Synthesis of CaCO3–P(MMA–BA) nanocomposite and its application in water based alkyd emulsion coating

As part of broader effort to synthesize a new class of water-based composite, hybrid emulsion polymerization was carried out with acrylic monomers [methyl methacrylate (MMA), n-butyl acrylate (BA)]. Nanocomposite of P(MMA–BA)/nano CaCO₃ was synthesized by in situ emulsion polymerization. Water-based alkyd coating with various proportions nano CaCO₃, P(MMA–BA) and its nanocomposite was formulated. Extent of polymerization with and without nano CaCO₃ was measured using gravimetric method. Thermal properties of neat polymer, nanocomposite and coating films were evaluated by TGA and DSC, DTA analysis. Uniform dispersion of nano CaCO₃ in polymer matrix was ensured from SEM/TEM images. Incorporation of nanoparticles to hybrid polymer and nanocomposite to alkyd emulsion showed significant enhancement in mechanical and thermal properties. Dual role of nanocomposite in coating; as a partial binder and a filler to improve property profile of neat coating has been reported.     

New approach for simultaneous enhancement of anticorrosive and mechanical properties of coatings: Application of water repellent nano CaCO3–PANI emulsion nanocomposite in alkyd resin

New alkyd coatings were prepared by addition of water-based polyaniline–4% CaCO₃ (PAC) nanocomposites into alkyd resin. Pure polyaniline (PANI) and PAC were synthesized using ultrasound assisted emulsion polymerization and added to alkyd resin to form nanocomposite coating. Nano CaCO₃ was added in different percentage ranging from 0% to 8% of monomer during the synthesis of polyaniline. XRD and TEM reveals that water repellent nano CaCO₃ is thoroughly dispersed in PANI matrix. The effect of PANI and PAC nanocomposite on mechanical and anticorrosion performance of alkyd coating was evaluated. An electrochemical measurement (Tafel Plots) shows that corrosion current I_corr was decreased from 0.89 to 0.03 μA/cm², when PAC nanocomposite was added to neat coatings. Positive shift of E_corr. also indicates that PAC nanocomposite acts as an anticorrosive additive to alkyd coating. Presence of water repellant nano CaCO₃ in PAC nanocomposite has exhibited dual effect, such as improvement in mechanical and anticorrosion properties. The experimental results have shown superiority of PAC nanocomposite over PANI when PAC nanocomposite added to alkyd coatings.     

Water-Based PMMA-Nano-CaCO3 Nanocomposites by In Situ Polymerization Technique: Synthesis,Characterization and Mechanical Properties

Water-based nanocomposite was synthesized using in-situ polymerization of Methyl Methacrylate. Nano-CaCO₃ was added during polymerization along with aqueous solution of surfactant. Quantity of nano-CaCO₃ was varied as 0, 2 and 4% of monomer quantity. XRD gram shows the presence of nano-CaCO₃, which causes the crystalline nature to nanocomposites. TEM images of nano-CaCO₃ show cubic structure. Synthesis of nanocomposite follows pseudo–first-order kinetics polymerization. PMMA-4% CaCO₃ nanocomposite showed significant improvement in UV absorbance and in mechanical properties like adhesion, scratch resistance as compared to neat PMMA and 2% CaCO₃ nanocomposite.     

Preparation and characterization of nano‐CaCO3 encapsulated with polyacrylic and its application in PVC toughness

The properties and morphology of nano‐calcium carbonate (nano‐CaCO₃) modified with the titanate coupling agent isopropyl trioleoyl titanate (IPTT) were characterized by Fourier transform infrared, thermogravimetric analyses, surface tension, and transmission electron microscopy. The results showed that the grafting ratio of IPTT on the surface of nano‐CaCO₃ (IPTT‐Ca) increased with IPTT content. IPTT‐Ca/PBA/PMMA (IPTT‐Ca/ACR, PBA/PMMA core‐shell polymer, referred to ACR) latexes were prepared by seeded emulsion polymerization. They were then used to mix with PVC resin. The outer layer (PMMA) enhanced the dispensability of IPTT‐Ca/ACR in the PVC matrix by increasing the interfacial interaction of these composite particles with PVC. The notched impact strengths of the blends were influenced by the weight ratio of IPTT‐Ca to BA/MMA monomers, the weight ratio of BA/MMA. The relationships between the mechanical properties and the core‐shell composite structures were elaborated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Performance properties of acrylic and acrylic polyol–polyurethane based hybrid system via addition of nano‐caco3 and nanoclay

