Structure and morphology of nanocomposite films prepared from polyvinyl alcohol and silver nitrate: Influence of thermal treatment

Hybrid organic/inorganic films have been prepared from an aqueous solution of polyvinyl alcohol (PVA) and silver nitrate (AgNO₃). The silver nanoparticles have been generated in the PVA matrix by thermal treatments. The structure and the morphology of the hybrid films have been studied as a function of the silver precursor concentration and of the annealing conditions for a wide range of annealing temperatures. It was shown that in the uncured hybrid film most of the silver ions were initially coordinated with the polymer OH groups to form a chelate structure. A nanostructuration effect leading to the formation of crystalline silver nanoparticles was evidenced for annealing treatments performed at temperatures higher than 90 °C. For a curing temperature equal to 110 °C, the sizes of the formed nanoparticles were only slightly increasing as a function of annealing time and the effect of AgNO₃ complex amount in this curing condition was also significant, but slight. Annealing at a temperature equal to 160 °C thus at a temperature for which a part of the crystalline phase of PVA was melt led to an important increase of the size of the generated metal nanoparticles. The evolution of the morphology was discussed for each curing temperature as a function of the kinetics of the nanostructuration, of the size of the matrix amorphous lamellae and of the polymer chain mobility. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2657–2672, 2007     

Development and analysis of cellulose nanocomposite films with in situ generated silver nanoparticles using tamarind nut powder as a reducing agent

Cellulose/Tamarind nut powder (TNP)/Silver nanoparticles (AgNPs) nanocomposites were prepared by in situ generation of AgNPs using regeneration method, followed by solution casting method. In this, TNP was used as a reducing agent. These nanocomposites were characterized using FT-IR spectroscopy, XRD and SEM and studied their mechanical properties and antibacterial activity for medical and packing applications. The FT-IR spectral studies revealed the involvement of functional groups – Polyphenols, Flavonoids and –OH in the process of reducing the metal salts into metal nanoparticles. These nanocomposites showed good antibacterial activity against five bacteria. Improved mechanical properties with good antibacterial activities make these composites suitable for medical, food and packaging applications.     

Preparation and dielectric properties of polyimide/silica nanocomposite films prepared from sol–gel and blending process

Using poly(amic acid) (PAA) as a precursor followed by thermal imidization, the polyimide/silica nanocomposite films were prepared via an improved sol–gel process and a blending process, respectively. FT‐IR, TEM and TGA measurements were used to characterize the structure and properties of the obtained films. The results confirmed that the introduction of silica did not yield negative effects on the conversion of the PAA precursor to the polyimide. With the increase of silica content, the aggregation of silica appeared in the polyimide matrix, and the thermal stability decreased slightly for both kinds of films. The dielectric constant (ε) of both films increased slowly with the increase of the silica concentration. The dielectric constant of the obtained polyimide/silica nanocomposite films displayed good stability within a wide range of temperatures or frequency. Based on modeling relation between ε and silica content, the difference in dielectric properties for two kinds of nanocomposites are discussed. Copyright © 2007 John Wiley & Sons, Ltd.     

Surlyn®/silicate nanocomposite materials via a polymer in situ sol–gel process: Morphology

Surlyn®/silicate hybrid materials were produced via diffusion‐controlled polymer in situ sol–gel reactions for tetraethylorthosilicate. The heterogeneous morphologies of these materials were inspected with transmission electron (TEM), atomic force (AFM), and environmental scanning electron microscopic methods. The silicate uptake was highly dependent on the water affinity of the particular Surlyn® form (acid or ionic) rather than on the affinity of the solvent. The morphology consisted of silicate particles with diameters that were on the order of tens of nanometers. Hence, these materials can be classified as nanocomposites. The particle size distributions in both the TEM and AFM images for all composites appeared to be narrow, with un‐neutralized Surlyn® exhibiting a broader distribution. Larger particles were found near the film surfaces, and the silicon elemental distribution across the film thickness indicated higher concentrations near the surfaces, which is most likely due to the fact that the sol–gel reaction is diffusion controlled in these polymeric media. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1563–1571, 2003     

