) and advanced functionalized clay mineral were used to obtain clay–epoxy nanocomposites. Cloisite 93A was modified with three different alkoxysilanes and was incorporated in Epon 862 epoxy resin which was crosslinked using tetraethylenepentamine as a curing agent. The determination of color grades of the composite samples was followed. The morphology of the composites was analyzed using X-ray diffraction and ESEM micrographs which provided insight into the fracture mechanism. Thermal behavior was evaluated by TGA and DSC and thermo-mechanical properties of the cured samples have been evaluated by DMA technique. The data indicated that intercalated or agglomerated silylated Cloisite–epoxy nanocomposites were obtained. The silylated Cloisite samples are more compatible with the polymer matrix due to their enhanced hydrophobic behavior leading to an improvement in storage modulus and stiffness but also to the increase of glass transition temperature up to 30 °C.

In this study, the organophilization procedure of kaolin rocks with a monofunctional ethoxysilane- 3 aminopropyl dimethyl ethoxysilane (APMS) is depicted for the first time. The two-step organophilization procedure, including dimethyl sulfoxide intercalation and APMS grafting onto the inner hydroxyl surface of kaolinite (the mineral) layers was tested for three sources of kaolin rocks (KR, KC and KD) with various morphologies and kaolinite compositions. The load of APMS in the kaolinite interlayer space was higher than that of 3-aminopropyl triethoxysilane (APTS) due to the single-point grafting nature of the organophilization reaction. A higher long-distance order of kaolinite layers with low staking was obtained for the APMS, due to a more controllable organiphilization reaction. Last but not least, the solid state (29)Si-NMR tests confirmed the single-point grafting mechanism of APMS, corroborating monodentate fixation on the kaolinite hydroxyl facets, with no contribution to the bidentate or tridentate fixation as observed for APTS.

Obtaining composite materials based on multiwalled carbon nanotubes (MWCNT) from water dispersion is viable nanotechnology with low impact on the environment and with concrete directions for advanced materials used in coating application. Emulsion, miniemulsion, or microemulsion polymerization techniques can offer by their nature the reducing of the interfacial tension (between MWCNTs and monomers). By free radical polymerization, MWCNT-polymer composites can be obtained in a greener manner by cutting off several supplementary technological steps involved by functionalizing (toxic reagents, energy consuming), solvent phase purification, and separation of the fillers. Providing such examples involving large tonnage polymers like polystyrene, SAN copolymer, polyacrylonitrile, poly(methyl methacrylate) and other, a detailed picture of the state of the art can be achieved for synthesis and application in automotive industry, aerospace, coating materials, antistatic materials, sensors, actuators, membrane production, fibers industry, and others. The chapter tries to answer to some technological bottlenecks: decreasing the environment impact and extending the areas of application by reducing the costs of MWCNTs processing for polymer composites as a natural step for the sustainable development of an MWCNT-composite industry.

The stability of the organosilica–gallic acid (GA) complex, and thus the strength of initial interactions which influences directly the sorption parameters of imprinted materials, is mostly given by the nature of co-monomers. Therefore, combining tetraethoxysilane, tetrametoxysilane, vinyl triethoxysilane and vinyl benzyl triethoxysilane as functional monomers, six formulations were obtained in order to optimise the nature of imprinted sieves. Vinyl benzyl trimethylammonium chloride and tertamethyl ammonium hydroxide directed the mesophase formation. Morphology and thermal properties of imprinted organosilica sieves were evaluated and compared to those of blank polymers synthesised in the same conditions as the imprinted ones but without GA. Thermal analysis results corroborated with the morphology of imprinted sieves were confirmed by specific GA sorption tests.

The increased interest in silica nanowires for nanophotonics, mechanical applications, microsurgery, chemical and biological sensors strongly motivates the search for new discoveries involving complex silica nanowire-clay mineral layers (SiNW), particularly focusing on their growth mechanism, their involvement during polymer synthesis and the generation of a new class of polymer nanocomposites. This paper addresses the major findings involving the growth mechanism of silica nanowires on the clay mineral layers as well as their high segmental mobility and influence on the kinetics of butylacrylate mini-emulsion radical polymerisation. The growth mechanism for the silica nanowires was a sol-gel process involving tetraethylorthosilicate at the edge groups of the clay layers after blocking the reactive sites with a monofunctional alkoxysilane. To demonstrate the mobility of the network, an indirect method was utilised, specifically the interaction between the ethoxylated molecules and Tween 60. No cross-linking side effects occurred in the silica nanowires. SiNW enhance the free radical polymerisation of butylacrylate in dispersed media, increasing the monomer conversion from 2.5% to 33%. The kinetics of the polymerisation process can be tuned by SiNW, modulating the system between emulsion- and mini-emulsion-like systems by acting on the pseudo-steady state interval of the radicals (10%–40% conversion).

