Thermal and dynamic mechanical characterization of polyurethane–urea–imide coatings

A series of NCO terminated polyurethane (PU)–imide copolymers were synthesized by a systematic three‐step process and were chain extended with different diol/diamine chain extenders. In the first step, isocyanate terminated PU prepolymers were prepared by reacting soft segments such as polyester (PE) polyols and polyether polyols such as polypropylene glycol (PPG‐1000) with hard segments like 2,4‐tolylene‐diisocyanate (TDI) or isophorone‐diisocyanate (IPDI) with NCO/OH ratio 2:1. In the second step, thermally stable heterocyclic imide ring was incorporated using isocyanate terminated PU prepolymers by reacting with pyromellitic dianhydride (PMDA) in a excess‐NCO:anhydride ratio of 1:0.5. The surplus NCO content after imidization was both moisture cured or partially reacted with chain extender and moisture cured. The films were characterized by thermogravimetric (TG), differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) instruments. The adhesion strength of these coatings on mild steel (MS), copper (Cu), and aluminum (Al) is dependent on the nature of the substrate. The TGA analysis show good thermal stability. The DMTA results show the microphase separation between the different hard and soft segments. Finally, a structure to property correlation was drawn based on the structure of the soft, hard, and chain extender and the observed properties are useful for understanding and design of intelligent coatings. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3158–3167, 2006     

Adhesion and permeability of polyimide–clay nanocomposite films for protective coatings

A polyimide (PI)–clay nanocomposite was prepared from a solution of poly(amic acid), a precursor of 2,2‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]propane dianhydride and p‐phenylenediamine, and dodecylamine–montmorillonite. Fourier transform infrared spectroscopy, thermogravimetric analysis, X‐ray diffraction, and atomic absorption spectroscopy were used to verify the incorporation of the modifying agents into the clay structure and the intercalation of the modified clay into the PI matrix. Both PI and PI–clay films were subsequently prepared by solution casting. The gas permeability, resistivity, and adhesion properties were determined. In the case of gas permeability, only a 3 wt % addition of clay reduced oxygen permeability to less than half that of unfilled PI. Furthermore, this hybrid showed an improvement in electrical resistivity because of the prevention of electrical tree growth by clay particles. More importantly, adhesion between the films and silicon increased with increasing clay content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2875–2881, 2003     

Aliphatic polyurethane–montmorillonite nanocomposite coatings: Preparation,characterization, and anticorrosive properties

Polyurethane (PU)–clay nanocomposite coatings were prepared by a sonication method. The stability and morphology of these coatings was characterized by turbidometry, X‐ray diffraction, and transmission electron microscopy. The anticorrosive properties of these coatings were investigated by salt‐spray and electrochemical impedance spectroscopy methods. According to the results, dispersed nanoclay layers in the matrix of the nanocomposite coating compositions led to superior anticorrosive characteristics compared to those of pure PU coatings. The best results were obtained with coatings containing about 5 wt % clay. The resistance of the coating containing 5% clay was about 9.002 GΩ after 225 days of immersion in a 3.5 wt % NaCl solution, whereas it was only 97 kΩ for the pure PU coating. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The characterization of organic modified clay and clay‐filled PMMA nanocomposite

Recently, polymer–clay hybrid materials have received considerable attention from both a fundamental research and application point of view. 1 - 3 This organic–inorganic hybrid, which contains a nanoscale dispersion of the layered silicates, is a material with greatly improved physical and mechanical characteristics. These nanocomposites are synthesized through in situ polymerization or direct intercalation of the organically modified layered silicate (OLS) into the polymer matrix. Thus, understanding the relationship between the molecular structure and the thermal stability (decomposition temperature, rate, and the degradation products) of the OLS is critical. In this study, modern thermal analysis techniques combined with infrared spectroscopy and mass spectrometry (TGA‐FTIR‐MS) were used to obtain information on the thermal stability and degradation products of organic modified clay. Furthermore, the thermal and mechanical properties of clay‐filled PMMA nanocomposites were determined by using TGA and DSC. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1702–1710, 2002     

