Synthesis and characterization of epoxy based nanocomposites

Epoxy‐clay nanocomposites were synthesized to examine the effects of the content and type of different clays on the structure and mechanical properties of the nanocomposites. Diglycidyl ether of bisphenol‐A (epoxy) was reinforced by 0.5–11 wt % natural (Cloisite Na⁺) and organically modified (Cloisite 30B) types of montmorillonite. SEM results showed that as the clay content increased, larger agglomerates of clay were present. Nanocomposites with Cloisite 30B exhibited better dispersion and a lower degree of agglomeration than nanocomposites with Cloisite Na⁺. X‐ray results indicated that in nanocomposites with 3 wt % Cloisite 30B, d‐spacing expanded from 18.4 Å (the initial value of the pure clay) to 38.2 Å. The glass transition temperature increased from 73°C, in the unfilled epoxy resin, to 83.5°C in the nanocomposite with 9 wt % Cloisite 30B. The tensile strength exhibited a maximum at 1 wt % modified clay loading. Addition of 0.5 wt % organically modified clay improved the impact strength of the epoxy resin by 137%; in contrast, addition of 0.5 wt % unmodified clay improved the impact strength by 72%. Tensile modulus increased with increasing clay loading in both types of nanocomposites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1081–1086, 2005     

Polyurethane/clay nanocomposites with improved helium gas barrier and mechanical properties: Direct versus master‐batch melt mixing route

Thermoplastic polyurethane (TPU)/clay nanocomposite films were produced by incorporation of organo‐modified montmorillonite clay (Cloisite 30B) in TPU matrix by two different melt‐mixing routes (direct and master‐batch‐based mixing), followed by compression molding. In master‐batch mixing where the master‐batch was prepared by mixing of clay and TPU in a solvent, better dispersion of clay‐layers was observed in comparison to the nanocomposites produced by direct mixing. As a consequence, superior mechanical and gas barrier properties were obtained by master‐batch mixing route. The master‐batch processing resulted in 284 and 236% increase in tearing strength and tearing energy, respectively, with 5 wt % clay‐loading. Interestingly, in case of master‐batch mixing, the tensile strength, stiffness as well as breaking extension increased simultaneously up to 3 wt % clay‐loading. The helium gas permeability reduced by about 39 and 31% for the TPU/clay nanocomposites produced by mater‐batch and direct mixing routes, respectively, at 3 wt % loading of clay. Finally, the gas permeability results have been compared using three different gas permeability models and a good correlation was observed at lower volume fraction of clay. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46422.     

Synthesis and properties of polyurethane/clay nanocomposite by clay modified with polymeric methane diisocyanate

A polyurethane (PU)/clay nanocomposite was synthesized from polyol, polymeric 4,4′‐diphenyl methane diisocyanate (PMDI), and modified clay with PMDI. To achieve the modified clay with PMDI, the silanol group of the clay and the NCO group of the PMDI were reacted for 24 h at 50°C to form urethane linkage. Fourier transform IR analysis of the clay modified with the PMDI demonstrated that the NCO characteristic peak was observed in the clay after a modification reaction with PMDI. The results of the X‐ray pattern suggested that the clay layers were exfoliated from the PU/clay nanocomposite. From the results of the mechanical properties, the maximum values of the flexural and tensile strength were observed when 3 wt % clay based on PMDI was added into the PU/clay nanocomposites. The glass‐transition temperature and change in the heat capacity at glass transition temperature (ΔC_p) of the PU/clay nanocomposite decreased with an increase in the modified clay content. We suggested that the decrease in the ΔC_p with the modified clay content might be due to the increase of steric hindrance by the exfoliated clay layers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2879–2883, 2006     

A novel mechanism of exfoliation and physical properties of PU/organoclay nanocomposites