Polymer-clay nanocomposites were synthesized by solution polymerization method using advanced functionalized clay and vinyl benzyl trimethyl ammonium chloride as monomer. First stage consisted in the silylation of a commercial organo-modified clay-Cl 20A using alkoxysilanes with different chain lengths. In the second step, the synthesis and characterization of polymer-nanocomposites were followed. To evaluate the clay functionalization process as well as the final polymer-clay products, thermogravimetric, X-ray diffraction, dynamic light scattering, Fourier transform infrared spectroscopy and three test liquid contact angles analyses were used. The loss of ammonium ions from commercial clay, the grafting degree, the lengths and the nature of alkyl chain influence the dispersion of the advanced modified clay into the polymer solution and, furthermore, the properties of the final polymer-clay nanocomposite film.

This paper reports the synthesis of coating silica particles, in order to design hybrid materials with hydrophobic surface properties. The silica particles were prepared in basic conditions under atmosphere of carbon dioxide (CO 2 ), using tetraethylorthosilicate (TEOS) as a precursor and octyltriethoxysilane (OTES) as a surface modifying agent. It was demonstrated that the contact angles of silica hybrid films could be changed by varying temperature and pressure of CO 2 . The investigation of the prepared hybrid materials by dynamic light scattering (DLS) and environmental scanning electron microscopy (ESEM), respectively, showed that they consisted mainly of particles with a diameter of 100–250 nm. Fourier transform infrared (FT-IR) spectra indicate that the interaction between the coupling reagents, at different conditions, is mainly through chemical bonding.

The objective of this study is to design new hybrid silica materials as templates with hydrophobic properties, prepared at room temperature by a base catalyzed sol–gel process. As silica sources, organoalkoxysilanes functionalized with short hydrophobic chains were used: tetraethylorthosilicate (TEOS), methyltriethoxysilane (MTES), vinyltriethoxysilane (VTES), octyltriethoxysilane (OTES) and isobutyltriethoxysilane (iTES). It was shown that hydrophobicity of the functionalized silica nanoparticles increased as a function of length of the aliphatic chains (MTES < iTES < OTES) or when, instead of a hydrophobic alkyl chains (substituting group of silica precursors), a monounsaturated group was used (VTES). It was observed that the samples responded in a specific way to each type (hydrophilic or hydrophobic) of the dropped liquid. Even though the experiments were limited to short hydrocarbon chains, they showed that there is a threshold to reach high hydrophobicity of the hybrid surface.

Hybrid thin films, silica–titanium oxides and silica–aluminum oxides, designed based on the sol–gel process are evaluated as catalysts in the photo-degradation of the cationic dyes. Silica matrices from different precursors with various organic functional groups and cross-linked with titanium or aluminum agents (tetraisopropyl orthotitanate and aluminum sec-butoxide) allow the surface property tailoring related to the high capacity of the dye adsorption respective, high photo-degradation activity. The cationic dyes (methylene blue, rhodamine B, crystal violet, malachite green) embedded on the hybrid silica matrix, under ultraviolet light, have a first order kinetics of photodegradation. The cross-linking agents play a key role in the photocatalytic degradation and silica matrix as dye absorbent. The photo-degradation rate for the binary system derived from methyltriethoxysilane/vinyltriethoxysilane precursors with both cross linkers showed a significant improvement by comparison with other hybrid materials. The significant increasing in the photodecomposition rate is related to the capacity to generate additional oxidizing species by each silica hybrid compounds.

In this report, we present the versatile and effective technique, using environmental friendly reductant glucose, to prepare stable silver nanodispersions by reduction of Ag+ ions. Alternant copolymers of maleic anhydride with vinyl acetate and styrene sulphonate sodium acid salt polyelectrolytes were synthesized in aqueous solution and used as stabilizers. The formation of nano silver particles was confirmed by UV-Vis spectrophotometry and TEM measurements. Dynamic Light Scattering (DLS) measurements were needed to study how the reagents and their concentrations influence particle size. SEM images show the nanostructure of the hybrid films and indicate a strong interaction between the polyelectrolyte and the silver NPs. Moreover, the silver NPs could be stored for one year without observation of aggregates or sedimentation. The final solid products obtained after evaporating to dryness can be used to produce stable dispersions upon mixing with water. Few of the final products were found to exhibit a high antibacterial and antifungal activity.

