Nanocomposite hydrogel from grafting of acrylamide onto HPMC using sodium montmorillonite nanoclay and removal of crystal violet dye

Hydrogel nanocomposites were synthesized from grafting of acrylamide onto hydroxypropyl methylcellulose using methylenebisacrylamide crosslinker and sodium montmorillonite (Na-MMt) nanoclay. The effect of nanoclay content on the swelling of nanocomposites was investigated and an optimum swelling capacity was obtained at 12.7 wt% of Na-MMt. The effect of salt solutions on the swelling of nanocomposites revealed that the degree of swelling of samples depends only slightly on the salinity. The structure of nanocomposites was characterized by XRD, SEM, FTIR, and TEM techniques. The XRD and TEM results confirmed the exfoliation of Na-MMt nanoclay in nanocomposite matrix. The morphology of the nanocomposites was characterized by SEM technique and according to the results a loose surface was observed. The nanocomposite hydrogels were evaluated to remove cationic crystal violet dye from water. The investigation of the dye adsorption capacity and rate of nanocomposite hydrogels as a function of Na-MMt content revealed that the both adsorption capacity and rate is enhanced as the nanoclay content is increased in nanocomposite composition. The experimental equilibrated adsorption capacity of nanocomposites was analyzed using Freundlich and Langmuir isotherm models. The best fit to the experimental data was obtained with the Langmuir model.     

Influence of the nanoparticle type on the thermal decomposition of the green starch/poly(vinyl alcohol)/montmorillonite nanocomposites

In this study, some aspects concerning the thermal decomposition of starch/poly(vinyl alcohol) (PVA)/montmorillonite (MMT) nanocomposites with 2 wt% nanoclay, prepared by melt mixing method, were studied. For these loadings, the inorganic fillers are well dispersed through the PVA/starch matrix, i.e., the nanocomposites formed are mostly intercalated hybrids. The aim of this article is to establish the effect of the nanofiller nature on the thermal decomposition of the starch/PVA/MMT nanocomposites. The thermal behavior of the 50 wt% starch/50 wt% PVA blend and its nanocomposites with 2 wt% nanoclay has been investigated by thermogravimetric analysis coupled with Fourier transform-infrared spectroscopy and mass spectrometry (MS). The volatile compounds resulting during the thermal degradation were studied by in situ vapor phase FT-IR spectroscopy and MS technique under a controlled temperature/time program. Apart from the identification of the volatile compounds, some conclusions on the nanoclays effect on the degradation mechanism and formation of the volatile compounds in accordance with the previously developed general mechanisms for PVA and starch degradation have been formulated. The clay–PVA/starch nanocomposites show completely different degradation product distribution patterns, which may be attributed to the presence of the head-to-head structures and Si–O–C linkages formed between clay and blend components.     

Effect of nanoclay and barium sulfate nanoparticles on the thermal and morphological properties of polyvinylidene fluoride nanocomposites

The thermal, morphological and optical studies of BaSO₄ and MMT (nanoclay) embedded in PVDF were investigated. Nanocomposites samples of PVDF–BaSO₄–MMT were prepared by varying the loadings (1–4 mass%) in case of BaSO₄ and MMT nanomaterials, respectively. Polyvinylidene fluoride–barium sulfate-montmorillonite (PVDF–BaSO₄–MMT) nanocomposites were prepared by solvent-mixing technique. Nanoparticles were synthesized by in situ deposition technique with the help of nonionic polymeric surfactant, and the particle size of nanoparticles was recognized by scanning electron microscopy (SEM) analysis which confirms that the particle has diameter of 80–90 nm. As prepared, nanocomposites films (thickness, 25 μm) were characterized by Fourier transform infrared microscopy (FTIR), SEM and electron diffraction spectroscopy (EDS). FTIR shows that all the chemical constituents were present in the nanocomposites, whereas SEM analysis suggested that the nanofillers dispersed well in polymer matrix and EDS showed the elemental composition of nanocomposite samples. Thermal properties of nanocomposites were studied by using TG/DTA/DTG. TG/DTA studies showed decomposition temperature of pure PVDF is 473.5 °C. The decomposition temperature (T _d) of nanocomposites was increased by 93 °C in case of nanocomposites with addition of both BaSO₄ and MMT nanomaterials. The difference in the thermal degradation temperature was found to be 1.2% higher in case of addition of BaSO₄ nanoparticle as compared to nanoclay. The obtained transparent nanocomposite films were characterized by using UV–Vis spectrophotometer which shows that transparencies of nanocomposites are maintained in visible region, the intensity of absorption band in UV region is increased with the addition of BaSO₄ nanoparticles, while in case of addition of nanoclay the UV region does not show drastic changes. Addition of both nanoparticle and nanoclay shows higher absorption in comparison with the individual samples. But further, doubling the amount of nanoparticle and nanoclay shows decrease in UV absorption. Overall, the results of thermal studies show that the incorporation of BaSO₄ and MMT could significantly improve the thermal properties of nanocomposites.     