The novel mechanism of exfoliation of silicate was investigated. Exfoliation and intercalation was achieved even at 15 wt % in the polyurethane (PU) matrix via in situ polymerization. Through using IR consumption graph of curing agent, crosslinking equation could be derived. The diffusion rate of curing agent, Isophorone diisocyanate, brought the different morphologies as well as crosslinking densities of nanocomposites. Dodecylamine, the organifier having similar hydrogen‐bonding component with Isophorone diisocyanate than octadecylamine, affected the faster diffusion of isophorone diisocyanate in hydroxyl terminated polybutadiene/organoclay composite. This phenomenon was confirmed by DSC graph, XRD, SAXS, and TEM images. The nanocomposites showed high physical properties until at 10 wt % clay. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermal and surface characterization of polyurethane–urea clay nanocomposite coatings

This paper reports synthesis and characterization of polyurethane–urea (PU‐urea) and the nanocomposites derived from the PU‐urea with silicate clays. Organophilic montmorillonite cotreated by cetyl trimethyl ammonium bromide (CTAB) was synthesized and used to prepare PU‐urea/montmorillonite nanocomposites coatings. PU‐ureas were prepared from polyethylene glycol (PEG), polypropylene glycol (PPG), trimethylol propane (TMP), and 4,4′‐diphenylmethane diisocyanate (MDI) by reacting excess diisocyanate with polyether glycols. The excess isocyanate of the prepolymers was cured with atmospheric moisture. The synthesized moisture cured PU‐urea and nanocomposites were characterized by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetric (DSC), and angle resolved X‐ray photoelectron spectroscopy (AR‐XPS). The thermal stability of the PU‐urea nanocomposites was higher relative to the mother PU‐urea films. DSC results showed a slight enhancement in the soft segment glass transition temperature after 3 wt % clay loading. The surface properties showed an enrichment of the soft segment toward the surface. An enhancement in the hard segment composition in the nanocomposite coatings has resulted in enhancing the phase mixing process. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2393–2401, 2006     

Preparation and properties of elastomeric polyurethane/organically modified montmorillonite nanocomposites

Elastomeric polyurethane (PU) was mixed with 1, 3, 5, 7, and 10 wt% of Cloisite 30B to obtain PU-based nanocomposites. The thermal stabilities of the obtained products were characterized by thermal analysis using a thermogravimetric analyzer (TGA), which showed that the addition of 5 wt% of organoclay to the PU increased its stability, whereas thermal stabilization was less efficient at 10 wt%. The electrical conductivities of these composites were studied as a function of temperature, and it was found that the conductivity of PU was enhanced upon using 5 wt% of organoclay. The tensile strength, elongation (%), and Young’s modulus were considerably enhanced upon increasing the organoclay content to 5 wt%, but were then decreased to some extent upon further increasing the nanoparticle loading to 10 wt%. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to study these nanocomposite structures, and it was found that the PU molecular chains were intercalated into the galleries of the silicate layers in all of the nanocomposites, and that this reached a maximum when 5 wt% of Cloisite 30B was used.     

Synthesis and characterization of polyurethane/Mg‐Al layered double hydroxide nanocomposites

Layered double hydroxide (LDH) is a new type of nanofiller, which improves the physicochemical properties of the polymer matrix. In this study, 1, 3, 5, and 8 wt % of dodecyl sulfate‐intercalated LDH (DS‐LDH) has been used as nanofiller to prepare a series of thermoplastic polyurethane (PU) nanocomposites by solution intercalation method. PU/DS‐LDH composites so formed have been characterized by X‐ray diffraction and transmission electron microscopy analysis which show that the DS‐LDH layers are exfoliated at lower filler (1 and 3 wt %) loading followed by intercalation at higher filler (8 wt %) loading. Mechanical properties of the nanocomposite with 3 wt % of DS‐LDH content shows 67% improvement in tensile strength compared to pristine PU, which has been correlated in terms of fracture behavior of the nanocomposites using scanning electron microscope analysis. Thermogravimetric analysis shows that the thermal stability of the nanocomposite with 3 wt % DS‐LDH content is ≈ 29°C higher than neat PU. Limiting oxygen index of the nanocomposites is also improved from 19 to 23% in neat PU and PU/8 wt% DS‐LDH nanocomposites, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Bio‐based polymer nanocomposites based on layered silicates having a reactive and renewable intercalant