Modifications to the refractive indices of meso-structured organic–inorganic films caused by variations in the mole fraction of precursors in ethanolic solutions were investigated. The refractive indices were dependent on the mole fraction of C16TMS (hexadecyltrimethoxysilane) and of the C16TMS/TMOS (tetramethoxysilane) (1/1) mixture in ethanol. The dependency was determined to be nonlinear, and the phenomenon was attributed to self-assembly caused by the long alkyl groups (C16) on the C16TMS. Changes in the maximum decreasing rate of dn/dx values [(dn/dx)max—for dn/dx estimation, the curves from Fig. 1 were associated with a polynomial; using a dedicated program, dn/dx was calculated; maximum values of dn/dx were taken into account and were included in Table 1)] were used to distinguish the behavior of alcoholic precursor mixtures. In the case of using pyrene as a fluorescent probe, the ratio between two peaks from the pyrene emission spectra (I1/I3) strongly decreased as hydrophobic micro-surroundings formed due to the self-assembly process. The UV–VIS spectra of a cationic dye solution, R6G, was studied because dilute solutions of the dye in equilibrium form measurable ratios of dimers and monomers. The absorbance was modified as micro-surroundings with different polarities were formed. These three methods demonstrated that nano-structuration was present prior to the occurrence of the sol–gel process. The combination of C16TMS with other alkyltrialkoxysilane precursors having hydrocarbon chain lengths between C1 and C8 provided further evidence for a nonlinear dependence of the refractive indice and fluorescence spectra of pyrene. The properties of the final hybrids obtained by the sol–gel process were significantly affected by the precursor hydrocarbon chain lengths. DSC, XRD and FTIR measurements were used to show the plasticizing phenomena of C16 as other alkyltrialkoxysilanes (i.e., C1–C8) were added.

Ultra-hydrophobic bilayer coatings on a glass surface were fabricated by sol–gel process using hexadecyltrimethoxysilane (C16TMS) and tetramethoxysilane (TMOS) (1:4 molar ratio) as precursors. After coating, silica nanoparticles (SiO2 NPs) functionalized with different mono-alkoxy derivatives (methoxytrimethylsilane, TMeMS; ethoxydimethylvinylsilane, DMeVES; ethoxydimethylphenylsilane, DMePhES; and methoxydimethyloctylsilane, DMeC8MS) were added, assuring the microscale roughness on the glass surface. Influences of the functionalized SiO2 NPs and surface morphology on the hydrophobicity of the hybrid films were discussed. The successful functionalization of SiO2 NPs with hydrophobic alkyl groups were confirmed by Fourier transform infrared spectroscopy (FTIR). The thermal stability of hydrophobic SiO2 NPs showed that the degradation of the alkyl groups takes place in the 200–400 °C range. Bilayer coating with C16TMS/TMOS and SiO2 NPs modified with alkoxysilane substituted with C8 alkyl chain (SiO2 NP-C8) has micro/nano structure. Hydrophobicity of functionalized SiO2 NPs-C8 and its higher degree of nanometer-scale roughness gave rise to ultra-hydrophobicity performance for bilayer coating C16TMS/TMOS + SiO2 NPs-C8 (145°), compared to other similar hybrid structures. Our synthesis method for the functionalization of SiO2 NPs is useful for the modification of surface polarity and roughness.

Liquid crystals/magnetic particles composites have been shown to exhibit very interesting behaviors when subjected to different external fields, finding new applications in the field of functional nanomaterials. We present a new colloidal composite formed by combining polymer-magnetite nanoparticles and a lyotropic nematic liquid crystals. TEM investigations on the polystyrene magnetite show magnetite nanocrystals anchored in polymeric chains. The optical transmission of the ferronematic was investigated when the samples were subjected to different values of static magnetic field and the critical magnetic field corresponding to the Freedericksz transition was estimated.

Bulk and microemulsion systems were studied in order to obtain molecularly imprinted copolymers selective for gallic acid. Both systems contained acrylic acid as the functional monomer and ethylene glycol dimethacrylate as crosslinker. Microemulsion formation was confirmed by refractive index measurements and by conductivity analyses. Simple uptake tests revealed higher affinities for the microemulsion polymers; a 3.55 imprinting factor and a 0.275 g gallic acid (g polymer)–1 adsorption capacity were recorded. Competitive uptake tests, from an oak bark extract, were in agreement with the simple uptake results and BET analyses. Microemulsion polymer particles selectively bind 4.58 times more gallic acid molecules relative to other competitor species.

Magnetite alternating copolymers divinylbenzene–maleic anhydride (DVB–MA) composites were prepared by dispersion polymerization. Because magnetite is used as a complex with oleic acid (Fe3O4OLA), the final hybrids show good dispersion of inorganic nanofillers in the polymer matrix. The obtained composites were analyzed by infrared absorption spectrometry, diffuse reflectance in visible light, thermogravimetry, X-ray fluorescence, X-ray diffraction, dynamic light scattering, scanning electron microscopy and vibrating sample magnetometry. The obtained results indicate the successful preparation of magnetite nanoparticles with an average size of about 23 nm dispersed in micrometer size copolymer spherical particles, which relative content can be controlled via the processing parameters. A relationship between the relative content of magnetite nanoparticles and the size of the polymer particles, with direct influence on the diffuse reflectance in the visible domain, was observed. A superparamagnetic behavior was evidenced at room temperature with a blocking temperature lower than as expected from the bulk anisotropy constant and the average size of the magnetite nanoparticles. Both the unexpected low blocking temperature and the observed low specific magnetizations were explained by a defected and poor crystalline structure of the magnetite nanoparticles, giving rise to spin disorder and diminished crystalline anisotropy constant.

