Flammability and phase-transition studies of nylon 6/montmorillonite nanocomposites

Nylon 6 (PA6)/clay hybrids have been prepared using a direct melt intercalation technique by two processes. One is PA6 melt-mixing with modified clay, the other is PA6 melt-mixing with natural (Na⁺ base) clay using an ammonium salt bearing long alkyl chains as a polymer/clay reactive compatibilizer. Their structure and flammability properties are characterized by X-ray diffraction, transmission electron microscopy and cone calorimeter experiments. The results of the cone calorimeter experiments show that hybrids made by these two processes have a lower heat release rate peak and higher thermal stability than that of original PA6. Meanwhile, X-ray diffraction was used to investigate PA6/clay hybrids with various cooling histories from the melt, including medium-rate cooling (air cooling) and rapid cooling (water-quenched). In contrast to pure PA6 dominated by the α phase, the addition of clay silicate layers by these two methods favors the formation of the γ crystalline phase in PA6/clay hybrids. Flammability and phase-transition studies confirm that silicate layers added by these two methods have a similar nanoeffect and nanodispersion in the PA6 matrix.     

Flame-retardancy and photocatalytic properties of cellulosic fabric coated by nano-sized titanium dioxide

We have investigated the effect of titanium dioxide as a durable finish on the flammability and photocatalytic self-cleaning of cellulosic fabric. Nano-sized titanium dioxide particles were successfully synthesized and deposited onto cellulosic fibers with good compatibility, significant photocatalytic self-cleaning activity, and flame-retardancy properties using the sol–gel process at low temperature. The photocatalytic activity was tested by measuring the photodegradation of methylene blue under ultraviolet–visible illumination, and also flame-retardancy effect was tested by flammability tester. The samples have been characterized by several techniques such as scanning electron microscopy, transmission electron microscopy, diffuse reflectance spectroscopy, X-ray diffraction, and thermogravimetric analysis. The titanium dioxide nanoparticles with 10–20 nm in size have been found to form a homogeneous thin film on the fiber surface which shows efficient photocatalytic and flame-retardancy properties. This preparation technique can also be applied to new fabrics to create self-cleaning and flame-retardancy properties in them.     

Polyimide/montmorillonite nanocomposites with photolithographic properties

Polyimide/montmorillonite nanocomposites with photolithographic properties (PSPI/MMT) were prepared by in situ polymerization using an intrinsic photosensitive polyimide (PSPI) based on 4,4^′-diamino-3,3^′-dimethyldiphenylmethane (MMDA) and benzophenone-3,3^′,4,4^′-tetracarboxylic dianhydride (BTDA). XRD, TEM were used to obtain the information on morphological structure of PSPI/MMT nanocomposites. The exfoliated structure was obtained in the MMT content range studied. Satisfactory photolithographic patterns were obtained when the MMT content was below 2 wt.%. Universal tester, TGA, DSC were applied to characterize the mechanical and thermal properties of the nanocomposites. The introduction of MMT led to increase in tensile strength to the PSPI matrix while the elongation at break was not obviously effected. The introduction of MMT also resulted in improved thermal stability, marked decrease in coefficient of thermal expansion, decrease in solvent uptake, slight increase in glass transition temperature and increase in modulus.     

Characterization and thermal properties of Ni-exchanged montmorillonite with benzimidazole

Thermal analysis (TG, DTG), powder diffraction analysis (XRD) and infrared (IR) spectra were used to study of composition and release of benzimidazole from Ni(II)-exchanged montmorillonite under heating. Diffraction analysis indicated that benzimidazole molecules are intercalated into the interlayer space of montmorillonite. IR spectra and the analytical characteristics have shown that different type of interactions of benzimidazole is connected with different reaction conditions (acid or neutral solution). The release of benzimidazole from Ni(II)-montmorillonite under heating from studied samples proceeds in three distinct steps. The first step can be assigned to the release of water molecules while the last (third) one corresponds to the lattice dehydroxylation. The second step can be assigned to release of chemically bonded benzimidazole.     