Mechanical, thermal, and moisture absorption properties of nano-clay reinforced nano-cellulose biocomposites

In this research, fully environment-friendly, sustainable and biodegradable ‘green’ composites were fabricated. A novel material comprised of microfibrillated cellulose and laponite clay with different inorganic/organic ratios (m/m) was prepared. The composites were characterized by tensile, bending and water absorption tests as well as dynamic mechanical analysis. The morphologies of these nanocomposites were evaluated through scanning electron microscopy. Results showed considerable improvement of mechanical properties; specifically in elastic modulus, tensile strength and flexural modulus with the addition of nanoclay up to 7.5 wt% nano-clay. The modulus of elasticity increased significantly by about 26 % at 5 wt% nanocaly. The flexural modulus increased by about 90 % at 7.5 wt% nanoclay. However, with an increased load of clay in the nanocomposite, the mechanical properties decreased due to the agglomeration of excessive nanoclay. The storage modulus was significantly increased at high temperature with increasing the load of nanoclay.     

Tailoring thermoresponsive nanostructured poly(N-isopropylacrylamide) hydrogels made with poly(acrylamide) nanoparticles

The thermoresponsive behavior and mechanical properties of nanostructured hydrogels, which consist of poly(acrylamide) nanoparticles embedded in a cross-linked poly(N-isopropylacrylamide) hydrogel matrix, are reported here. Nanostructured hydrogels exhibit a tuned volume phase transition temperature (T _VPT), which varies with nanoparticle content in the range from 32 up to 39–40 °C. Moreover, larger equilibrium water uptake, faster swelling and de-swelling rates, and larger equilibrium swelling at 25 °C were obtained with nanostructured hydrogels compared with those of conventional ones. Elastic and Young’s moduli were larger than those of conventional hydrogels at similar swelling ratios. The tuned T _VPT and the de-swelling rate were predicted with a modified Flory–Rehner equation coupled with a mixing rule that considers the contribution of both polymers. These behaviors are explained by a combination of hydrophilic/hydrophobic interactions and by the controlled inhomogeneities (nanoparticles) introduced by the method of synthesis.     

Preparation and characterization of the bacterial cellulose/polyurethane nanocomposites

New nanocomposites based on bacterial cellulose nanofibers (BCN) and polyurethane (PU) prepolymer were prepared and characterized by SEM, FT-IR, XRD, and TG/DTG analyses. An improvement of the interface reaction between the BCN and the PU prepolymer was obtained by a solvent exchange process. FT-IR results showed the main urethane band at 2,270 cm^?1 to PU prepolymer; however, in nanocomposites new bands appear as disubstituted urea at 1,650 and 1,550 cm^?1. In addition, the observed decrease in the intensity of the hydroxyl band (3,500 cm^?1) suggests an interaction between BCN hydroxyls and NCO-free groups. The nanocomposites presented a non-crystalline character, significant thermal stability (up to 230 °C) and low water absorption when compared to pristine BCN.     

Carbon nanofibers reinforced soy polyol-based polyurethane nanocomposites

Vapor-grown carbon nanofiber (CNF)-modified soy polyol-based polyurethane (PU) nanocomposites with different hydroxyl value of polyols (OH) were synthesized. The glass transition, thermal stability, mechanical properties, and morphology of the PU nanocomposites were characterized through differential scanning calorimetry, thermogravimetry, universal test machine, and scanning electron microscopy. The addition of CNFs increased the glass transition temperature as well as significantly improved tensile strength and Young’s modulus of PU nanocomposites. Meanwhile, thermal and mechanical properties of PU composites were influenced by the different hydroxyl value of polyols due to those different structures. In particular, in the case of 2 mass% CNF addition in PU derived from soy polyol with the OH number of 164 mg KOH g^?1, 20.8 °C improvement in the glass transition temperature, 115 % increment in tensile strength, and nearly eightfold increase in Young’s modulus were obtained.     