Thermosetting acrylic (TSA) resin was prepared by solution polymerisation of acrylic acid and methyl methacrylate (MMA). Hybrid polymer consisting of acrylic polyol–polyurethane was prepared by addition of hydroxy ethyl acrylate and hexamethylene diisocyanate (HMDI). Incorporation of Functionalised nanocalcium carbonate and bentonite nanoclay were accomplished by in situ method during the synthesis of both the polymers. Loading of nano‐CaCO₃ and nanoclay was varied from 0 to 4 wt.% to investigate variation in mechanical, optical and high performance properties. The superiority of nanoclay in enhancing the mechanical and performance properties like the salt spray and humidity resistance in comparison to that of nano‐CaCO₃ was clearly established. It was also observed that, addition of nanomaterials in hybrid resins system shows superior results compared to neat acrylic system and in situ additions of these nanomaterials improve the dispersion and stability in the matrix.     

The influence of the different modifying agents on the synthesis of poly(methylmethacrylate)‐calcium carbonate nanocomposites via soapless emulsion polymerization

The synthesis of poly(methylmethacrylate)‐calcium carbonate nanocomposites via the soapless emulsion polymerization was investigated after the CaCO₃ nanoparticles were modified with different modifying agents. Such three kinds of modifying agents as sodium stearate (SS), oleic acid (OA), and PMMA were used to improve the surface property of CaCO₃ nanoparticles. What was the most important factor to improve the amount of nanoparticles in the composites is one of the general goals. As determined by Field‐emission scanning electron microscopy (FESEM), the nanocomposites size of the diluted polymer emulsion was over 250 nm, while the sample without CaCO₃ had a diameter of about 150 nm. It was worth pointing out that the surface morphology of polymer changed from slick to scraggy, when the nano‐CaCO₃ particles participated in the polymerization process. The increase of the droplet size and the change of the polymer morphology indicated that the CaCO₃ nanoparticles were present in the emulsion droplets. The X‐ray diffraction results of the nanocomposites showed the existence of typical calcite peaks. The results of the TGA, FTIR, and the contact angles indicated that the hydrophobic surface of CaCO₃ nanoparticles was crucial to improve the compatibility between the CaCO₃ and MMA monomer in emulsion system. The results of the TGA, FTIR, and the contact angles indicated that the hydrophobic surface of CaCO₃ nanoparticles was crucial to improve the compatibility between the CaCO₃ and MMA monomer in emulsion system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Preparation and comparative evaluation of well-defined fluorinated acrylic copolymer latex and solution for ancient stone protection

In this work the well-defined fluorinated acrylic copolymer latex and solution were prepared by the radical initiated seed emulsion polymerization and solution polymerization, respectively, using the same monomers of dodecafluoroheptyl methacrylate (DFHM), butyl acrylate (BA) and methyl methylacrylate (MMA). The copolymer latex BA/MMA/DFHM was designed as core–shell structure and the copolymer solution poly(BA–MMA–DFHM) was structured with low molecular weight. The chemical and morphology structures as well as the film properties obtained from latex and solution were analyzed and compared by spectroscopic techniques (FT-IR and NMR), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), gel permeation chromatography (GPC), scanning electron microscopy coupled with energy-dispersive X-ray detector (SEM–EDX) and static contact angles (CAs) instrument. Moreover, the BA/MMA/DFHM latex and poly(BA–MMA–DFHM) solution (with 29 wt% of DFHM) were applied onto two kinds of sandstone samples by capillary absorption, and their preliminary protecting efficiency was evaluated. It is demonstrated that the comprehensive performances of BA/MMA/DFHM latex films were quite comparable to those of poly(BA–MMA–DFHM) solution cast films, the latter exhibited a better protective performance.     

Mechanical properties and linear infrared dichroism of thin films of polyurethane nanocomposites

Morphological, mechanical, and Fourier transform infrared dichroic investigations were performed on neat polyurethane (PU) polymer matrix and PU+CaCO₃ nanocomposite thin films to determine how the nanofiller influenced the mechanical properties. The measurements were performed on strips that were cut from the prepared films in parallel and perpendicular directions with respect to the direction of film preparation. Optical microscopy of PU and the PU+CaCO₃ nanocomposite revealed the strain‐induced transition from a continuous spherulitic morphology to a fiberlike structure. The stress–strain behavior of the neat PU and PU+CaCO₃ nanocomposite films showed significant differences at large strain regimes. The experimental results suggest that the mechanical properties were strongly related to the orientational behavior of the separated phases. The orientation of the hard and soft segments was analyzed by the orientation function calculated from the IR absorbances. A correlation between the orientations of segments, tensile properties, and hardness of the investigated polymer films was established. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and properties of nano‐CaCO3/acrylonitrile‐butadiene‐styrene composites