Preparation and properties of silver nanocomposite fabrics with in situ-generated silver nano particles using red sanders powder extract as reducing agent

Nanocomposite cotton fabrics with in situ-generated silver nanoparticles (AgNPs) were prepared by using Pterocarpus santalinus (Red sanders) extract in water as a reducing agent. The formation of AgNPs was analyzed by scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy. The SEM analysis of nanocomposites showed the presence of spherical AgNPs with a size range of 71–90?nm. FTIR spectra showed the involvement of hydroxyl and methylene groups of cellulose matrix in reducing the silver salt into AgNPs in the presence of red sanders powder extract as reducing agent for the in situ generation of AgNPs. These nanocomposite fabrics exhibited good antibacterial activity against Gram positive and Gram negative bacteria.     

Characteristics and degradation of hybrid composite films prepared from PVA,starch and lignocellulosics

A research cooperation between USDA and the University of Pisa led to the development of several composite blends of poly(vinyl alcohol) (PVA) and lignocellulosic fibers. The cast films were prepared by blending orange fibers (OR-fibers) and PVA with and without cornstarch to yield flexible and cohesive films. To improve properties, films were also prepared by crosslinking PVA, starch and OR-fibers with hexamethoxymethylmelamine (HMMM). Films were evaluated for their thermal stability, water permeability and biodegradation. Thermal gravimetric analyses indicated the potential usefulness of such blends in several thermoplastic applications. Films were permeable to water, and retained the moisture content in the soil while retaining their integrity. Films generally biodegraded within 30 days in compost, achieving between 50-80% mineralization. Both neat PVA and blends that had been crosslinked showed comparatively slow degradation. A possible stimulating effect of lingocellulosic fillers on the biodegradation of PVA in blends has been observed.     

Preparation of siloxane‐based urethane dimethacrylates carrying carboxylic groups and the effect of silver nanoparticles on the properties of composite polymer films

This work reports on the synthesis of three acid oligosiloxane‐urethane dimethacrylates and their use to obtain hybrid nanocomposite films, in which the presynthesized silver nanoparticles (NPs) were incorporated before photopolymerization, or produced via in situ photoreduction of the silver nitrate (AgNO₃) precursor into the formulation, without any conventional reducing agent. All samples were characterized by ¹H NMR, FT‐infrared and UV spectroscopies, photodifferential scanning calorimetry (photo‐DSC), transmission electron microscopy (TEM), and energy‐dispersive X‐ray (EDX) analysis. Fourier transformed infrared spectroscopy and photo‐DSC results showed that dimethacrylates having hydrophilic segment of poly(ethylene oxide) type in structure are more reactive than the acid oligosiloxane dimethacrylate. When another urethane dimethacrylate is taken as a comonomer, the photopolymerization rate (0.112–0.132 s^?1) and the degree of conversion (82–93%) significantly increased. Experimental evidence of the existence of nanosilver into the polymer matrix generated upon UV irradiation has been supported by UV spectroscopy, EDX and TEM analysis, the last allowing a visualization of the formation of silver NPs with size between 2 and 15 nm. Mechanical parameters and wettability of the photocrosslinked films are also discussed in the prospect of further potential applications in the biomedical field. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis,thermal properties and crystalline morphology of poly(trimethylene terephthalate)/ZnO nanocomposites prepared by dual in situ polymerization

Poly(trimethylene terephthalate)/ZnO nanocomposites were successfully prepared by dual in situ polymerization. Firstly, ZnO nanoparticles were synthesized by a simple polyol method using 1,3‐propanediol (PDO) as solvent and stabilizer. Then, PTT/ZnO nanocomposites were prepared by in situ polymerization. The results of Fourier transform infrared spectra showed that PTT molecular chains were grafted to the surface of ZnO nanoparticles. The results of ¹H NMR spectra confirmed that propyl ester molecules (as reaction product) were incorporated into PTT molecular chains. It was found that the intrinsic viscosity and molecular weight of synthesized PTT decreased with the addition of ZnO nanoparticles and the incorporation of propyl ester molecules. TEM results showed that ZnO nanoparticles with particle size of 20 ~ 30 nm were well dispersed and fully distributed in the polymer matrix. Besides, the melting temperatures and crystallization temperature decreased gradually and then increased slightly with the increasing loading of ZnO nanoparticles. Because of the strong interaction between ZnO nanoparticles and PTT matrix, the thermal stability of PTT/ZnO nanocomposites was improved. Interestingly, the results of Polarized Optical Microscopy showed that banded spherulites morphology can be observed in all PTT/ZnO nanocomposite samples. However, at higher loading of ZnO nanoparticles, band spacing became larger and was finally disturbed. Copyright © 2016 John Wiley & Sons, Ltd.     