Influence of Nanoclay on the Mechanical Performance of Wild Cane Grass Fiber-Reinforced Polyester Nanocomposites

Natural fiber-reinforced nanocomposites were prepared by incorporating wild cane grass fiber and organically modified montmorillonite (MMT) nanoclay into polyester resin. The composites were formulated up to a maximum volume of fiber of approximately 40% and their mechanical properties were investigated. The mean tensile strength and tensile modulus of nanoclay-filled wild cane grass fiber composites are 6.3% and 18.3% greater than those of wild cane grass fiber composites, respectively, without addition of nanoclay at maximum percentage volume of fiber. The mean flexural strength of nanocomposites at maximum percentage volume of fiber was increased to a maximum of 221 Mpa and flexural modulus to 4.2 Gpa. The mean impact strength of nanoclay-filled wild cane grass fiber composites was increased to 376.7 J/m at maximum percentage volume of fiber. The weight loss of nanoclay-filled wild cane grass fiber/polyester composites was 30% and 22% less than that of composites without nanoclay at maximum percentage volume of fiber. The results indicated that the use of nanoclay showed significant improvement in all the mechanical properties of wild cane grass fiber-reinforced composites.     

Thermal Degradation Behavior and Kinetic Analysis of Ultra High Molecular Weight Polyethylene Based Multi-Walled Carbon Nanotube Nanocomposites Prepared Via in-situ Polymerization

Thermal degradation behavior of multi-wall carbon nanotubes (MWCNTs)/ultra high molecular weight polyethylene (UHMWPE) nanocomposites, with different nanotubes contents (0.5, 1.5 and 3.5 wt%) prepared via in-situ polymerization technique have been investigated using thermal gravimetric analysis (TGA). TGA spectra revealed that these nanocomposites had enhanced thermal stability and no significant mass loss (<0.4 wt%) occurred up to 350°C. Thermal degradation of these UHMWPE/MWCNT nanocomposites was investigated in terms of parameters such as the onset temperature of degradation (T₁₀), the decomposition temperature at 50% wt loss (T₅₀), the degradation temperature of maximum rate of the weight loss (T_m), and the residual yields (W_R) from TGA. The degradation activation energies (E) of virgin UHMWPE and its nanocomposites were estimated using the Friedman, the Ozawa, Flynn, and Wall (OFW), and the Kissinger's methods. Results indicated that the degradation activation energy for the virgin UHMWPE was 281.3 kJ/mol. The activation energy increased with increasing nanotube loading up to 1.5 wt% indicating that MWCNTs had a stabilizing effect on the degradation of the matrix. However, loadings of 3.5 wt% of nanotube or more could slightly decrease the activation energy. The decrease in the activation energy for degradation of nanocomposites with higher MWCNT concentrations might be attributed to the catalytic effects of nanotubes and polymerization catalyst residues. The “model fitting” method indicated a mechanism of n ^th-order auto-catalysis from the form of the conversion curves for UHMWPE/MWCNTs nanocomposites prepared via in-situ polymerization.     

Thermal Degradation Kinetics of Polyurethane/Organically Modified Montmorillonite Clay Nanocomposites by TGA

Polyurethane (PU) has been prepared by using polyether polyol (jagropol oil) and 1,6- hexamethylene diisocyanate (HMDI) as a cross-linker. The organically modified montmorillonite clay (MMT) is well-dispersed into urethane matrix by an in situ polymerization method. A series of PU/MMT nanocomposites have been prepared by incorporating varying amounts of nanoclay viz., 1, 3, 5 and 6 wt %. Thermogravimetric analysis (TGA) of the PU/MMT nanocomposites has been performed in order to establish the thermal stability and their mode of thermal degradation. The TGA thermograms exhibited the fact that nanocomposites have a higher decomposition temperature in comparison with the pristine PU. It was found that the thermal degradation of all PU nanocomposites takes place in three steps. All the nanocomposites were stable up to 205°C. Degradation kinetic parameters of the composites have been calculated for each step of the thermal degradation processes using three mathematical models namely, Horowitz–Metzger, Coats–Redfern and Broido's methods.     