Soybean oil‐based polymer nanocomposites were synthesized from acrylated epoxidized soybean oil (AESO) combined with styrene monomer and montmorillonite (MMT) clay by using in situ free radical polymerization reaction. Special attention was paid to the modification of MMT clay, which was carried out by methacryl‐functionalized and quaternized derivative of methyl oleate intercalant. It was synthesized from olive oil triglyceride, as a renewable intercalant. The resultant nanocomposites were characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The effect of increased nanofiller loading in thermal and mechanical properties of the nanocomposites was investigated by thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The nanocomposites exhibited improved thermal and dynamic mechanical properties compared with neat acrylated epoxidized soybean oil based polymer matrix. The desired exfoliated nanocomposite structure was achieved when the OrgMMT loading was 1 and 2 wt % whereas partially exfoliated nanocomposite was obtained in 3 wt % loading. It was found that about 400 and 500% increments in storage modulus at glass transition and rubbery regions, respectively were achieved at 2 wt % clay loading compared to neat polymer matrix while the lowest thermal degradation rate was gained by introducing 3 wt % clay loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2031–2041, 2013     

Studies of particle dispersion in plasticized poly(vinyl chloride)/montmorillonite nanocomposites

Poly(vinyl chloride)(PVC) and dioctyl phthalate (DOP) were mixed with 5 and 10 wt % of Cloisite Na⁺, Cloisite 30B or Cloisite 93A. The obtained nanocomposites were characterized by thermal analysis using a thermogravimetric analyzer which showed that addition of 5 wt % of nanoclay to PVC increased its thermal stability in the sequence: Cloisite Na⁺< Cloisite 93A< Cloisite 30B. The electrical conductivity of these composites was studied as a function of temperatures and showed that the conductivity of PVC was enhanced upon using 5 wt % of nanoclay in the sequence: Cloisite Na⁺< Cloisite 30B < Cloisite 93A. The activation energy of interaction of PVC with nanoclay was found to be lowest for the composite containing 5 wt % of nanoclay in the same sequence. The tensile strength, elongation (%), and Young's modulus were considerably enhanced upon increasing the clay content to 5 wt % in the sequence: Cloisite Na⁺< Cloisite 93A < Cloisite 30B. X‐ray diffraction (XRD) and scanning electron microscopy (SEM) were used to study these nanocomposite structures, and it was found that the organoclay layers are homogeneously dispersed in the PVC matrix when 5 wt % of Cloisite 30B or Cloisite 93A was used. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of structure of organic modifiers and polyurethane on the clay dispersion in nanocomposites via in situ polymerization

Influence of polyurethane (PU) structure on the nature of PU/clay nanocomposite was studied using varying amounts of trimethylol propane (TMP) as branching agent. The effect of hydroxyl groups in the modifier of organoclays on the structure of PU/clay nanocomposites was studied. Nanocomposites were characterized using wide‐angle X‐ray diffraction measurements (WAXD) and transmission electron microscopy (TEM). The results show that formation of completely exfoliated and well dispersed polyurethane/clay nanocomposites via in situ polymerization, is facilitated by the presence of tethering groups on the clay surface and an ability to form branched and crosslinked structures. Incorporation of long alkyl chains in addition to tethering hydroxyl groups in the modifier structure of the clay did not significantly improve the compatibility of linear PU with the clay. Intercalated thermoplastic polyurethane/clay nanocomposites, prepared using poly(caprolactone diol) as soft segment and isophorone diisocyanate and 1,4‐butanediol as hard segments show increase in storage tensile moduli at temperatures before glass transition temperature when functional groups capable of chemically reacting with the growing polymer chains are present in the clay modifier. This is indicative of improved interaction of the polymer with the clay surface when the modifier has larger number of hydroxyl groups. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Novel polyether polyurethane/clay nanocomposites synthesized with organicly modified montmorillonite as chain extenders

