Growth and fire resistance of colloidal silica-polyelectrolyte thin film assemblies

Thin films of colloidal silica were deposited on cotton fibers via layer-by-layer (LbL) assembly in an effort to reduce the flammability of cotton fabric. Negatively charged silica nanoparticles of two different sizes (8 and 27 nm) were paired with either positively charged silica (12 nm) or cationic polyethylenimine (PEI). PEI/silica films were thicker due to better (more uniform) deposition of silica particles that contributed to more than 90% of the film weight. Each coating was evaluated at 10 and 20 bilayers (BL). All coated fabrics retained their weave structure after being exposed to a vertical flame test, while uncoated cotton was completely destroyed. Micro combustion calorimetry confirmed that coated fabrics exhibited a reduced peak heat release rate, by as much as 20% relative to the uncoated control. The 10 BL PEI-8 nm silica recipe was the most effective because the coating is relatively thick and uniform relative to the other systems. Soaking cotton in basic water (pH 10) prior to deposition resulted in better assembly adhesion and flame-retardant behavior. These results demonstrate that LbL assembly is a useful technique for imparting flame retardant properties through conformal coating of complex substrates like cotton fabric.     

pH Tailoring Electrical and Mechanical Behavior of Polymer–Clay–Nanotube Aerogels

Aerogels are low density (<0.1 g · cm⁻³), highly porous materials that are especially interesting for insulating applications. Combinations of clay and water‐soluble polymers are commonly used to produce aerogels, but these materials are often mechanically weak. Single‐walled carbon nanotubes (SWNT) were combined with clay and found to significantly improve mechanical behavior and impart electrical conductivity to these aerogels. Poly(acrylic acid) (PAA) as the matrix polymer provides a means of tailoring the electrical conductivity and mechanical behavior by altering the pH of the aqueous aerogel precursor suspensions prior to freeze drying. An aerogel, made from a pH 9 aqueous suspension containing 0.5 wt.‐% PAA, 5 wt.‐% clay, and 0.05 wt.‐% SWNT, has a compressive modulus of 373 kPa. In the absence of nanotubes, this modulus is reduced to 43 kPa. Reducing suspension pH to 3, prior to freeze drying, also reduces modulus for these aerogels, but electrical conductivity is increased when nanotubes are present. It was found that bundled nanotubes provide better reinforcement for these low‐density composites, which may provide some new insight into the use of nanotubes in materials that will be exposed to compressive loading.

     

Recent Advances in Gas Barrier Thin Films via Layer‐by‐Layer Assembly of Polymers and Platelets

Layer‐by‐layer (LbL) assembly has emerged as the leading non‐vacuum technology for the fabrication of transparent, super gas barrier films. The super gas barrier performance of LbL deposited films has been demonstrated in numerous studies, with a variety of polyelectrolytes, to rival that of metal and metal oxide‐based barrier films. This Feature Article is a mini‐review of LbL‐based multilayer thin films with a ‘nanobrick wall’ microstructure comprising polymeric mortar and nano­platelet bricks that impart high gas barrier to otherwise permeable polymer substrates. These transparent, water‐based thin films exhibit oxygen transmission rates below 5 × 10^‐3 cm³ m^‐2 day^‐1 atm^‐1 and lower permeability than any other barrier material reported. In an effort to put this technology in the proper context, incumbent technologies such as metallized plastics, metal oxides, and flake‐filled polymers are briefly reviewed.

     

Environmentally-benign,water-based covalent polymer network for flame retardant cotton

Cellulose - Relatively simple flame retardant finishing technologies for cotton are greatly desired in a variety of fire-sensitive applications (e.g., transportation, workwear, etc.). Many current...     

Comparison of Covalently and Noncovalently Functionalized Carbon Nanotubes in Epoxy

Carbon nanotubes typically require the use of a dispersing or stabilizing agent to prevent significant aggregation during incorporation into a polymer matrix. These additives must be strongly associated, either covalently or physically, to achieve their purpose. In this study, multi‐walled carbon nanotubes (MWNTs) were dispersed into an epoxy matrix using polyethylenimine (PEI) as a dispersant that was either covalently attached to the nanotubes or physically mixed to result in only noncovalent interaction. Epoxy composites containing covalently modified MWNTs exhibited greater storage modulus and reduced electrical conductivity.