Rigid polyurethane–clay nanocomposite foams: Preparation and properties

Rigid polyurethane–clay nanocomposite foams considered in this work are made with different clay types and for different clay concentrations. The densities of the foams are in the range of 140–160 kg/m³ with possible application as structural materials and for underwater buoyancy‐related uses. Wide‐angle X‐ray diffraction and transmission electron microscopy studies confirm the formation of nanocomposites. The compressive modulus and the storage modulus of the foams increase and the mean cell size decreases with addition of clay. However, the hydraulic resistance of the nanocomposite foams, a measure of the strength of the foam lamellae, is lower than that of the foams without clay. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2802–2809, 2007     

Preparation and properties of (BATB–ODPA) polyimide–clay nanocomposite materials

A series of polymer–clay nanocomposite (PCN) materials consisting of 1,4‐bis(4‐aminophenoxy)‐2‐tert‐butylbenzene–4,4′‐oxydiphthalic anhydride (BATB–ODPA) polyimide (PI) and layered montmorillonite (MMT) clay were successfully prepared by an in situ polymerization reaction through thermal imidization up to 300°C. The synthesized PCN materials were subsequently characterized by Fourier‐Transform infrared (FTIR) spectroscopy, wide‐angle powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of material composition on thermal stability, mechanical strength, molecular permeability and optical clarity of bulk PI and PCN materials in the form of membranes were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), molecular permeability analysis (GPA) and ultraviolet‐visible (UV/VIS) transmission spectra, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1072–1079, 2004     

Rubber–clay nanocomposite by solution blending

Ethylene vinyl acetate rubber (45% vinyl acetate content, EVA‐45) and organomodified clay (12Me‐MMT) composites were prepared by solution blending of the rubber and the clay. A combination of X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy studies showed that the composites obtained are on the nanometer scale. The measurements of the dynamic mechanical properties for different compositions over a temperature range (?100 to +100°C) showed that the storage moduli of these rubber–clay nanocomposites are higher above the glass to rubber transition temperature compared to the neat rubber. The tensile strength of the nanocomposites is about 1.6 times higher than that of the EVA‐45. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2216–2220, 2003     

Polyacrylamide–clay nanocomposite materials prepared by photopolymerization with acrylamide as an intercalating agent

A series of nanocomposite materials consisting of water‐soluble polyacrylamide (PAA) and layered montmorillonite (MMT) clay platelets were prepared by the effective dispersion of the inorganic nanolayers of the MMT clay in the organic PAA matrix via in situ ultraviolet‐radiation polymerization. The acrylamide monomers functioned as both the intercalating agent and the reacting monomers. As a representative procedure for the preparation of the nanocomposites, organic acrylamide monomers were first intercalated into the interlayer regions of acrylamide‐treated organophilic clay hosts, and this was followed by one‐step ultraviolet‐radiation free‐radical polymerization with benzil as a photoinitiator. The as‐prepared polyacrylamide–clay nanocomposite (PCN) materials were subsequently characterized by Fourier transform infrared spectroscopy, wide‐angle powder X‐ray diffraction, and transmission electron microscopy. The effects of the material composition on the thermal stability, optical clarity, and gas‐barrier properties of pristine PAA and PCN materials, in the forms of fine powders and membranes, were also studied by differential scanning calorimetry, thermogravimetric analysis, ultraviolet–visible transmission spectroscopy, and gas permeability analysis. The molecular weights of PAA extracted from PCN materials and pristine PAA were determined by gel permeation chromatography with tetrahydrofuran as an eluant. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3489–3496, 2004     

Thermal and thermomechanical properties of hyperbranched polyurethane‐urea/cenosphere hybrids

Hyperbranched polyurethane (HBPU)‐urea/cenosphere hybrid coatings were synthesized by incorporating various concentrations of cenosphere into HB polyester matrix by ultrasonication technique, and this polyester was further used for the preparation of isocyanate terminated HBPU prepolymers by reacting with excess isophorone diisocyanate (IPDI) in a NCO/OH ratio of 1.6 : 1. The desired hybrid coating is obtained by moisture curing the excess NCO present in the prepolymer through film casting. The structure of the hyperbranched polyester (HBPE) was conformed by ¹H, ¹³C NMR and FTIR spectroscopy and the degree of branching (DB) was calculated using Frechet and Frey equations. These hybrid films were characterized by powder XRD, FTIR, SEM, DMTA, and TGA. The structure property correlation, intermolecular/intramolecular hydrogen bonding, the surface morphology, and viscoelastic properties were studied. These results showed an increase in T_g and thermal stability of the hybrid coatings than the base polymer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effective enhancement of anticorrosive properties of polystyrene by polystyrene–clay nanocomposite materials