Thermal and morphological investigation of the effect of POSS-(PEG2000)8 addition to UV curable PEGMEA/PEGDA formulation and simultaneously in situ formed silver nanoparticles

In this study, hybrid nanocomposites were synthesized by photo-crosslinking of poly (ethylene glycol) methyl ether acrylate/poly (ethylene glycol) diacrylate monomer system using 2- (carboxymethoxy) thioxanthone and POSS-(PEG₂₀₀₀)₈. Additionally, AgNO₃ was added to this formulation and in situ formation of silver nanoparticles onto hybrid nanocomposites were achieved in one-step. UV–Vis spectroscopy technique was used as a very useful tool for surface plasmon resonance band detection of silver nanoparticles. In addition to thermogravimetric analyses which were performed in nitrogen atmosphere to determine the thermal stability of the nanocomposites, dynamic light scattering, and scanning electron microscopy techniques were also used for size and morphology of silver nanoparticles in a hybrid network. TGA analyses proved that even the addition of a very low amount of POSS-(PEG₂₀₀₀)₈ made noteworthy contribution to thermal stability especially in the presence of silver nanoparticles in the hybrid network. The swelling capacities of the prepared films were examined at 1, 3 and 24 h in phosphate buffer solution (pH = 7.4). It was found that film containing only POSS-(PEG₂₀₀₀)₈ had the highest swelling ratio in the shortest time.     

Novel silver/polyurethane nanocomposite by in situ reduction: Effects of the silver nanoparticles on phase and viscoelastic behavior

A novel silver/poly(carbonate urethane) nanocomposite was prepared through in situ reduction of a silver salt (AgNO₃) added to a solution consisting of a commercial poly(carbonate urethane) dissolved in N,N‐dimethylformamide (DMF). In this system, the presence of the poly(carbonate urethane) was proved to protect the silver nanoparticles, whose formation was confirmed by means of UV–vis spectroscopy, from aggregation phenomena. The silver morphology developed in the solid state after DMF casting was imaged by FESEM. Homogeneous dispersion of silver nanoprisms in the poly(carbonate urethane) matrix was clearly observed. The effects of dispersion of silver nanoparticles within the poly(carbonate urethane) matrix were investigated by means of ATR‐FTIR and multifrequency dynamic mechanical thermal analyses. The obtained results revealed that the presence of silver nanoparticles modifies both the phase and the viscoelastic behaviors of poly(carbonate urethane). As a matter of fact, the hydrogen bond formation in the hard and soft segments was found to be hindered and the molecular motions of the soft segments were restricted, because a comparatively higher activation energy was required for the related α‐relaxation process. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 344–350, 2008     

Preparation and characterization of high‐molecular‐weight atactic poly(vinyl alcohol)/sodium alginate/silver nanocomposite by electrospinning