Flammability properties analysis of methylphenol-carbonate in diphenylcarbonate production process

Diphenylcarbonate (DPC) has been regarded as a potential substitute material for highly toxic phosgene, reacting with bisphenol A (BPA) in a phosgene-free process to produce polycarbonate (PC). For synthesizing DPC, methylphenylcarbonate (MPC) was the critical intermediate with potential flammability in a transesterification reaction from dimethylcarbonate (DMC) and phenol. Under the National Fire Protection Association (NFPA) criterion, MPC is viewed as one sort of combustible liquid (Class IIIB). Once it fires or burns during storage, operation or transportation, it can cause a serious fire and explosion. However, researches are still scanty in mentioning the basic but crucial fire and explosion features of MPC to date. A sound background of material safety properties is essential for safe handling; in particular, flammability information is extremely crucial for a specific chemical during a unit operation to prevent any fire and explosion hazards. In this study, we investigated the explosion limits (LEL, UEL), maximum explosion pressure (P _max), maximum rate of explosion pressure rise ((dP/dt)_max), and gas or vapor explosion constant (K _g) of MPC, according to its practical operating conditions (1 atm, 250°C, 21 vol.% O₂) and by means of a 20 L vessel (20-L-Apparatus). By surveying and defining the experimental data through flammability tests, these basic but crucial safety-related parameters on flammability characteristics of MPC were proposed, so as to advance understanding and to avoid fire and explosion accidents for such relevant processes.     

Evaluation of a non-woven fabric coated with a chitosan bi-layer composite for wound dressing

This study presents a novel design of an easily stripped bi-layer composite that consists of an upper layer of a soybean protein non-woven fabric coated with a lower layer, a genipin-crosslinked chitosan film, as a wound dressing material. This study examines the in vitro properties of the genipin-crosslinked chitosan film and the bi-layer composite. Furthermore, in vivo experiments are conducted to study wounds treated with the composite in a rat model. Experimental results show that the degree of crosslinking and the in vitro degradation rate of the genipin-crosslinked chitosan films can be controlled by varying the genipin contents. In addition, the genipin contents should exceed 0.025 wt.-% of the chitosan-based material if complete crosslinking reactions between genipin and chitosan molecules are required. Water contact angle analysis shows that the genipin-crosslinked chitosan film is not highly hydrophilic; therefore, the genipin-crosslinked chitosan layer is not entangled with the soybean protein non-woven fabric, which forms an easily stripped interface layer between them. Furthermore, this new wound dressing material provides adequate moisture, thereby minimizing the risk of wound dehydration, and exhibits good mechanical properties. The in vivo histological assessment results reveal that epithelialization and reconstruction of the wound are achieved by covering the wound with the composite, and the composite is easily stripped from the wound surface without damaging newly regenerated tissue.     

Binding and degradation of DNA on montmorillonite coated by hydroxyl aluminum species

Adsorption, desorption and degradation by DNase I of DNA on montmorillonite (M) and different hydroxyaluminum-M complexes (Al(OH)_x-M) containing 2.5, 10.0 and 20.0 mmol coated Al/g clay (AM_2.5, AM₁₀ and AM₂₀) were studied. The adsorption isotherms of DNA on montmorillonite and Al(OH)_x-M complexes conformed to the Langmuir equation. The amount of DNA adsorbed followed the sequence of montmorillonite > AM₂₀ > AM₁₀ > AM_2.5. A marked decrease in the adsorption of DNA on montmorillonite and Al(OH)_x-M complexes was observed with the increase of pH from 4.0 to 9.0. Calcium ion significantly promoted DNA adsorption. The adsorption enthalpy of DNA on montmorillonite was endothermic, whereas that on Al(OH)_x-M complexes was exothermic. The percent desorption of DNA from clays was in the order of montmorillonite > AM_2.5 > AM₁₀ > AM₂₀, suggesting that OH–Al loading on montmorillonite surface increased the binding affinity of DNA. Fourier transform infrared (FTIR) spectra showed that the binding of DNA on AM₁₀ and AM₂₀ changed its conformation from the B-form to the Z-form. The presence of montmorillonite and Al(OH)_x-M complexes provided protection for DNA against degradation by DNase I. The higher level of protection was found with Al(OH)_x-M complexes compared to montmorillonite. The higher stability of DNA in the system of Al(OH)_x-M complexes seemed to be attributed mainly to the conformational change of bound DNA and their greater adsorption capacity for DNase I. The information obtained in this study is of fundamental significance for understanding the behavior of extracellular DNA in soil environments.     