A series of polymer–clay nanocomposite (PCN) materials consisting of polystyrene (PS) and layered montmorillonite (MMT) clay was prepared by effectively dispersing the inorganic nanolayers of MMT clay in the organic PS matrix via in situ thermal polymerization. Organic styrene monomers were first intercalated into the interlayer regions of organophilic clay hosts, followed by a typical free radical polymerization with BPO as the initiator. The as‐synthesized PCN materials were characterized by infrared spectroscopy (IR), wide‐angle powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). PCN coatings with low clay loading (1 wt %) on cold‐rolled steel (CRS) were found to be superior in anticorrosion to those of bulk PS, based on a series of electrochemical measurements of corrosion potential, polarization resistance and corrosion current in a 5 wt % aqueous NaCl electrolyte. The molecular weights of PS extracted from PCN materials and bulk PS were determined by gel permeation chromatography (GPC) with tetrahydrofuran (THF) as the eluent. The effects of material composition on molecular barrier and thermal stability of PS and PCN materials, in the form of both free‐standing films and fine powders, were also studied by molecular permeability analysis, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1970–1976, 2004     

Preparation and characterization of rubber–clay nanocomposites

Rubber–clay nanocomposites were prepared by two different methods and characterized with TEM and XRD. The TEM showed clay had been dispersed to one or several layers. The XRD showed that the basal spacing in the clay was increased. It was evident that some macromolecules intercalated to the clay layer galleries. The clay layer could be uniformly dispersed in the rubber matrix on the nanometer level. The mechanical tests showed that the nanocomposites had good mechanical properties. Some properties exceeded those of rubber reinforced with carbon black, so the clay layers could be used as an important reinforcing agent as the carbon black was. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1879–1883, 2000     

Preparation and characterization of polyethylene–clay nanocomposites by using chlorosilane‐modified clay

Clay was modified by trimethylchlorosilane; after modification, hydroxyl groups at the edge of layers were reacted and CEC value was drastically decreased. Polyethylene–clay composites were prepared by melt compounding. Wide angle X‐ray diffraction (WAXD) and transmission electron microscopy (TEM) showed that intercalated nanocomposites were formed using organoclay ion‐exchanged from chlorosilane‐modified clay, but conventional composites formed using organoclay directly ion‐exchanged from crude clay. Dynamic mechanical analysis (DMA) of PE and PE–clay composites was conducted; the results demonstrated that nanocomposites were more effective than conventional composites in reinforcement and addition of organoclay resulted in the increase of glass transition temperature (T_g), but crude clay had no effect on T_g of PE–clay composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 676–680, 2004     

Synthesis of triazole ring‐containing pentol chain extender and its effect on the properties of hyperbranched polyurethane‐urea coatings

This article describes the synthesis and property evaluation of different hyperbranched polyurethane‐urea (HBPUU) coatings based on a newly synthesized triazole ring‐based pentol chain extender. For this initially, the chain extender was synthesized using acetylene azide click reaction and the structure of the intermediate compounds were confirmed by ¹H‐, ¹³C‐NMR, FTIR, and ESI‐mass spectrometry. In the further steps, the required HBPUU coatings were prepared by a systematic three‐step reaction process. In the first step, a isocyanate terminated prepolymer resin was synthesized at NCO/OH ratio of 1.2 : 1, while the second and third step involves the partially chain extension followed by moisture curing. The excess NCO content in the prepolymer was calculated by standard dibutylamine titration method and partially (10, 20, 30, 50, and 70% of the excess NCO content) chain extended with the pentol chain extender and remaining was moisture cured. The structure property relation of different HBPUU coating films were analyzed by FTIR peak deconvulation technique using Gaussian curve fitting procedure while, their viscoelastic and thermo‐mechanical properties were measured by dynamic mechanical thermal analysis, thermo gravimetric analysis, differential scanning calorimetric, and universal testing machine instruments. These results showed that thermal stability, glass transition temperature (T_g), elongation at break increases but the storage and tensile modulus decreases with increasing the percent loading of the triazole chain extender. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of waterborne polyurethane/clay nanocomposite: Effect on water vapor permeability