We report the synthesis of molecularly imprinted sorbents, selective for gallic acid. The particles were prepared by using acrylic acid, acrylonitrile, and hydroxyethyl methacrylate as functional monomers, whereas ethyleneglycol dimethacrylate and 1,4-buthanediol dimethacrylate were used as crosslinkers. Preparation and manipulation protocols were adjusted considering template's nature. To highlight the influence of monomer/crosslinker nature upon imprinted particles, the adsorption capacity, the imprinting factor, and the distribution and selectivity coefficients were calculated. An imprinting factor of 3.53 and a selectivity coefficient of 6.86 were found for hydroxyethyl methacrylate/ethylene glycol methacrylate system. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci. 2013

The paper deals with the rheological properties of epoxy resin additivated with organically modified montmorillonites, carbon nanotubes and nanocarbon. The paper also presents the influence of nanoadditives over composites mechanical properties. The epoxy polymer is diglycidyl ether of bisphenol A (DGEBA) and the curing agent is an aliphatic tetraamine. Organically modified montmorillonites Cloisite 30B and Cloisite 93A, MWCNTs and laser synthesized nanocarbon were used to synthesize nanocomposites by dispersing each in an epoxy resin. The dispersion was achieved through mechanical and sonic methods. The epoxy resin additivated with nanosized fillers was rheologically tested to study the dispersion influence. The sonic dispersion of nanoadditives is observed to drastically influence the rheological behavior of the suspensions. Newtonian fluid behavior disappears as the additive loading increases. The work mentions the influence of nanoadditives on the manufacturing process of epoxy /glass fibre and epoxy/ carbon fibre laminated composites.

Sodium montmorillonite (NaMMT clay) derivatives were encapsulated in polymer particles obtained through dispersion copolymerization of divinyl benzene (DVB) with maleic anhydride (MA). To evidence the effect of alkyl monoalkoxysilanes upon MMT reaction, a variety of MMT clay functional derivatives were investigated. Particles with an increased size of modified MMT clay dispersed in dichloromethane were obtained using alkyl monoalkoxysilanes with a longer hydrocarbon chain. Relatively long hydrocarbon chains can exhibit a low substitution degree of MMT clay with alkyl monoalkoxysilanes. MMT class with a low substitution degree leads in the presence of alkoxysilanes to particles with average size between 700 and 1200 nm, and when DVB–MA copolymer is added the particles size decreases (~480 nm). The influence of layered silicates on the thermal stability of DVB–MA copolymer as a function of the used vinyl siloxanes derivatives for functionalization of MMT, on one hand, and the nonlinear variation of refractive index of used silanes on the other hand, pointing out the autoassociation during initial reaction of substitution.

Polymer composites from polylactic acid (PLA) and two types of cellulose fibers obtained either by acid hydrolysis of microcrystalline cellulose (HMCC) or by mechanical disintegration of regenerated wood fibers (MF) were prepared and characterized. To enhance the compatibility of the cellulose fibers with PLA matrix, a surface treatment based on 3-aminopropyltriethoxysilane (APS) was performed. The Fourier Transform Infrared (FTIR) spectroscopy was used to determine the chemical groups involved in the surface modification reaction. The silanization treatment resulted in different modifications on both types of cellulose fibers because of their different structural and morphological characteristics. The composites were prepared by incorporating 2.5% of the treated or untreated HMCC and MF into a PLA matrix using a melt-compounding technique. An improved adhesion between the two phases of the composite materials was observed by scanning electron microscopy thanks to treatment. The dynamic mechanical thermal analyses showed that both untreated and silane treated fibers led to an improvement of the storage modulus of PLA in the glassy state. A higher enhancement of the storage modulus in the case of PLA/HMCC composites than the composites containing MF was obtained as a result of the high aspect ratio of these fibers which allows better matrix-to-filler stress transfer. Furthermore, the storage modulus of PLA composites was enhanced by silanization even at higher temperatures especially after thermal treatment. The cellulose fibers addition in PLA matrix modified significantly the relaxation phenomenon as observed in tan δ curves, emphasizing strongly modified molecular mobility of PLA macromolecules and crystallization changes. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers.