A kind of novel polyether polyurethane (PU)/clay nanocomposite was synthesized using poly(tetramethylene glycol), 4,4′‐diphenylmethane diisocyanate (MDI), 1,6‐hexamethylenediamine, and modified Na⁺‐montmorillonite (MMT). Here, organicly modified MMT (O‐MMT) was formed by applying 1,6‐hexamethylenediamine as a swelling agent to treat the Na⁺‐MMT. The X‐ray analysis showed that exfoliation occurred for the higher O‐MMT content (40 wt %) in the polymer matrix. The mechanical analysis indicated that, when the O‐MMT was used as a chain extender to replace a part of the 1,2‐diaminopropane to form PU/clay nanocomposites, the strength and strain at break of the polymer was enhanced when increasing the content of O‐MMT in the matrix. When the O‐MMT content reached about 5%, the tensile strength and elongation at break were over 2 times that of the pure PU. The thermal stability and the glass transition of the O‐MMT/PU nanocomposites also increased with increasing O‐MMT content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 6–13, 2006     

Preparation,crystallization, and properties of biodegradable poly(butylene adipate‐co‐terephthalate)/organomodified montmorillonite nanocomposites

Intercalated and exfoliated nanocomposites of biodegradable poly(butylene adipate‐co‐terephthalate) (PBAT) and Cloisite 30B (C30B) were fabricated by a solution‐casting method to study the effects of the clay loading on the crystallization behavior, thermal stability, and dynamic mechanical properties of PBAT in PBAT/C30B nanocomposites. X‐ray diffraction and transmission electron microscopy results indicated the formation of exfoliated nanocomposites at low clay loadings (<5 wt %) and a mixture of exfoliated and intercalated nanocomposites with a clay content of 8 wt % throughout the PBAT matrix. Nonisothermal melt crystallization studies indicated that C30B enhanced the crystallization of PBAT, apparently because of a heterogeneous nucleation effect. Moreover, an attempt was made to quantitatively study the influence of the presence of C30B and its contents on the nucleation activity of PBAT in the PBAT/C30B nanocomposites. The thermal stability of PBAT decreased slightly in the nanocomposites. However, the storage modulus of PBAT apparently increased with the C30B loading increasing in the PBAT/C30B nanocomposites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Properties of Waterborne Polyurethane/Clay Nanocomposite Adhesives

A series of waterborne polyurethane (WBPU)/clay nanocomposite dispersions using two different organically modified clays, namely Cloisite 15A and Cloisite 30B, were prepared. It was found that the properties of WBPU/clay nanocomposites were highly dependent on both the clay content and the clay surface characteristic (hydrophilic/hydrophobic). A WBPU/clay nanocomposite dispersion with a higher clay content showed a less negative zeta potential. A lower zeta potential for dispersion with Cloisite 30B compared to Cloisite 15A was observed indicating a higher stability of the dispersion. The tensile strength, Young's modulus and adhesive strength of WBPU/clay nanocomposite containing Cloisite 30B were also higher than those of nanocomposite containing Cloisite 15A. The optimum clay contents, with respect to these properties, for nanocomposites with Cloisite 15A and Cloisite 30B were found to be 2 wt% and 3 wt%, respectively.     

Synthesis and Thermal Characterization of Polyurethane/Clay Nanocomposites Based on Palm Oil Polyol

Polyurethanes (PUs) are very versatile polymeric materials with a wide range of physical and chemical properties. PUs also have desirable properties, such as high abrasion resistance, tear strength, shock absorption, flexibility, and elasticity. Although they have poor thermal stability, it can be improved by using treated clay.

The objective of the present work is to study the thermal stability of polyurethane, polyurethane/montmorillonite (PU CTAB-mont 3% wt), and polyurethane/montmorillonite containing moca (PU Moca CTAB-mont 3% wt) nanocomposites based on palm oil polyol.