CaCO₃/acrylonitrile‐butadiene‐styrene (ABS) and CaCO₃/ethylene‐vinyl acetate copolymer (EVA)/ABS nanocomposites were prepared by melting‐blend with a single‐screw extruder. Mechanical properties of the nanocomposites and the dispersion state of CaCO₃ particles in ABS matrix were investigated. The results showed that in CaCO₃/EVA/ABS nanocomposites, CaCO₃ nanoparticles could increase flexural modulus of the composites and maintain or increase their impact strength for a certain nano‐CaCO₃ loading range. The tensile strength of the nanocomposites, however, was appreciably decreased by adding CaCO₃ nanoparticles. The microstructure of neat ABS, CaCO₃/ABS nanocomposites, and CaCO₃/EVA/ABS nanocomposites was observed by scanning electron microscopy. It can be found that CaCO₃ nanoparticles were well‐dispersed in ABS matrix at nanoscale. The morphology of the fracture surfaces of the nanocomposites revealed that when CaCO₃/EVA/ABS nanocomposites were exposed to external force, nano‐CaCO₃ particles initiated and terminated crazing (silver streak), which can absorb more impact energy than neat ABS. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Fabrication and characterization of in situ synthesized nano‐CaCo3‐reinforced polypropylene composite materials

To improve the impact toughness of polypropylene (PP), nano‐CaCO₃ was prepared by an in situ synthesis. The surface of the nano‐CaCO₃ was modified by KH‐550 silane coupling agent and NDZ‐401 titanium acid ester coupling agent. Nano‐CaCO₃/PP composite materials were fabricated through a melt‐blending method and characterized, and their mechanical properties were analyzed. The impact toughness and the tensile strength of the PP were improved significantly by the incorporation of nano‐CaCO₃. When the weight fraction of nano‐CaCO₃ was 2%, the maximum impact toughness and tensile strength of the PP nanocomposites were 293% and 259%, respectively, of the values for neat PP. Observation of the impact fracture surface of the nanocomposites indicated that the dispersion of nano‐CaCO₃ modified by NDZ‐401 coupling agent was more homogeneous than that of nano‐CaCO₃ modified by the KH‐550 silane coupling agent. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Hydrophilic CaCO3 nanoparticles designed for poly (ethylene terephthalate)

In this work, a new kind of the hydrophilic CaCO₃ nanoparticles modified by polyethylene glycol phosphate (PGP) was designed for the in-situ preparation of poly (ethylene terephthalate) (PET). It was confirmed that PGP induced the growth of calcite and coated the surface of calcite by the covalent bond. PGP not only adjusts the morphology and the size of CaCO₃ nanoparticles, but also solve the main problems in the in-situ preparation of CaCO₃/PET: (a) the reaction of CaCO₃ with TPA; (b) the agglomeration of CaCO₃ nanoparticles. Compared to the nanocomposite filled with the pure CaCO₃, the resulting nanocomposite filled with the modified CaCO₃ exhibits a better dispersion of the nanoparticles, a higher polymerization degree and a better thermal stability. The results related to the covalent bond formed by PGP on the surface of CaCO₃ and PET during the polymerization of the nanocomposite.     

Preparation of epoxy resin/CaCO3 nanocomposites and performance of resultant powder coatings

Epoxy resin/CaCO₃ nanocomposites were prepared by the methods of extruding, solution blending, and in situ and inclusion polymerization, respectively. The contents of nanoparticles in the nanocomposites were varied from 5 wt % to 15 wt %. Powder coatings with different content of nanoparticles were made from the nanocomposites. The results showed that the cupping property and impact resistance decreased with the increase of coating film thickness. The dispersion of nanoparticles in epoxy matrix affected the impact resistance and cupping property of the obtained coating films greatly. The coating films made from the nanocomposite prepared by in situ and inclusion polymerization showed that the best impact resistance and the maximum cupping property was achieved when nano‐CaCO₃ content was 5 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2656–2660, 2006     

Study on electrochemical behavior of Nano‐ZnO modified alkyd‐based waterborne coatings