Molecular dynamics simulation of thermomechanical properties of montmorillonite crystal. 3. montmorillonite crystals with PEO oligomer intercalates

We present the results of molecular dynamics (MD) simulation of the structure and thermomechanical behavior of Wyoming-type Na+-montmorillonite (MMT) with poly(ethylene oxide) (PEO) oligomer intercalates. Periodic boundary conditions in all three directions and simulation cells containing two MMT lamellae [Si248Al8][Al112Mg16]O640[OH]128 oriented parallel to the XY-plane were used. The interlamellar space, or gallery, between neighboring MMT lamellae was populated by 24 Na+ counterions and PEO macromolecules of different lengths, ranging from 2 up to 240 repeat units. We considered three different loadings of PEO within the gallery: 80, 160, and 240 repeat units, corresponding to 13, 23, and 31 wt % PEO based on total mass of the nanocomposite, respectively. In the cases of 13 and 23 wt %, the polymer chains formed one or two well-defined amorphous layers with interlayer distances of 1.35 and 1.8 nm, respectively. We have observed also formation of a wider monolayer gallery with interlayer distances of 1.6 nm. Three-layer PEO films formed in the case of 31 wt % loading. The thermal properties were analyzed over the range 300-400 K, and the isothermal linear compressibility, transversal moduli, and shear moduli were calculated at 300 K. These properties are compared with the results of our simulation of thermal and mechanical properties of MMT crystal with galleries filled by one or two water layers as well as with those of an isolated clay nanoplate.     

The elastic properties of sodium montmorillonite suspensions

Shear wave rigidity moduliG have been determined using a shear wave propagation technique for sodium montmorillonite suspensions. Measurements were made as a function of time at various values of pH, NaCl concentration (C) and solids concentration and the data used to estimateG _e the value of the modulus att=. The dependency ofG _e on pH,C and solids concentration is interpreted in terms of the mode of interaction between particles and the associated volume filling structure. The results suggest that whether a coagulated or dispersive structure develops in these suspensions depends not only on pH andC but also on the degree of delamination of the clay.     

The effect of phosphorus content on the thermal and the burning properties of cotton fabric coated with an ultrathin film of a phosphorus-containing polymer

The effect of phosphorus content on thermal degradation and burning behavior of poly(acryloyloxyethyl diethyl phosphate) or PADEP-coated cotton was studied. The results showed that PADEP-coated cotton prepared by admicellar polymerization using hexadecyltrimethylammonium bromide (HTAB) as a surfactant has higher amounts of phosphorus than that prepared using dodecyltrimethylammonium bromide (DTAB). Higher phosphorus content led to lower decomposition temperatures and greater amounts of char formation after thermal degradation. The effectiveness of the amount of phosphorus on the burning behavior of the treated cotton was investigated by an ASTM flammabilty test. In the case of PADEP-coated cotton prepared with DTAB, the flame spread slowly and extinguished with char formation on the fabric. For untreated cotton however, the flame spread quickly and burned the fabric entirely without char formation. Cotton coated with PADEP using HTAB exhibited self-extinguishing behavior after removing the ignition source. Decrease in decomposition temperature, increase in char formation and the burning behavior of PADEP-coated cotton are all consistent with phosphorus content on the treated fabric.     