High‐molecular‐weight poly(vinyl alcohol) (PVA)/sodium alginate (SA)/ silver nanocomposite was successfully prepared via electrospinning technique. Water‐based colloidal silver in a PVA/SA blend solution was directly mixing without any chemical and structural modifications into PVA/SA matrix to form an organic‐metallic nanocomposite. The effect of the addition of silver colloidal solution on the PVA/SA/silver nanocomposite was investigated through a series of experiments varying molecular weight of PVA and electrospinning processing parameters such as concentration of PVA solution, PVA/SA blend ratio, applied voltage, and tip‐to‐collector distance. In the case of PVA with number‐average degree of polymerization of 1700, by increasing the amount of SA in spinning solution, the morphology was changed from fine uniform fiber to beaded fiber or bead‐on‐string fiber structure. Increase of the amount of silver colloidal solution resulted in higher charge density on the surface of ejected jet during spinning, thus more electric charges carried by the electrospinning jet. As the charge density increased, the diameter of the nanocomposites became smaller. Transmission electron microscopy images showed that the dense silver nanoparticles were well separately dispersed in PVA/SA matrix. Energy‐disperse X‐ray analysis indicated that carbon, oxygen, natrium, and silver were the principle element of PVA/SA/silver nanocomposite. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1916–1926, 2009     

From nanoplates to microtubes and microrods: a surfactant-free rolling mechanism for facile fabrication and morphology evolution of Ag2S films

By a simple and facile wet-chemistry technique without any surfactant, various shapes of Ag(2)S crystals--including leaflike pentagonal nanoplates, crinkly nanoscrolls, hexagonal prismlike microtubes, and microrods--were fabricated in situ on a large-area silver-foil surface separately. Detailed experiments revealed that the Ag(2)S nanoplates were formed just by immersing the silver foil in a sulfur/ethanol solution at room temperature and atmospheric pressure, and they subsequently rolled into nanoscrolls and further grew into microtubes and microrods under solvothermal conditions. Inspired by the natural curling of a piece of foliage, we proposed a surfactant-free rolling mechanism to interpret the observed morphological evolution from lamellar to tubular structures. Based on these simple, practical, and green chemical synthetic routes, we can easily synthesize lamellar, scrolled, tubular, and clubbed Ag(2)S crystals by simply adjusting the reaction temperature, pressure, and time. It is very interesting to note that the current rolling process is quite different from the previous reported rolling mechanism that highly depends on the surfactants; we revealed that the lamellar Ag(2)S could be rolled into tubular structures without using any surfactant or other chemical additives, just like the natural rolling process of a piece of foliage. Therefore, this morphology-controlled synthetic route of Ag(2)S crystals may provide new insight into the synthesis of metal sulfide semiconducting micro-/nanocrystals with desired morphologies for further industrial applications. The optical properties of the pentagonal Ag(2)S nanoplates/film were also investigated by UV/Vis and photoluminescence (PL) techniques, which showed large blue-shift of the corresponding UV/Vis and PL spectra.     

Hybrid films of polyetherimide containing in situ grown Ag,Pd, and AgPd alloy nanoparticles: Synthesis route,morphology, and gas transport properties

In this study, bimetallic/polymer films are synthesized from polyetherimide (PEI), palladium acetate and silver nitrate for a wide range of total metal amount (from 0 to 30 wt %) and different Ag to Pd molar ratios. Hybrid precursor films are first prepared from polymer/metal complex solutions and the metal nanoparticles are then generated within the PEI matrix by annealing the precursor film under specific conditions. Reference neat PEI films and monometallic films are prepared in the same conditions. Interestingly, formation of AgPd alloys directly within the polymer films is for the first time obtained from a very simple and environmentally friendly route. Based on X‐ray diffraction and transmission electron microscopy analyses, a nanostructuration mechanism is proposed. The interactions of hydrogen towards the nanocomposites are investigated and discussed as a function of the nanoparticle composition. The impact of the nanostructuration is also studied on H₂, CO₂, and He permeation properties. Significant improvement of barrier properties is achieved. The pertinent parameters of the gas transport are identified and modelled for each gas/composite system. Finally, from both morphological and gas transport analyses, it is concluded that in situ generation AgPd alloys with Pd to Ag ratio above 1 leads to very interesting and promising materials. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1211–1220     

Influence of the PVOH molar mass on the morphology and functional properties of EVOH/PVOH films prepared by melt blending