A nano‐composite coating was formed using nano‐ZnO as pigment in different concentrations, to a specially developed alkyd‐based waterborne coating. The nano‐ZnO modified composite coatings were applied on mild steel substrate by dipping. The dispersion of nano‐ZnO particles in coating system was investigated by scanning electron microscopic and atomic force microscopic techniques. The effect of the addition of these nano‐pigments on the electrochemical behavior of the coating was investigated in 3.5% NaCl solution, using electrochemical impedance spectroscopy. Coating modified with higher concentration of nano‐ZnO particles showed comparatively better performance as was evident from the pore resistance (R_po) and coating capacitance (C_c) values after 30 days of exposure. In general, the study showed an improvement in the corrosion resistance of the nano‐particle modified coatings as compared with the neat coating, confirming the positive effect of nano‐particle addition in coatings. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Kinetic investigations of acrylic–polyurethane composite latex

The effect of various reaction parameters on the rate of polymerization, R_p, and on the particle size and morphology of aqueous acrylic–polyurethane hybrid dispersions, prepared by semibatch emulsion polymerization, was investigated. The particles of polyurethane dispersion were used as seeds during the polymerization of acrylic component: methyl methacrylate (MMA), butyl acrylate (BA), and a mixture of MMA and BA with the ratio of 1:1. These emulsions were found to form structured polymer particles in aqueous media using scanning electron microscopy. The kinetics of the emulsion polymerization was studied on the basis of Wessling's model. The influence of emulsifier and initiator concentrations, including the monomer feed rates, R_m, on the rates of polymerization and on the properties of the resulting dispersions were studied. The number of particles and the particle size were also measured during the polymerization process. The final values were found to be independent of the concentration of the emulsifier, initiator and the monomer feed rate in monomer starved conditions. In the steady‐state conditions, during the seeded semibatch hybrid emulsion polymerization, the rate of polymerization and the monomer feed rate followed the Wessling relationship 1/R_p = 1/K + 1/R_m. The dispersions MMA/PU, BA/PU, and MMA/BA/PU have K values of 0.0441, 0.0419 and 0.0436 mol/min, respectively. The seeded BA/PU hybrid polymerization proceeded according to Smith‐Ewart Case I kinetics, while the MMA/PU hybrid emulsions demonstrate Case II of the Smith‐Ewart kinetic model. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2639–2649, 2002     

Preparation and properties of core–shell nanosilica/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) latex

A core–shell nanosilica (nano‐SiO₂)/fluorinated acrylic copolymer latex, where nano‐SiO₂ served as the core and a copolymer of butyl acrylate, methyl methacrylate, and 2,2,2‐trifluoroethyl methacrylate (TFEMA) served as the shell, was synthesized in this study by seed emulsion polymerization. The compatibility between the core and shell was enhanced by the introduction of vinyl trimethoxysilane on the surface of nano‐SiO₂. The morphology and particle size of the nano‐SiO₂/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) [P(MMA–BA–TFEMA)] core–shell latex were characterized by transmission electron microscopy. The properties and surface energy of films formed by the nano‐SiO₂/P(MMA–BA–TFEMA) latex were analyzed by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy/energy‐dispersive X‐ray spectroscopy, and static contact angle measurement. The analyzed results indicate that the nano‐SiO₂/P(MMA–BA–TFEMA) latex presented uniform spherical core–shell particles about 45 nm in diameter. Favorable characteristics in the latex film and the lowest surface energy were obtained with 30 wt % TFEMA; this was due to the optimal migration of fluorine to the surface during film formation. The mechanical properties of the films were significantly improved by 1.0–1.5 wt % modified nano‐SiO₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Investigation of the addition of nano‐CaCo3 at dry mixing or onset of fusion on the dispersion,torque, and mechanical properties of compounded PVC

A Brabender torque rheometer equipped with an internal mixer was used to study the influence of compounding method on the properties of (rigid PVC)/(treated and untreated nano‐CaCO₃) nanocomposites. Two different methods were studied for the addition of surface treated and untreated nano‐CaCO₃ during the melt mixing of rigid PVC. Direct dry mixing of rigid PVC and nano‐CaCO₃, and addition of nano‐CaCO₃ at the onset of PVC fusion were investigated. Dispersion of treated and untreated nano‐CaCO₃ was studied by X‐ray diffraction and scanning electron microscopy. Results showed that using direct dry mixing improved the dispersion of nano‐CaCO₃ in the PVC matrix by lowering the fusion time. The mechanical properties of the nanocomposite samples such as impact strength, tensile strength, and elongation at break were improved by using this method. The addition of treated nano‐CaCO₃ at the onset of fusion caused a simultaneous decrease in torque. Also, rigid PVC nanocomposites prepared with treated nano‐CaCO₃ showed better mechanical properties than those of nanocomposites prepared with the untreated nano‐CaCO₃. J. VINYL ADDIT. TECHNOL., 18:153–160, 2012. © 2012 Society of Plastics Engineers     