Study of thermal stabilization for polystyrene/carbon nanocomposites via TG/DSC techniques

The degradability and durability for polymer–nanocomposites under various environmental conditions are from the essential fields of research. This study was carried out to examine the thermal stability of polystyrene loaded by carbon (C) nanoparticles up to 20 wt% content. The thermal degradation of PS/C nanocomposites were studied by thermogravimetry analysis and differential scanning calorimetry (DSC) under non-isothermal condition and inert gas atmosphere at constant heating rate 10 °C min^?1. The variation of degradation characteristic temperatures as a function of C content has been a non-monotonic behavior. The obtained results suggested that the C nanoparticles act as a promoter slowing down the degradation and providing a protective barrier to the nanocomposite, except 5 wt% C content. The latter exception was confirmed by DSC curve through the emergence of a small endothermic peak before the fundamental endothermic, melting, one.     

Sol–gel synthesis and enhanced properties of a novel transparent PMMA based organic–inorganic hybrid containing phosphorus,nitrogen and silicon

A novel flame-retardant silane containing phosphorus and nitrogen, tetramethyl(3-(triethoxysilyl)propylazanediyl) bis(methylene) diphosphonate (TMSAP), is firstly synthesized and then incorporated into poly(methyl methacrylate) (PMMA) matrix through sol–gel method to produce organic–inorganic hybrids. The chemical structure of TMSAP was confirmed by Fourier transform infrared spectra, ¹H nuclear magnetic resonance (NMR) and ³¹P NMR spectra. The hybrids obtained maintain relatively high transparency, and exhibit a significant improvement in thermal properties, mechanical performance and flame retardancy when compared to pure PMMA, including increased glass transition temperature (T _g ) by 11.4 °C, increased onset thermal degradation temperature (T_0.1) by 82.6 °C, increased half thermal degradation temperature (T_0.5) by 42.0 °C, increased hardness, increased limited oxygen index and decreased heat release rate. Morphological studies of hybrids by scanning electron microscopy (SEM) and ²⁹Si MAS NMR suggest that cross-linked silica network is formed in the hybrids and the inorganic silica particles are distributed well in the polymer matrix. Thermal degradation behaviors investigated by thermogravimetric analysis and char structure analysis studied by SEM and X-ray photoelectron spectroscopy demonstrate the catalytic charring function of TMSAP, and synergistic effect between phosphorus, nitrogen and silicon element. The formation of network structure, homogeneous distribution of silica and the char formation during degradation play key roles in these property enhancements. Detailed mechanisms for these enhancements are proposed.     

Superabsorbent Hydrogels Based to Polyacrylamide/Cashew Tree Gum for the Controlled Release of Water and Plant Nutrients

Agricultural production is influenced by the water content in the soil and availability of fertilizers. Thus, superabsorbent hydrogels, based on polyacrylamide, natural cashew tree gum (CG) and potassium hydrogen phosphate (PHP), as fertilizer and water releaser were developed. The structure, morphology, thermal stability and chemical composition of samples of polyacrylamide and cashew tree gum hydrogels with the presence of fertilizer (HCGP) and without fertilizer (HCG) were investigated, using X-ray diffractometry (XRD), Fourier Transformed Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Thermogravimetric Analysis (TGA/DTG) and Energy Dispersive Spectroscopy (EDS). Swelling/reswelling tests, textural analysis, effect of pH, release of nutrients and kinetics were determined; the ecotoxicity of the hydrogels was investigated by the Artemia salina test. The results showed that PHP incorporation in the hydrogel favored the crosslinking of chains. This increased the thermal stability in HCGP but decreased the hardness and adhesion properties. The HCGP demonstrated good swelling capacity (~15,000 times) and an excellent potential for reuse after fifty-five consecutive cycles. The swelling was favored in an alkaline pH due to the ionization of hydrophilic groups. The sustained release of phosphorus in HCGP was described by the Korsmeyer–Peppas model, and Fickian diffusion is the main fertilizer release mechanism. Finally, the hydrogels do not demonstrate toxicity, and HCGP has potential for application in agriculture.     