This paper describes a method to prepare silica particles able to encapsulate 3 different hydrophobic dyes: Disperse Red, Solvent Red and 2-{4-[4-(Benzyl-ethyl-amino)-phenylazo]-benzenesulfonyl}-ethanol (HESA). Dye doped silica particles were prepared by the sol–gel process in aqueous medium, with a base catalyst, using various concentrations of a “home made” surfactant (named NP9-Si). The surfactant is the addition byproduct of –OH groups of polyethylene glycol nonylphenyl ether Tergitol® NP-9 with -NCO groups from (3-isocyanatopropyl) triethoxysilane and was added to increase both the stabilization of the silica particles and the compatibility of the inorganic network versus the dopant (the aromatic dye). It was shown that there is an optimum range of the amount of surfactant which should be added in the sol–gel reaction system. If a higher amount of surfactant is used, it forms probably micelles which entrap the dye and prevent its encapsulation in the formed silica particles. Because the silica particles are designed to encapsulate systems containing aromatic derivatives (aromatic dyes) we used phenyltriethoxy silane and tetraethylorthosilicate as silica precursors. As coupling agent for the silica network we used a bis (trialkoxysilane) derivative—1,2-bis (triethoxy silyl) ethane.

New nanocomposites based on polyacrylates and five types of montmorillonites modified by edge covalent bonding, were obtained. The alkoxysilanic substituent strongly influenced the physical–chemical properties of the final material. All modified clay minerals exhibit a lower wettability compared to pure montmorillonite. FTIR and TGA analyses confirmed the incorporation of montmorillonite in the polyacrylate matrix. Rugged spherical particles indicated that the platelets were predominantly on the polymer particles.

Nanocomposites of divinylbenzene-maleic anhidride (DVB-MA) copolymers were synthesized in aqueous medium by generating silver nanoparticles from AgNO3-NaBH4 reaction. SEM images evidence the forming of metal nanoparticles on the particles surface of DVB-MA copolymers. The copolymer particles have larger diameters in the presence of monoesther maleic of nonyl phenol ethoxylate or sodium montmorillonite than DVB-MA copolymer particles although the nanoparticles' forming is still possible. The average size and the Zeta potential of the hybrid particles decrease in water, toward the initial copolymers sustains the forming of nanocomposites with Ag nanoparticles on the surface.

The sol–gel synthesis strategies combined with the templated growth of organic–inorganic hybrid networks provide access to an immense new area of innovative multi-functional advanced materials. One possible way to prepare such new advanced materials is to encapsulate liquid active agents (such as monomers, dyes, catalysts and hardeners) in microcapsules. Silica microcapsules of tetraethylortosilicate (TEOS) and 3-(trimethoxysilyl)propyl methacrylate (MPTS) were prepared in a precursor-monomer/NH4OH water microemulsion system. Trimethylolpropane triacrylate (TMPTA)—a trifunctional monomer useful in manufacturing of coatings, inks and adhesives—and a corresponding photoinitiator (DAROCUR 1173) were entrapped inside the obtained microcapsules. MPTS was used to increase compatibility between TMPTA and the sol–gel precursors. As stability agent we added a “home made” product resulted from functionalization of poly (ethylene glycol) methyl ether (MPEG) with (3-isocyanatopropyl) triethoxysilane (NCOTEOS). Were obtained microcapsules containing incorporated monomer and having average particle size in range of 0.5–50 μm. Thermal analysis, morphology study and the increase of the silica microcapsules average diameter, measured by DLS technique confirm the monomer encapsulation.

Silver nanoparticles were prepared by the chemical reduction of silver nitrate, AgNO3, with excess of sodium borohydride, NaBH4, in dilute aqueous solutions containing triblock copolymers poly(ethylene oxide) (PEO)–poly(propylene oxide) (PPO)–poly(ethylene oxide) (PEO) Pluronic L64. The synthesis was completed in ∼24 h and produced highly stable particle dispersion. The growth of nanoparticles was assessed by combining Mie theory, UV–vis spectroscopy and dynamic light scattering, and the average particle size was determined from transmission electron microscopy. The silver nanoparticles were sterically stabilised as a result of the block copolymer adsorption onto the nanoparticle surface. Besides the stabilizing character, the copolymer affected the kinetics of particle growth, the size and optical properties of as-synthesized Ag nanoparticles. It was revealed that the particle formation took place in two distinct stages. The first step was dominated by Ag ion reduction and growth driven by accretion, while in the second stage coagulated clusters of nanoparticles were obtained obtained. The as-synthesized particles were polydisperse, the individual ones had a size of ∼7.6 nm as given by transmission electron microscopy, and the hydrodynamic radius of clusters amounted to 60 nm. The silver nanoparticles exhibited broad and structured emission bands centered at 300 and 330 nm for excitation wavelengths in two different ranges, 220–240 nm and 260–290 nm, respectively. This process may be assigned to two emission components corresponding to two different excitation wavelength domains.