The influences of the molar mass (low, medium, and high) and content of poly(vinyl alcohol) (PVOH) dispersed by melt-blending in an ethylene vinyl alcohol (EVOH) copolymer on the morphology, microstructure, thermal, mechanical, and oxygen barrier properties were investigated. Multilayer films with external low-density polyethylene layers and inner EVOH/PVOH blend layer and respective monolayer films were elaborated and characterized. EVOH/PVOH blends exhibited a good compatibility because of the initial presence of PVOH segments in EVOH. The detailed quantitative analysis of the morphology performed for all blends showed that the finest dispersion was obtained with the PVOH with the lowest molar mass. The properties of the films as a function of the PVOH content and its molar mass were determined herein. Significant improvement of barrier properties was obtained at moderated water activities (up to a_w = 0.6) by using the PVOH with the lowest molar mass. Compared to the neat EVOH material, the oxygen permeability coefficients decreased by a factor 2 by adding 15 vol% PVOH while the thermal and mechanical properties remained similar.     

Multihollow structured poly(methyl methacrylate)/silver nanocomposite microspheres prepared by suspension polymerization in the presence of dual dispersion agents

Poly(methyl methacrylate) (PMMA)/silver nanocomposite microspheres with unique multihollow structures were prepared by suspension polymerization in the presence of dual dispersion agents. The addition of a lipophilic emulsifier, polyethylene glycol (30EO) dipolyhydroxystearate (Arlacel P135), not only stabilized water-in-oil (W/O) emulsion, but also converted silver nanoparticles from hydrophilic to lipophilic. When a suspension polymerization dispersion agent, poly(vinyl alcohol), was added to the above W/O emulsion system, a water-in-oil-in-water suspension was formed with silver nanoparticles dispersed in the oil phase. The suspension polymerization was carried out at low temperature with 2,2’-azobis(2,4-dimethylvaleronitrile) as the initiator. When modified silver nanoparticles were added, the rate of polymerization increased slightly. High monomer conversion (about 85%) was obtained in spite of low polymerization temperature of 30 °C. Under controlled conditions, PMMA/silver microspheres with various hollow structures were synthesized. The PMMA/silver microspheres with multihollow structure showed high antibacterial ability.     

In situ generation of silver nanoparticles in cellulose matrix using Azadirachta indica leaf extract as a reducing agent

In the present work, silver nanoparticles (AgNPs) were in situ generated in cellulose matrix using leaf extract of Azadirachta indica as a reducing agent. The cellulose/AgNP composite films prepared were characterized by FTIR, X-ray diffraction (XRD), scanning electron microscope, and antibacterial tests. The infrared spectra indicated the association of organic materials with silver nanoparticles to serve as capping agents. Scanning electron micrographs showed that synthesized silver nanoparticles were nearly uniform and spherical in shape with diameter in the range of 61–110?nm. XRD confirmed the formation of AgNPs and Ag–O nanoparticles. The nanocomposite films showed good antibacterial activity against Escherichia coli bacteria.     

Fracture morphology and mechanical properties of ethylene/vinyl acetate rubber vulcanizates reinforced by in situ prepared sodium methacrylate

Ethylene/vinyl acetate rubber (EVM) was reinforced by sodium methacrylate (NaMAA) that was in situ prepared through the neutralization of sodium hydroxide and methacrylic acid in EVM during mixing. The mechanical properties of EVM vulcanizates with different NaMAA loadings and at different crosslink densities were studied and compared with those of high abrasion furnace carbon black (HAF) filled EVM vulcanizates. The fracture surfaces of gum and filled EVM vulcanizates were observed with scanning electron microscopy. The results showed that NaMAA‐reinforced EVM vulcanizates had better mechanical properties than HAF/EVM vulcanizates. When the NaMAA loading was 50 phr, the tensile strength of the NaMAA/EVM vulcanizate was 30 MPa, the tear strength was 102 kN/m, and the elongation at break was over 400%. Fourier transform infrared analysis confirmed that NaMAA formed in the compounding process and underwent polymerization during vulcanization. Scanning probe microscopy analysis revealed that nanoscale particles dispersed in the NaMAA/EVM vulcanizates. The mechanical properties were correlated with the fracture morphology of all the vulcanizates. The tensile rupture of NaMAA‐filled EVM vulcanizates occurred through tearing from a crack in the bulk of the samples. Tear deviation occurred with the addition of NaMAA and resulted in a rough surface, leading to an improvement in the tear strength of NaMAA‐filled EVM vulcanizates. The micrographs of the tear surfaces of the vulcanizates indicated that the different fracture modes depended on the NaMAA loading and the crosslink density. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1715–1724, 2004     