Morphology and thermal characterization of montmorillonite/polybenzimidazole nanocomposite

In this study, thermal and morphological properties of organically modified montmorillonite (mMMT)/poly(2,5-benzimidazole) (ABPBI) composite were investigated. The morphology and structure of mMMT/ABPBI composites were characterized by infrared, X-ray diffraction, scanning electron microscopy, and thermogravimetric analysis techniques. At low mMMT loading levels, exfoliation was the predominant mechanism of mMMT dispersion. At high mMMT loading levels, nonintercalated microcomposite morphology is partially favored in expense of the intercalated nanocomposite. Thermal degradation of nanocomposite occured in three stages. In the second stage of thermal degradation, the onset temperature of degradation for the mMMT/ABPBI nanocomposites was lower than that of ABPBI polymer. In the last stage, the improvement in thermal stability by the introduction of mMMT into the ABPBI was different from the second stage. The activation energy for degradation of ABPBI increased from 62.6 to 77.7 kJ mol^?1 after loading of 5 mass% of mMMT into ABPBI matrix under air atmosphere.     

Physical–chemical characterization of new anti-inflammatory agent (LPSF/GQ-130) and evaluation of its thermal compatibility with pharmaceutical excipients

LPSF/GQ-130 is a drug candidate, according to reports about its significant anti-inflammatory activity and non-toxicity demonstrated in an acute preclinical study. Despite this, knowledge of its physical–chemical properties is insufficient for the development of medicines. Thus, this work aimed to characterize the raw material at its molecular, particle, and agglomerate level as well as evaluate its thermal compatibility to pharmaceutical excipients. Through spectrometric techniques the molecular structure of the substance was confirmed. For thermal analysis its melting (171.3–176.5 °C) and degradation (238.3–297.4 °C) ranges, besides its purity (99.37 %), were determined. The kinetic non-isothermal degradation supplied the order of thermal reaction (0), the activation energy (96.14 kJ mol^?1) and the frequency factor (3.130 × 10^?7 min^?1). The diffraction of X-rays presented well defined signs in the angles 5.5°, 16.3°, and 44.18° 2θ, suggesting crystalline structure. Scanning electronic microscopy exhibited needle morphology. LPSF/GQ-130 presented Type-III isotherm adsorption/desorption, with a superficial area of 81.3529 m² g^?1 and water content calculated at 1 % using the Karl Fisher method. Laser granulometry calculated its granulometry between 11.65 and 13.10 μm, thus it was characterized as a very fine powder. The prototype was classified as insoluble in water (<0.0187 μg mL^?1) and soluble in acetone and acetonitrile, and exhibits instability in basic pH (100 %) and oxidative conditions (30–70 %). In thermal compatibility the excipients PVP K-30, Compritol^® 888 ATO, and MYRJ^® 59 seem to exercise a protective thermal activity for the prototype.     

Thermogravimetric analysis and differential scanning calorimetric studies on nanoclay-filled TPU/PP blends

Thermal stability of ester-thermoplastic polyurethane (TPU)/polypropylene (PP) and ether-TPU/PP blends was evaluated by thermogravimetric studies. Thermal studies were made as a function of blend ratio. Effects of compatibilization using MA-g-PP and nanoclay addition on thermal stability were evaluated. Mass loss at 400 °C was found to decrease with increasing PP content were determined. Finally the compatibility and crystallization behavior of the blends were studied by differential scanning calorimetry. Compared to the ether-TPU blend nanocomposites, the ester-TPU blends showed better compatibility and thermal stability.     

Effect of water release on thermal properties of polyaniline

Conducting polyaniline (PANI) was studied by thermal expansion measurement, thermogravimetric analysis and by electrical conductivity measurement. Relative elongation and coefficient of thermal expansion (CTE) were determined from room temperature to 60 °C. Various temperature profiles were used. During heating, the treatment of samples at a constant temperature higher than the room temperature, or evacuation, water was released from the samples. Water release was detected by mass and thermogravimetric analysis. Water release was connected with shrinkage of the PANI samples and apparent negative CTE in the first thermal cycle. In the following thermal cycles, it increased and reached a positive value. CTE of PANI attained values in the range of ?30 × 10^?6 K^?1 up to 20 × 10^?6 K^?1 in dependence on water content in the sample before measurement and on experimental conditions of measurement. Irreversible shrinkage of the polymer was the largest in the first thermal cycle. Water release exhibited a strong time and temperature dependence, and it was only partially reversible. The electrical conductivity was measured by a four-point van der Pauw method. Relative electrical conductivity decreased with amounts of water release. Relative decrease of electrical conductivity reached as far as 20% after evacuation 7 h at the room temperature.     