Flammability, structure and mechanical properties of PP/OMMT nanocomposites

Polypropylene/organoclay (PP/OMMT) nanocomposites were prepared in a twin-screw corotating extruder using two methods. The first method was the dilution of commercial (PP/50% Nanofil SE3000) masterbatch in PP (or PP with commercial flame retardant). The second method consists of two stages was the extrusion of maleic anhydride grafted polypropylene (PP-g-MAH) with commercially available organobentonite masterbatch in first stage and dilution of the masterbatch in PP (or PP with commercial flame retardant) in second stage. XRD results showed no intercalation in composites obtained from commercial masterbatch without compatibilizer and semi - delamination for compatibilized systems. Tensile tests revealed that nanocomposites with 5% of organoclay have a slightly higher tensile modulus and tensile strength than pristine PP, however addition of the commercial flame retardant (FR) reduces mechanical parameters to roughly the level of those for neat PP. PP/OMMT composites have approx. 25% higher oxygen index than pristine PP, and this changes slightly after the addition of FR. The cone calorimeter tests showed a decrease of a heat release rate (HRR) and a mass loss rate (MLR) after the addition of FR.     

Ultrasound-assisted pullulan/montmorillonite bionanocomposite coating with high oxygen barrier properties

In this paper, the preparation and characterization of oxygen barrier pullulan sodium montmorillonite (Na(+)-MMT) nanocomposite coatings are presented for the first time. Full exfoliation of platelets during preparation of the coating water dispersions was mediated by ultrasonic treatment, which turned out to be a pivotal factor in the oxygen barrier performance of the final material even at high relative humidity (RH) conditions [oxygen permeability coefficients ~1.43 ± 0.39 and 258.05 ± 13.78 mL·μm·m(-2)·(24 h)(-1)·atm(-1) at 23 °C and 0% RH and 70% RH, respectively]. At the micro- and nanoscale, the reasons are discussed. The final morphology of the coatings revealed that clay lamellae were stacked on top of one another, probably due to the forced confinement of the platelets within the coating thickness after solvent evaporation. This was also confirmed by modeling the experimental oxygen permeability data with the well-known Nielsen and Cussler permeation theoretical models, which suggested a reasonable aspect ratio (α) of ~100. Electron microscopic analyses also disclosed a peculiar cell-like arrangement of the platelets. The stacking of the clay lamellae and the cell-like arrangement create the excellent oxygen barrier properties. Finally, we demonstrated that the slight haze increase in the bionanocomposite coating materials arising from the addition of the clays depends on the clay concentration but not so much on the sonication time, due to the balance of opposite effects after sonication (an increase in the number of scattering centers but a reduction in their size).     

Nanocomposite hydrogel consisting of Na‐montmorillonite with enhanced mechanical properties

A new kind of nanocomposite (NC) hydrogel with Na‐montmorillonite (MMT) is presented in this article. The NC hydrogels were synthesized by free radical copolymerization of acrylamide and (3‐acrylamidopropyl) trimethylammonium chloride (ATC) in the presence of MMT and N,N′‐methylene‐bis‐acrylamide used as chemical cross‐linker. Due to the cation‐exchange reaction between MMT and ATC (cationic monomer) during the synthesis of NC hydrogels, MMT platelets were considered chemical “plane” cross‐linkers, different from “point” cross‐linkers. With increasing amount of MMT, the crosslinking degree enhanced, causing a decrease of the swelling degree at equilibrium. Investigations of mechanical properties indicated that NC hydrogels exhibited enhanced strength and toughness, which resulted from chemical interaction between exfoliated MMT platelets and polymer chains in hydrogels. Dynamic shear measurements showed that both storage modulus and loss modulus increased with increasing MMT content. The idea described here provided a new route to prepare hydrogels with high mechanical properties by using alternative natural Na‐MMT. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1020–1026     

Thermal properties of Co-, Ni- and Cu-exchanged montmorillonite with 3-hydroxypyridine