Synthesis of nanocomposites based on polystyrene/polybutylacrylate with layered silicates using emulsion polymerization procedure in aqueous medium allowed obtaining stable nanolatexes with sodium dodecyl sulfate as surfactant. Monomer and layered silicate nature influences the average diameter of the particles and the zeta potential appeared on the particle-disperse medium interface, as it was shown by dynamic light scattering analyses. In order to evidence the layered silicate structure, two structural evaluation methods were used. A new approach was used based on Fourier transform infrared analyses as a method to asses the clay delamination. The method was followed in conjunction with X-ray diffraction patterns and showed the pronounced delamination of the clay in the polymer matrix. The thermal stability was investigated by thermogravimetric analyses and the morphologies in solid state observed by environmental scanning electron microscope measurements.

We examined the electrical and optical properties of a new material containing polymer–clay nano-composite dispersed in a nematic liquid. The clay (Cloisite-type) was modified by copolymerization of maleic anhydride and divinyl benzene, using azobisisobutytironitrile as the initiator. The final polymer–clay nano-composite has an intercalated structure according to XRD patterns. We measured the thermally stimulated depolarization currents and determined the activation energies. Simultaneously we measured the optical transmission and we studied the influence of the previously applied polarizing electric fields.

Hybrid films containing different loadings of silver nanoparticles (0.5, 1 and 2.5 wt.%) have been prepared using a sol–gel method. Three types of materials were prepared in order to compare their properties: Ag nanoparticles (NPs) on hybrid film containing methyltrimethoxysilane (Ag-MeTMS), a similar hybrid material containing both MeTMS and 3-mercaptopropyltrimethoxysilane (MPTMS) as modifier (Ag-MeTMS/MPTMS) and finally a Ag-MeTMS film to which starch was added as modifier/reducing agent (Ag-MeTMS/starch). Characterized materials by TEM showed that, in general, Ag materials had a bimodal particle size distribution, with sizes of 7–8, 12–16 nm as well as some bigger agglomerates (on some of them) of 24–25 nm present at increasing silver loadings. The catalytic properties of the supported Ag NP were investigated in the oxidation of styrene. Ag-MeTMS/MPTMS materials were comparatively more active and selective than Ag-MeTMS or Ag-MeTMS/starch, regardless of the Ag content in the materials, providing high conversions and selectivities to styrene oxide.

We report surfactant-free emulsion polymerization of styrene by using five types of montmorillonite modified by grafting monofunctional alkoxysilanes. Dynamic light scattering (DLS) determinations were strongly influenced by the presence of modified montmorillonite. FTIR and XRD spectra confirmed the incorporation of montmorillonite in the polymer matrix. The morphology of the latex particles was changed. Spherical and snowman particles indicated that the platelets were both inside and outside of the polymer particles.

Styrene (St) and butyl acrylate (BuA) microemulsion polymerizations were investigated in presence of layered silicates (LS) and sodium dodecyl sulfate (SDS) as surfactant. Two main LS categories were used: one in the sodium form as Na montmorillonite (MMT) and the other in organomodified form LS (OLS) with quaternary ammonium salts having different hydrophobic modifiers. The swelling capacity of OLS in presence of monomers with different polarity is more pronounced for partners with closer hydrophobicity to St. The latexes obtained by microemulsion polymerization showed larger particles size for BuA polymer and BuA copolymer with sulfonated styrene than for St. Analyzing the dried hybrid polymers by XRD, we found structures which corresponds to exfoliated LS. The thermal behavior of hybrids, examined by TGA, showed higher rates of decomposing temperatures in the case of OLS, in comparison with the NaMMT hybrids. The obtained hybrids were evaluated by DLS, FTIR, DSC, and SEM.

Hybrid thin films containing palladium nanoparticles in different concentrations (0.5% and 1%) with and without nanoparticle stabiliser agent [mercaptopropyl trimethoxysilane, MPTMS] were prepared using a sol–gel process. Pd nanoparticles were found to be highly dispersed on the thin films with particles ranging from 7 to 10 nm. The catalytic properties of the thin films supported Pd nanoparticles were investigated in the Heck reaction of iodobenzene and methyl acrylate. Films containing Pd MNP (with and without MPTMS) gave quantitative conversion and complete selectivity to the targeted product (methyl cinnamate) in a short time of reaction (

A commercial vinylester-urethane (VEUH) hybrid resin was modified with organophilic layered silicates (OLS), incorporated in various amounts (0.1 to 5 wt.%). As organophilic intercalants of the layered silicate (synthetic fluorohectorite) trimethyl dodecylamine (TMDA) and octadecylamine - N,N-bis[allyl(2-hydroxypropyl)ether] (OAE) served. The latter quaternary amine was expected to support the intercalation/exfoliation of the silicate by participating in the crosslinking reactions. Both OLS types became intercalated based on X-ray diffractograms (XRD). Dynamic-mechanical thermal analysis (DMTA) displayed a slight increase in the stiffness by adding OLS up to 2.5 wt.%. However, at 5wt% OLS content the stiffness of the nanocomposites was below that of the unfilled hybrid resin. The glass transition temperature (Tg) did not change practically with the OLS type and content. Fracture mechanical tests were performed on compact tension (CT) specimens. The fracture toughness (Kc) increased slightly, while the fracture energy (Gc) markedly with increasing OLS content. Unexpectedly, TMDA proved to be a more suitable intercalant than OAE. The failure mode of the specimens was studied in a scanning electron microscope (SEM) and discussed. In addition, the water sorption behavior of the OLS modified VEUHs was determined and the diffusion coefficients (D) deduced.