Synthesis and properties of polyimide/silver nanocomposite containing dibenzalacetone moiety in the main chain

A new thermally stable polyimide–silver nanocomposite containing dibenzalacetone moiety in the main chain was synthesized by a convenient ultraviolet irradiation technique. A precursor such as AgNO₃ was used as the source of the silver nanoparticles. Polyimide 6 as a source of polymer was prepared by polycondensation reaction of 2,5-bis(4-aminobenzylidene) cyclopentanone 4 with pyromellitic anhydride 5 in m-cresol solution and in the presence of iso-quinoline as a base. The resulting nanocomposite film was characterized by FTIR spectroscopy, X-ray diffraction (XRD), Scanning electron microscopy (SEM), Thermal gravimetric analyses (TGA), differential gravimetric analyses (DTG) and differential scanning calorimetry (DSC). Scanning electron microscopy (SEM) confirmed the formation and dispersion of silver nanoparticles in polymer matrix having average size of ～20 nm. Incorporation of inorganic metal silver nanoparticles has improved the thermal behavior of the nanocomposite film as compared to pure polyimide film. Also 2,5-bis(4-aminobenzylidene) cyclopentanone 4 was synthesized by using a two-step reaction.     

Impact of the clay organic modifier on the morphology of polymer–clay nanocomposites prepared by in situ free‐radical polymerization in emulsion

Poly(styrene‐co‐butyl acrylate) copolymers were prepared by free‐radical random copolymerization of styrene and butyl acrylate in emulsion in the presence of 10% of surface‐modified sodium montmorillonite (Na‐MMT). The objective of this work was to evaluate the impact of the clay organic modifier in terms of its chemical structure, its degree of interaction within the clay galleries surface, and its ability to copolymerize with monomers, on the morphology and properties of the final nanocomposite prepared. Na‐MMT was modified using different organic modifiers, namely: sodium 1‐allyloxy‐2‐hydroxypropyl (Cops), 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPS), N‐isopropylacrylamide (NIPA), and sodium 11‐methacryloyloxy‐undecan‐1‐yl sulfate (MET), respectively. The morphology and properties of the nanocomposites obtained were found to be dependant on the clay organic modifier. X‐ray diffraction (XRD) and transmission electron microscopy indicated that, nanocomposites at 10% clay loading with Cops‐, NIPA‐, and MET‐modified clays, yielded intercalated to partially exfoliated structures, whereas AMPS‐modified clay gave a nanocomposite with a fully exfoliated structure. All polymer–clay nanocomposites were found to be more thermally stable than neat poly(S‐co‐BA) as were determined by TGA. However, nanocomposites with intercalated structures exhibited greater thermal stability relative to fully exfoliated ones. Furthermore, nanocomposites with exfoliated structures exhibited higher storage moduli (G^I) than partially exfoliated once, whereas intercalated structure showed the lowest G^I values. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3619–3628, 2008     

The effect of preparation temperature on the mechanical and antibacterial properties of poly(vinyl alcohol)/silver nitrate films

There has been a growing interest in developing antibacterial polymeric materials. The logical consequence following development of a new material is optimisation of its processing conditions and investigation of the influence of processing parameters on functionality of a given material. The present work deals with investigation of the effect of preparation temperature on the mechanical and antibacterial properties of polymer films based on poly(vinyl alcohol) (PVA) and silver nitrate (0, 1, 3, 5, 7, 9 wt.% silver content). The mechanical properties of the films prepared at various temperatures (25, 35, 50, 60, 75 °C) were characterized by using stress-strain analysis. Antibacterial properties were determined by using an agar diffusion test and a dilution and spread plate technique against both Gram positive (Staphylococcus aureus) and Gram negative (Escherichia coli, Pseudomonas aeruginosa and Klebsiella pneumoniae). The results show significant effect of the elevated temperature on the samples properties.