The interest of investigating the synthesis of polyurethane/clay nanocomposites based on palm oil polyol is to explore the use of palm oil polyol to partially replace petrochemical-based polyol.

Polyurethane/clay nanocomposites were prepared by a pre-polymer method and evaluated by Fourier Transform Infrared Spectra (FTIR) to determine micro-domain structures of segmented PU, PU CTAB-mont 3% wt, and PU Moca CTAB-mont 3% wt. The morphology of the nanocomposites was characterized by X-ray diffraction (X-RD), and flame retardant was investigated with thermogravimetric analysis (TGA). The result showed that in comparison with the virgin polyurethane, adding clay and moca demonstrated better thermal stability.     

Synthesis and characterization of nylon 6/clay nanocomposites prepared by ultrasonication and in situ polymerization

Nylon 6 nanocomposites were prepared by the in situ polymerization of ε‐caprolactam with ultrasonically dispersed organically modified montmorillonite clay (Cloisite 30B®). Dispersions of the clay platelets with concentrations in the range 1–5 wt % in the monomer were characterized using rheological measurements. All mixtures exhibited shear‐thinning, signifying that the clay particles were dispersed as platelets and forming a “house of cards” structure. Samples with Cloisite concentrations above 2 wt % showed a drop in viscosity between the initial shearing and repeated shearing, indicative of shearing breaking down the initial “house of cards” structures formed on sonication. DMTA measurements of the samples showed an increase in the β‐relaxation temperature with increasing clay concentration. The bending modulus, at temperatures below T_g, showed an increase with increasing clay concentration up to 4 wt %. X‐ray diffraction measurements showed that all nylon 6/Cloisite 30B samples were exfoliated apart from the 5 wt %, which showed that some intercalated material was present. The nylon crystallized into the α‐crystalline phase, which is the most thermodynamically stable form. Preference for this form may be a consequence of the long time associated with the postcondensation step in the synthesis or the influence of the platelets on the nucleation step of the crystal growth. DSC measurements showed a retardation of the crystallization rate of nanocomposite samples when compared with that of pure nylon 6, due to the exfoliated clay platelets hindering chain movement. This behavior is different from that observed for the melt‐mixed nylon 6/clay nanocomposites, which show an enhancement in the crystallization rate. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of elastomeric polyurethane/clay nanocomposites

An elastomeric polyurethane/clay (PU/clay) nanocomposite based on poly(propylene glycol) (PPG), glycerol propoxylate, and toluene‐diisocyanate (TDI) was synthesized by intercalative polymerization technology. The results of wide angle X‐ray diffraction (WAXD) studies showed that the gallery distance of the clay in the hybrid was enlarged from 1.9 to 4.5nm or more. Introducing clay in the PU matrix resulted in an increase in both the tensile strength and elongation at beak. When the clay content reached about 8%, the tensile strength and elongation at break were two times and five times respectively to that of the pure PU. In addition, the clay intercalative route to the nanocomposite synthesis also effected the thermal properties of the nanocomposites. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1444–1448, 2001     

Ternary elastomer nanocomposites based on NR/BR/SBR: Effect of nanoclay composition

Elastomer nanocomposites based on natural rubber (NR), butadiene rubber (BR), and styrene butadiene rubber (SBR) containing Cloisite 15A were prepared using a two‐roll mill. Mechanical, morphological, and rheological characterization of the prepared nanocomposites was carried out in order to study the effect of different nanoclay compositions, i.e., 1, 3, 5, 7, and 10 wt %. Intercalation of the elastomer chains into the silicate layers was evidenced by d‐spacing values calculated according to the results of the X‐ray diffraction (XRD) patterns. This was directly confirmed by transmission and scanning electron microscopy (TEM and SEM). The results depict a decreasing trend in the optimum cure time (t₉₀) and scorch time (t₅) values of the nanocomposite samples with increasing nanoclay loading; where the elastic modulus (G′) and complex viscosity (η*) of the samples considerably increased. The mechanical properties of the nanocomposites show a considerable increase in the tensile modulus of NR/BR/SBR/Cloisite 15A nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Gasoline permeation behavior and mechanical properties of polyamide 6/nanoclay,polyamide 6/PE‐g‐maleic anhydride blend,and polyamide 6/PE‐g‐maleic anhydride/clay nanocomposite