     

Highly selective multilayer polymer thin films for CO2/N2 separation

Multilayer thin films of poly(ethylene oxide) (PEO) and poly(methacrylic acid) (PMAA), deposited via layer‐by‐layer (LbL) assembly from aqueous solutions, are investigated for CO₂/N₂ separation. Eight and ten bilayer (217 and 389 nm thick, respectively) PEO/PMAA thin films deposited on a 25 μm polystyrene substrate exhibit CO₂/N₂ selectivities of 142 and 136, respectively. These are the highest reported to‐date for this gas pair separation using a homogeneous polymer film. While further work remains to improve CO₂ permeability, these results indicate the potential of LbL assemblies as standalone CO₂ separation membranes for low‐flux/high‐purity applications, or as part of a composite and/or mixed‐matrix membrane for high‐flux applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1730–1737     

Maintaining hand and improving fire resistance of cotton fabric through ultrasonication rinsing of multilayer nanocoating

Thin films of environmentally benign polyelectrolytes, cationic chitosan (CH) and anionic poly(sodium phosphate) (PSP), were deposited on cotton fabric via layer-by-layer (LbL) assembly to reduce flammability. This CH–PSP nanocoating promotes charring of the cotton, rendering the fabric self-extinguishing. The coated fabric was rinsed in an ultrasonication bath between deposition steps to improve the softness (i.e., hand) of the coated fabric. Ultrasonication is believed to remove weakly adhered polyelectrolyte, preventing the fabric from becoming stiff, while improving anti-flammable behavior at a given coating weight. At 17 bilayers, only 9.1 wt% was added to the cotton, yet the coated cotton consistently passed vertical flame testing. Electron microscopy provides evidence of intumescence and confirms the cleaner deposition afforded by ultrasonication. The reduction in peak heat release rate and total heat release, as measured by micro cone calorimetry, were 73 and 81 % respectively, which is a new benchmark in LbL flame retardant coating on cotton. The mechanical properties of the fabric were measured using the Kawabata evaluation system, which showed that ultrasonication rinsing significantly improved the hand. The ability to render cotton fabric self-extinguishing, while maintaining a soft hand, marks a major milestone in the development of these environmentally-benign nanocoatings.     

Method for combinatorial screening of moisture vapor transmission rate

A high-throughput method for screening the moisture vapor transmission rate of barrier films was developed. This moisture high-throughput screening (MHTS) technique is based upon a Nafion-crystal violet (CVN) sensor that changes color from yellow to green upon absorption of water. Using an appropriate set of known standards, the slope of absorbance (at 630 nm) as a function of time can be converted into moisture vapor transmission rate (MVTR) values that agree with those obtained using ASTM F1290. High-throughput screening was demonstrated by depositing 20 emulsion-based poly(vinylidene chloride) films, using a 48-well template, of varying thicknesses onto the CVN sensor film and aging at 40 degrees C and 90% relative humidity for 72 h. MVTR values were accurately determined to a level of 0.9 g/m(2).day, at which point side-diffusion of moisture between the barrier and sensor films prevented observation of lower values. Larger sample size and edge-sealing are two proposed methods for improving the sensitivity of MHTS.     

Layer-by-layer assembly of UV-resistant poly(3,4-ethylenedioxythiophene) thin films

The layer-by-layer assembly technique was used to create electrically conductive films with poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT-PSS) and branched polyethylenimine (BPEI). Titanium dioxide (TiO(2)) and carbon black were used to prevent UV-degradation of these PEDOT-PSS thin film assemblies. Film growth and conductivity were studied, while varying composition and examining the effect of UV absorbing particles on the electrical conductivity. All films showed similar initial sheet resistances, but after exposure to 365 nm UV light for 9 days (correlating to approximately 4 years of sunlight), the films containing TiO(2) were up to 250 times more conductive. Additionally, the TiO(2) containing films were 27% more optically transparent than films made with PEDOT in the absence of TiO(2). The addition of colloidal titania allows the useful life of the PEDOT films to be extended without the detrimental effects of decreased transparency. Doping the PEDOT with dimethylsulfoxide produced eight bilayer films that were almost 6 times more conductive. However, the degradation rate for the doped PEDOT films without TiO(2) was 10 times greater than the doped films with TiO(2).     

Hydrophobically modified polyelectrolyte for improved oxygen barrier in nanobrick wall multilayer thin films

The influence of attaching hydrophobic side groups to a polyelectrolyte, used for deposition of a multilayer oxygen gas barrier thin film, was investigated. Polyethyleneimine (PEI) was labeled with pyrene and deposited in “quadlayers” of PEI, poly(acrylic acid), PEI, and sodium montmorillonite clay using layer‐by‐layer assembly. Thin films made of three repeating quadlayers using unmodified PEI had much lower density (1.24 g/cm³) than pyrene‐labeled PEI‐based films (1.45 g/cm³), which is believed to be the result of greater chain coiling from the increased hydrophobicity of pendant pyrene groups. This increased density in pyrene‐labeled PEI layers allowed three quadlayers to match the oxygen transmission rate of a four quadlayer film made with unmodified PEI. This discovery provides an additional tool for tailoring the barrier behavior of clay‐based multilayer thin films that could prove useful for a variety of packaging applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1153–1156