We synthesized hybrid materials by sol-gel process, using: methyltriethoxysilane, tetraetylorthosilicate and vinyltriethoxysilane, in the presence of Rhodamine 6G. It was synthesized as well organic-inorganic hybrids with addition of tetraisopropyl orthotitanate and maleic anhydride UV-VIS spectra of dye show two absorption peaks at 499 nm (dimer) and 530 nm (monomer). Evaluating FTIR spectra of hybrid films, it was observed a band at 1077 cm−1, characteristic of the asymmetric Si-O-Si stretching vibration in oligomer. Fluorescence spectra show that tetraisopropyl orthotitanate presence in the composites modifies the nature of the inorganic matrix and affects the interaction with the added dye.

It was studied the polymerization of styrene (St) and of butyl acrylate (BuA) in nonionic microemulsions in the presence of a layered alumino silicates, montmorilonit (MMT) type. In time, the latexes separate in two distinct strata, MMT being distributed in the inferior strata where forms aggregates with on order of size bigger than the diameters of nanoparticles of latex. The solid products obtained are nanohybrids of intercalate type whose structural order increases direct proportional with the increase of hydrophobic character of the quaternary ammonium salts used for organophilization of MMT. The presence of nonionic surfactant, nonyl phenol with 25 mols of ethylene oxide, intercalated between the lamellar strata of MMT produces the decrease of thermal stability of hybrids and decreases the glass transition temperature of PSt which is more compatible than PBuA.

The effect was studied of various layered silicates (sodium montmorillonite and different organomodified montmorillonites) on kinetics of styrene (St) and butyl acrylate (BuA) in anionic (sodium dodecyl sulfate) microemulsion polymerization. The dependence of the polymerization rate on the conversion exhibits two rate intervals. The presence of layered silicates affects the conversion and polymerization rate of both St and BuA. The size of polymer particles increases with polarity of Cloisite and the increase is more pronounced in poly(butyl acrylate) particles. The kinetic, colloidal and molecular weight parameters are influence both by the monomer and layered silicate polarities. Different approaches (Ugelstadt, Nomura and Gilbert models) were used for evaluation of polymerization kinetics. The desorption constants (kdes) decrease in presence of the studied layered silicates (Cloisite Na, Cloisite 30B, Cloisite 20A). The decreasing values of the desorption constants in the presence of clays; demonstrate a clear effect, which implies the decreasing of the probability of the radical exit from particles in the presence of the layered silicates.

We have synthesized polymer particles of the type alternated copolymers DVB- maleic anhydride. The dimensions of the obtained particles have been determined by electron microscopy and are in the range 1–2 μm. These particles have been mixed by stirring and ultrasound with nematic liquid crystals ZLI 1221 (Merck), in a concentration of 5% b.w.(polymer/LC). We applied cycles of temperature and electric field, corresponding to the TSDC method. We measured the depolarization currents and simultaneously the optical transmission as a function of the electric field and temperature. We obtained information regarding the conduction mechanism, the activation energy and the pre-exponential frequency factor in the Arrhenius diagrams. The dipolar current obtained is consequent to a superposition of a dipolar distribution with a wide spectrum of relaxation times.

The work presents some preliminary results obtained in the attempt to perform hybrid polymer-based nanocomposites with laser synthesized carbon nanostructures and layered silicate. The preliminary results suggest that there is a close relation between the improved characteristics of the obtained nanocomposite and filler's properties. Laser synthesized nanocarbons, from almost amorphous up to fullerenic-like structure were used. As layered silicate, a modified Cloisite-type montmorillonite is mentioned. Preliminary results suggest that some of these addition agents lead to samples of nanocomposites with significant improvement of their aimed properties.

Mesoporous silica prepared in the dodecylamine/acetonitrile (ACN)/water/tetraethoxysilane (TEOS) system, has led, by functionalization, to a series of catalytically active materials with well-defined narrow pore size distributions. In this contribution, we follow the mechanism of templated synthesis of mesoporous silica in the nonfunctionalized parent system, for different ACN/water proportions. Electron paramagnetic resonance (EPR) of spin probes was employed to follow structural changes in the template structure during precipitation, while X-ray diffraction (XRD) and porosimetry determinations have in parallel reported on the time evolution of the mesoporous structure. Three solvent mixtures were studied, with largely different solvent compositions, and EPR data have shown that a 0.3 M dodecylamine (DDA) solution in (i) ACN/water = 1/1 v/v was a true micellar solution, in (ii) ACN/water = 2/8 v/v was a biphasic system with a lamellar liquid crystalline phase, and in (iii) ACN/water = 8/2 was a molecular...