In this article, polyamide 6 (PA6)/clay nanocomposites, PA6/polyethylene grafted maleic anhydride (PE‐g‐MA) blends, and PA6/PE‐g‐MA/clay nanocomposites were prepared and their gasoline permeation behavior and some mechanical properties were investigated. In PA6/clay nanocomposites, cloisite 30B was used as nanoparticles, with weight percentages of 1, 3, and 5. The blends of PA6/PE‐g‐MA were prepared with PE‐g‐MA weight percents of 10, 20, and 30. All samples were prepared via melt mixing technique using a twin screw extruder. The results showed that the lowest gasoline permeation occurred when using 3 wt % of nanoclay in PA6/clay nanocomposites, and 10 wt % of PE‐g‐MA in PA6/PE‐g‐MA blends. Therefore, a sample of PA6/PE‐g‐MA/clay nanocomposite containing 3 wt % of nanoclay and 10 wt % of PE‐g‐MA was prepared and its gasoline permeation behavior was investigated. The results showed that the permeation amount of PA6/PE‐g‐MA/nanoclay was 0.41 g m^?2 day^?1, while this value was 0.46 g m^?2 day^?1 for both of PA6/3wt % clay nanocomposite and PA6/10 wt % PE‐g‐MA blend. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40150.     

Synthesis of a polyurethane/clay nanocomposite used as coating: Interactions between the counterions of clay and the isocyanate and incidence on the nanocomposite structure

The use of nanocomposites in textile applications, and in particular of polyurethane (PU) coatings reinforced by various additives [clay and polyhedral oligomeric silsesquioxane (POSS)], has grown in recent years. Some interesting results have been obtained, especially with Cloisite 30B (a montmorillonite organo‐modified by an alkyl ammonium cation bearing two primary hydroxyl functions): the thermal behavior and the reaction to fire were improved, but the structure (microcomposite, exfoliated, intercalated) was not really determined. This study focuses on polyurethane coatings reinforced with Cloisite 30B. The interactions between the diisocyanate and the counterions of Cloisite 30B and the structure obtained were demonstrated and discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 238–244, 2005     

Effect of organoclays on the properties of polyurethane/clay nanocomposite coatings

Linear, one‐binding‐site or two‐binding‐site (N⁺) organifiers with two hydroxyl end groups were synthesized, and novel organoclays were prepared through a cation‐exchange reaction between pristine sodium montmorillonite and the synthesized organifiers. After sonication of the as‐prepared organoclay in N,N′‐dimethylformamide for 10 min, the average size of the clay decreased to about 1 μm. The X‐ray diffraction patterns confirmed that the d‐spacing of the silicate layers of the organoclay expanded from 1.1 to about 1.9 nm and the peak intensity decreased with the molecular weight of the organifier increasing. Polyurethane/clay nanocomposites were synthesized by a one‐shot polymerization method. Both intercalated and exfoliated structures of the layered silicates in the polyurethane matrix were observed from transmission electron microscopy micrographs, and the d‐spacing ranged from 4 to 10 nm. The thermal and mechanical properties of the nanocomposite were enhanced by the introduction of the organoclay into the polyurethane matrix. An approximately 40–46°C increase in the onset decomposition temperature, a 200% increase in the tensile strength with a 0.5 wt % clay loading, and a 49% increase in Young's modulus with a 3 wt % clay loading were achieved. The effects of the molecular weight and the number of binding sites of the organifier on the properties of the nanocomposites were also evaluated. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010