Synthesis and film performances of SiO2/P(MMA-BA) core–shell structural latex

In this study, we have successfully synthesized silica/poly(methyl methacrylate-butyl acrylate) (SiO₂/P(MMA-BA)) core–shell nanocomposite colloids via in situ emulsion copolymerization using cationic 2,2′-azobis(2-amidinopropane)dihydrochloride (AIBA) as the initiator and the 3-Glycidoxypropyl-trimethoxysilane (GPTMS)-modified SiO₂ nanoparticles as the seeds. The SiO₂ nanoparticles embedded can reach as high as 60 wt%. The nanocomposite film presents almost the same high transparency as the pure polymer film (>90% transmittance in visible range), and displays significantly improved mechanical and UV weathering resistant properties over its pure polymer film.     

Synthesis and dielectric properties of polyaniline/titanium dioxide nanocomposites

Two series of polyaniline–TiO₂ nanocomposite materials were prepared in base form by in situ polymerization of aniline with inorganic fillers using TiO₂ nanoparticles (P25) and TiO₂ colloids (Hombikat), respectively. The effect of particle sizes and contents of TiO₂ materials on their dielectric properties was evaluated. The as-synthesized polyaniline–TiO₂ nanocomposite materials were characterized by transmission electron microscopy (TEM), Fourier transform infrared (FTIR), thermal analysis (DTA/TGA), and X-ray diffraction (XRD). Dielectric properties of polyaniline–TiO₂ nanocomposites in the form of films were measured at 1 KHz–1 MHz and a temperature range of 35–150 °C. Higher dielectric constants and dielectric losses of polyaniline–TiO₂ nanocomposites than those of neat PANI were found. PANI–TiO₂ nanocomposites derived from P25 exhibited higher dielectric constants and losses than those from Hombikat TiO₂ colloids. Electrical conductivity measurements indicate that the conductivity of nanocomposites is increased with TiO₂ content. The dielectric properties and conductivities are considered to be enhanced due to the addition of TiO₂, which might induce the formation of a more efficient network for charge transport in the base polyaniline matrix.     

Effect of Nano CaCO<Subscript>3</Subscript> on thermal properties of Styrene Butadiene Rubber (SBR)

Styrene butadiene rubber (SBR) as matrix was reinforced separately with 9, 15 and 21 nm sizes of CaCO₃, which were synthesized by matrix mediated growth technique. The mixing and compounding was done on two-roll mill and sheets were prepared in compression molding machine. The effect of nature and loading of nano CaCO₃ on these rubber nanocomposites was investigated thoroughly by different characterizations such as DSC, TGA, XRD, and mechanical properties. An appreciable increase in glass transition temperature has been observed from DSC study. 9 nm sizes of CaCO₃/SBR composites show more increment in Tg as compared to pristine SBR as well as different sizes of CaCO₃ filled SBR. This increment in Tg is due to restricted mobility of nano CaCO₃ filled SBR nanocomposites. XRD study of nanocomposites showed that nano CaCO₃ dispersed uniformly throughout the matrix because of the small peak at lower 2θ. This uniform dispersion of nano CaCO₃ contributes towards the higher mechanical properties of rubber composites. From TGA study, it was observed that as the size of CaCO₃ reduces the thermal stability increases as compared to pristine SBR. The other results of these rubber nanocomposites were compared with commercial CaCO₃ filled SBR. Partly this research paper has been presented in International conference on ‘RubberChem 2006, Dec 5–6, 2006, Munich, Germany.     

A nanocomposite approach to tailor electrocaloric effect in ferroelectric polymer

The electrocaloric effect (ECE) is enhanced in ferroelectric relaxor terpolymer poly(vinylidene fluoride–trifluoroethylene–chlorofluoroethylene) (P(VDF–TrFE–CFE))/ZrO₂ nanocomposites. It was observed that the interface effects between the polymer matrix and nano-fillers enhance the polarization response and provide additional electrocaloric entropy changes. As a consequence, the nanocomposites exhibit a larger ECE than that of the neat terpolymer, i.e., the adiabatic temperature change of the nanocomposite with 3 volume percent of nano-fillers is 120% of that of the neat terpolymer. The results, for the first time, demonstrate that ECE can be tailored and enhanced through nanocomposite approach in the ferroelectric polymers.