Extraction of Co-Products from Biomass: Example of Thermal Degradation of Silymarin Compounds in Subcritical Water

In an effort to increase revenues from a given feedstock, valuable co-products could be extracted prior to biochemical or thermochemical conversion with subcritical water. Although subcritical water shows significant promise in replacing organic solvents as an extraction solvent, compound degradation has been observed at elevated extraction temperatures. First order thermal degradation kinetics from a model system, silymarin extracted from Silybum marianum, in water at pH 5.1 and 100, 120, 140, and 160 °C were investigated. Water pressure was maintained slightly above its vapor pressure. Silymarin is a mixture of taxifolin, silichristin, silidianin, silibinin, and isosilibinin. The degradation rate constants ranged from 0.0104 min⁻¹ at 100 °C for silichristin to a maximum of 0.0840 min⁻¹ at 160 °C for silybin B. Half-lives, calculated from the rate constants, ranged from a low of 6.2 min at 160 °C to a high of 58.3 min at 100 °C, both for silichristin. The respective activation energies for the compounds ranged from 37.2 kJ/gmole for silidianin to 45.2 kJ/gmole for silichristin. In extracting the silymarin with pure ethanol at 140 °C, no degradation was observed. However, when extracting with ethanol/water mixtures at and 140 °C, degradation increased exponentially as the concentration of water increased. An erratum to this article can be found at     

Synthesis and thermal studies of flexible polyurethane nanocomposite foams obtained using nanoclay modified with flame retardant compound

This work presents thermal studies of nanocomposites based on the flexible polyurethane (PU) matrix and filled using montmorillonite organically modified with organophosphorus flame retardant compound. Flexible PU nanocomposite foams were prepared in the reaction carried out between reactive alcoholic hydroxyl and isocyanate groups with the ratio of NCO to OH groups equal to 1.05. The amount of an organoclay ranging from 3 to 9 vol% was added to the polyol component of the resin before mixing with isocyanate. The apparent density of PU foams was ranging from 0.066 to 0.077 g cm^?1. Thermal properties of the flexible PU nanocomposite foams were investigated by thermogravimetry and dynamical mechanical analysis. Glass transition temperatures (T _g) were defined as maximum peak on tanδ curve. Thermal decomposition was observed at 310–320 °C (calculated from the onset of TG curve). Tensile strength of the PU foams was determined using mechanical test. The microstructure of the nanoparticles and the composites was investigated by X-ray diffraction. Finally, it was confirmed that the thermal and mechanical properties of flexible PU nanocomposite depend on the amount of nanoclay.     

Nanoclay modified silica phenolic composites: mechanical properties and thermal response under simulated atmospheric re‐entry conditions

Ablative nanocomposites based on nanoclay‐dispersed addition curable propargylated phenolic novolac (ACPR) resin, reinforced with chopped silica fiber, were investigated for their thermal response behavior under simulated heat flux conditions corresponding to typical atmospheric re‐entry conditions. Organically modified nanoclay (Cloisite 30B) was incorporated to different extents (1–10%) in the ACPR resin matrix containing silica fiber to form the composite. The composites displayed optimum mechanical properties at around 3 wt% of nanoclay loading. The resultant composites were evaluated for their ablative characteristics as well as mechanical, thermal and thermo‐physical properties. The reinforcing effect of nanoclay was established and correlated to the composition. The mechanical properties of the composites and its pyrolysed product improved at moderate nanoclay incorporation. Plasma arc jet studies revealed that front wall temperature is lowered by 20°C and that at backwall by 10–13°C for the 3 wt% nanoclay‐incorporated composites due to impedance by nanoclay for the heat conduction. Nanoclay diminished the coefficient of thermal expansion by almost 50% and also reduced the flammability of the composites. The trend in mechanical properties was correlated to the microstructural morphology of the composites. The nanomodification conferred better strength to the pyrolysed composites. Copyright © 2014 John Wiley & Sons, Ltd.