A series of waterborne polyurethane (WBPU)/clay nanocomposite coating materials were prepared by prepolymer process with different clay contents (0–2 wt %). The study investigated surface structure as well as water resistance, thermal, mechanical, and water vapor permeability (WVP) of composite materials as a function of clay contents. The glass transition temperature of composite materials was higher than pristine WBPU and also increased with increasing clay contents. Thermal stability, and water resistance of the nanocomposite films also increased, when compared with pristine WBPU, and these properties increased with an increase in clay content. The maximum tensile strength was found with optimum clay content (1 wt %) of composite films. The WVP of coated nylon fabrics depend on the clay content and temperatures. The rate (%) of WVP of coated nylon fabrics decreased with increasing clay content at a fixed temperature. However, at a fixed clay content the WVP increased with the increase of temperatures. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and properties of heterocyclically conjugated poly(3‐hexylthiophene)–clay nanocomposite materials

A series of heterocyclically conjugated polymer–clay nanocomposite (PCN) materials that consisted of organic poly(3‐hexylthiophene) (P3HT) and inorganic montmorillonite (MMT) clay platelets were prepared by in situ oxidative polymerization with FeCl₃ as an oxidant. The as‐synthesized PCN materials were characterized by Fourier transform infrared (FTIR) spectroscopy, wide‐angle powder X‐ray diffraction (WAXRD), and transmission electron microscopy (TEM). The effects of the material composition on the anticorrosion, gas barrier, thermal stability, flammability, mechanical strength, and electrical conductivity properties of the P3HT and PCN materials were studied by electrochemical corrosion measurements, gas‐permeability analysis (GPA), thermogrametric analysis (TGA), limiting oxygen index (LOI) measurements, dynamic mechanical analysis (DMA), and a four‐point probe technique, respectively. The molecular weights of extracted and bulk P3HT were determined by gel permeation chromatography (GPC) with THF as an eluant. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3438–3446, 2004     

Enhanced corrosion prevention effect of polysulfone–clay nanocomposite materials prepared by solution dispersion

A series of polymer–clay nanocomposite (PCN) materials containing polysulfone (PSF) and layered MMT clay were successfully prepared by effectively dispersing inorganic nanolayers of MMT clay in an organic PSF matrix via a solution dispersion technique. The synthesized PCN materials were subsequently investigated with a series of characterization techniques, including Fourier transform infrared (FTIR) spectroscopy, wide‐angle powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The prepared PCN coatings with low clay loading (1 wt %) on cold‐rolled steel (CRS) were found to be superior in corrosion prevention to those of bulk PSF, based on a series of electrochemical measurements of corrosion potential, polarization resistance, corrosion current and electrochemical impedance spectroscopy (EIS) in a 5 wt % aqueous NaCl electrolyte. The effects of material composition on the molecular barrier, mechanical strength and optical clarity of PSF and PCN materials, in the form of membranes, was also studied by molecular permeability analysis (GPA), dynamic mechanical analysis (DMA) and UV‐Visible transmission spectra, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 631–637, 2004     

Formation and characterization of polyurethane—vermiculite clay nanocomposite foams

Nanocomposites of rigid polyurethane foam with unmodified vermiculite clay are synthesized. The clay is dispersed either in polyol or isocyanate before blending. The viscosity of the polyol is found to increase slightly on the addition of clay up to 5 pphp (parts per hundred parts of polyol by weight). The gel time and rise time are significantly reduced by the addition of clay, indicating that the clay acts as a heterogeneous catalyst for the foaming and polymerization reactions. X‐ray diffraction and transmission electron microscopy of the polyurethane composite foams indicate that the clay is partially exfoliated in the polymer matrix. The clay is found to induce gas bubble nucleation resulting in smaller cells with a narrower size distribution in the cured foam. The closed cell content of the clay nanocomposite foams increases slightly with clay concentration. The mechanical properties are found to be the best at 2.3 wt% of clay when the clay is dispersed in the isocyanate; the compressive strength and modulus normalized to a density of 40 kg/m³ are 40% and 34% higher than the foam without clay, respectively. The thermal conductivity is found to be 10% lower than the foam without clay. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Effect of clay dispersion on the rheological properties and flammability of polyurethane‐clay nanocomposite elastomers