Carbon nanostructures with different morphologies to be used as reinforcing agent in hybrid polymer–carbon nanocomposites were prepared by CO 2 laser pyrolysis of a hydrocarbon-based mixture. Investigations on the epoxy-resin/nanocarbon composites have shown that their properties depend on the morphology of the nanopowders. Preliminary results suggest that some of these carbon nanopowders lead to samples of nanocomposites with significant improvement of their mechanical properties.

New hybrid materials based on polyether polyols were prepared by using a sol-gel reaction of alkyltriethoxysilanes, in the presence of propylenoxide-ethylenoxide trifunctional block copolymers. The resulting composites are transparent and have a filmogene behavior. Two types of filler systems were used: one based on silane precursors and one based on both the silane precursors and nanoclay (sodium montmorillonite). FT-IR spectra were evaluated to prove both the covalent interaction at the functional groups level and the presence of silica nanodomains formed by sol-gel process. The polarity changes were analyzed in the UV spectra, which shift according to the nature of different cationic dyes. Polyether hybrids were also obtained in the presence of some layered silicates. The X-ray diffraction reflects the changes in basal spacing of the Cloisite Na+, when it is added to different formulations. The modification of film morphology, depending on the reactants nature, can be observed in the SEM images.

The styrene (St), butyl acrylate (BuA), and methyl methacrylate (MMA) polymerization in microemulsion in the presence of sodium dodecylsulfate is studied. This process is conducted in the presence of some comonomers having groups that can participate in sol–gel processes: 3(trimethyloxysilyl) propyl methacrylate (MPTS), triethoxy vinylsilane (VTES), and a comonomer with a sulfate group, styrene sodium sulfonate (StSO3Na). It has been observed that stabile latexes are obtained by radical polymerization at pH = 7, followed by a sol–gel process in the presence of ammonia. Latex particles sizes and zeta potential grow with MTPS concentration and in StSO3Na presence. VTES effect depends on its reactivity in St, MMA, and BuA copolymerization. Glass transition temperature and thermal decomposing temperature are influences by functional comonomer concentration and chemical structure. The Fourier transform infrared spectrum and inorganic residue growth after organic part thermal decomposition shows the presence of silica in obtained latexes.

The emulsion polymerisation of vinyl acetate (VAc) in presence of sodium dodecylsulphate (SDS) and sodium montmorillonite (NaMMT) is used in order to achieve polymer‐clay hybrids. The influence of the polyvinylacetate (PVAc), SDS, and PVAc‐SDS complex on the NaMMT structure also was investigated. The VAc emulsion polymerization rate exhibits a maximum as the NaMMT concentration increases. The XRD patterns correspond to hybrids with intercalated structure. If a water soluble comonomer, ammonium sulphato ethylmethacrylate (ASEMA) is used for copolymerization with VAc, a exfoliated hybrid structure (from XRD spectra) is obtained. The solid materials were analysed by TGA, FTIR, XRD, SEM, and TEM.

Hybrid materials containing poly(vinyl acetate) and montmorillonite (MMT) were prepared using an one-batch emulsion polymerization recipe, assisted by a nonionic surfactant. To explain the results of our experiments, a thorough investigation of the specific interactions between the compounds was done, in the wet as well as the dried state of the end-products. In dispersion, polymer–surfactant interactions were found to be driven by hydrophobic coupling into superficial (mixt) admicelles. Another important finding is that the amount of clay used in the recipes and its relative concentration with respect to the other reaction partners influences drastically the morphological units in the end-products. For low [MMT], well-defined, spherical particles are formed. At the other extreme, for high [MMT], production of polymeric, water-swollen aggregates is favored. A small amount of reformed MMT tactoids was detected in all casted hybrid films, indicating that most of the inorganic is dispersed in the organic phase.

The influence of vinyl acetate grafting reactions or nonionic type emulsifiers on the kinetics and on properties of emulsions has been studied. The emulsifiers used were polyvinyl alcohol and block copolymers ethylene oxide–propylene oxide. Due to the grafting reactions the polymerization rate decreased or increased with the increase in polyvinyl alcohol concentration, depending on the emulsifier/monomer ratio. During polymerization, graft copolymers of the monomer on the emulsifier chain are obtained. These copolymers are either water-soluble, benzene-soluble, or insoluble in water and benzene. The number of grafting reactions increases with the rise in initiator concentration. This leads to a decrease of benzene-soluble fractions and to an increase of the water-soluble and water-and-benzene-insoluble fractions. The concentration of emulsifier in water-and-benzene-soluble fractions was established by NMR analysis. The IR spectra of products proved the formation of graft copolymers.