Thermal analysis (TG, DTG), powder diffraction analysis (RTG) and infrared absorption spectra (IR spectra) were used to study of release of 3-hydroxypyridine (3-OHpy) from Co-, Ni- and Cu-exchanged montmorillonite (Co-MMT, Ni-MMT, Cu-MMT). It was found that release of 3-OHpy under heating from Co- and Ni-MMT proceeds in three distinct steps while from Cu-MMT in four steps. The first step can be assigned to the release of physically sorbed 3-OHpy while the last one corresponds to the lattice dehydroxylation. The second step (Co-, Ni-MMT) and/or second and third steps (Cu-MMT) can be assigned to release of chemically bonded 3-OHpy. This investigation shows that studied exchanged montmorillonites predominantly exhibit Lewis acid character. This revised version was published online in August 2006 with corrections to the Cover Date.     

Rheological properties of nanopowder alumina coated with adsorbed fatty acids

The rheological properties of a nanosized alumina powder coated with fatty acid steric stabilizers of varying chain length were investigated. The storage and loss moduli of the complex modulus were measured to characterize the behavior of the flocculated systems. As chain length increased, there was a transition from an elastic response to fluid behavior. However, the fluid system developed elastic characteristics at relatively low volume fractions of 22%. The length of the steric barrier required to produce the fluid dispersion was estimated to be approximately 2 nm and correlates with attractive interactions on the order of the system thermal energy. Moreover, in the flocculated systems, the storage modulus was found to be higher than reported previously in the literature. These higher values were related to the additional attractive forces due to van der Waals attractions between the hydrocarbon tails of the adsorbed fatty acid layers.     

Thermophysical properties of polyethylene filled with metal coated polyamide particles

A new type of thermally conductive particles based on a polyamide core and a silver shell was prepared and characterized. The particles were employed for the preparation of thermally conductive polymeric composites based on a high density polyethylene matrix. It was shown that silver coated particles significantly improved thermal conductivity of composites despite the low silver volume content. Experimental data were discussed in respect with various theoretical models.     

Tensile properties of ligno-cellulosic fabrics coated with styrenated polyester resin

Ligno-cellulosic fabrics from the tree Hildegardia populifolia were coated with styrenated polyester resin, and their tensile strength, elastic modulus, and the percent elongation at break were determined. The effects of sodium hydroxide and a silane-coupling agent on the tensile properties of the fabric were also studied. It was observed that the tensile strength and the modulus decreased whereas the percent elongation at break increased with coating. The coupling agent improved the properties of the untreated and polyester-coated fabric, but a reverse trend was observed when the fabric was treated with sodium hydroxide. The possible reasons for this behavior are discussed.     

Flammability of diene rubbers

This paper presents the results of testing the flammability and fire hazard of butadiene (BR), butadiene-acrylonitrile (NBR) and butadiene- styrene (SBR) rubbers with the use of oxygen index test, ignition temperature measurement, cone calorimetry and inverse liquid chromatography. Toxicometric indices, RTFH _CO/CO2, W_LC50SM and the concentration of polycyclic aromatic hydrocarbons (PAH) have been determined. The results obtained have been interpreted from the point of view of the chemical constitution of the polymers tested.     

Ni-exchanged montmorillonite with methyl-, dimethyl- and trimethylamine and their thermal properties

The influence of different steric properties of methylamine (MA), dimethylamine (DIMA) and trimethylamine (TRMA) on the type of interactions with Ni-exchanged montmorillonite and thermal properties of these materials were studied. The results of diffraction, spectral (IR) and thermal (TG, DTG) analysis show that MA, DIMA and TRMA are intercalated into the interlayer space of montmorillonite. Thermal decomposition in the temperature interval 20–450°C of studied samples with MA and DIMA proceeds in three steps (the release of chemisorbed amines, coordinated amines and alkylammonium cations) while the sample with TRMA decompose only in two steps (the peak corresponds to the release of coordinated TRMA is absent). The effect of different steric properties of individual amines is evident.