Polyurethane‐clay nanocomposite elastomers were synthesized using polyol‐clay blends with different levels of dispersion, which affected the final elastomer microstructure. A PU‐clay microcomposite elastomer containing partially dispersed clay showed poorer mechanical and similar fire properties to the unmodified polyurethane. More complete dispersion of the clay into the polyol led to an exfoliated structure in the final elastomer. This showed a higher modulus and kept a viscoelastic behavior to higher temperature than the pristine PU. The enhancement of mechanical and thermal properties in the nanocomposite elastomer can be attributed to the degree of clay exfoliation, and this also prevented dripping during the UL 94 fire test. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Properties of poly(vinyl alcohol)—Bentonite clay nanocomposite films in relation to polymer–clay interactions

This study describes an effective way for the preparation of well‐dispersed, high‐loaded PVA/bentonite nanocomposites with improved properties, based on nanoscale interactions. To this end, a series of Poly(vinyl alcohol)—bentonite clay nanocomposites have been prepared via solvent casting technique and their properties were thoroughly investigated by atomic force microscopy, transmission electron microscopy, X‐Ray diffraction, oxygen and water permeability, water sorption along with mechanical and thermal studies. Microscopic and XRD techniques revealed highly organized regions. Clay content up to 10% led to nanocomposites with high degree of exfoliation. In addition samples with increased filler content (20%) demonstrated also, apart from the delaminated, well‐organized intercalated regions. The nanocomposites exhibited increased mechanical, thermal and gas barrier properties, though they retained their optical clarity. Thus, the Young's modulus of the sample containing 20% clay was increased by 193 times, while the oxygen permeability was decreased about seven times, in regard to the corresponding values of the neat polymer. The obtained results were explored on the basis of nanoscale phenomena and it was concluded that the organized structures and intercalated regions observed on highly loaded samples are attributed to the competitive effect between weaker polymer–polymer interactions in relation to stronger polymer–clay ones. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of length of hydroxyalkyl groups in the clay modifier on the properties of thermoplastic polyurethane/clay nanocomposites

Polyether‐ and polyester‐based thermoplastic polyurethane (TPU) nanocomposites containing the montmorillonite modified with quaternary ammonium salts having a relatively long hydroxyalkyl branch (MMT‐OH) were prepared via solution mixing. Quaternary ammonium salts with dimethyl, octyl, hydroxyundecyl branches were synthesized by the addition reaction of dimethyloctylamine and 11‐bromo‐1‐undecanol and were used for the preparation of MMT‐OH. In this MMT‐OH clay, hydroxyl groups are located at the outer end of the relatively long undecyl branch, which may make the hydroxyl groups more exposed to the matrix polymers compared to the clays with the modifiers having shorter hydroxyalkyl chain such as C30B. Actually, more hydroxyl groups in MMT‐OH's are thought to be exposed outside the modified clay, since MMT‐OH's were observed to be somewhat dispersed in water, while clays with shorter alkyl chains were not. From XRD and TEM results, the silicate layers of MMT‐OH were shown to be very well dispersed in ether‐TPU and ester‐TPU nanocomposites prepared from dimethyl acetamide solution. In the case of ester‐TPU nanocomposites, much better clay dispersion was observed for nanocomposites containing MMT‐OH than the ones with C30B in the TEM images. The tensile properties measurement showed the similar trend. Although MMT‐OH has only one hydroxyl group while C30B has two, above results of better tensile properties and water dispersibility of MMT‐OH than C30B having two hydroxyls indicate that the position of hydroxyls may be a important factor in determining the properties of TPU/clay nanocomposites. Fourier transform infrared spectroscopy analyses showed that the long hydroxyalkyl chain modifiers may provide more hydrogen bonding sites than short hydroxyalkyl chain modifiers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008