Variation of anions in layered double hydroxides: Effects on dispersion and fire properties

Layered double hydroxides (LDHs) are interesting materials for nanocomposite formation because one can vary the identity of the metals, the anions and the stoichiometry to see the effect of these on the ability of the nano-material to disperse in a polymer and to see what effect dispersion has on the properties of the polymer. In this study, the anions 2-ethylhexyl sulfate (SEHS), bis(2-ethylhexyl) phosphate (HDEHP) and dodecyl benzenesulfonate (SDBS) have been utilized as the charge balancing anions to synthesize organo-LDHs. Nanocomposites of poly(methyl methacrylate) (PMMA) and polystyrene (PS) with organo-LDHs were prepared both by melt blending and bulk polymerization. X-ray diffraction and transmission electron microscopy were used to characterize the morphology of the nanocomposites while the thermal stability and fire properties of nanocomposites were studied by thermogravimetric analysis and cone calorimetry; the mechanical properties are also investigated. In general, it is easier to disperse these organo-LDHs in PMMA than in PS, but the sulfate cannot be dispersed at the nanometer level in either material. The addition of these organo-LDHs does not affect the mechanical properties. The best fire properties are obtained with the sulfonate LDH, SDBS; the reduction in the peak heat release rate is almost 50% for both polymers

Flame-retarded Polystyrene: Investigating Chemical Interactions between Ammonium Polyphosphate and MgAl Layered Double Hydroxide

Potential flame retardants, MgAl-LDH and ammonium polyphosphate (APP), were added to neat polystyrene (PS) individually or in combinations at weight fractions no greater than 10%. Structural morphologies of MgAl-LDH and the corresponding PS nanocomposites were established via X-ray diffraction (XRD) and transmission electron microscopy (TEM). Thermogravimetric analysis (TGA) and cone calorimetry were used to study the thermal stability and fire performance of the composites. Time to ignition is greatly reduced for PS composites when compared to the virgin polymer. Synergistic effects were observed in both TGA and cone calorimetry for formulations containing both MgAl-LDH and APP. Physical and chemical interactions between MgAl-LDH and APP are responsible for the observed synergy in thermal stability and fire performance

Effect of organoclay on the physical properties of UV-curable coatings

The combination of UV-curing and nanocomposite technology has been studied to produce cost-effective coatings with superior physical and mechanical properties. The clay was modified with dimethyl dihydrogenated-tallow quaternary ammonium salt and made organophilic. The effect of the organoclay(2-10 phr) on curing rate, mechanical, thermal and physical properties of a urethane-acrylate coating has been determined. X-ray diffraction analysis, AFM, SEM and TEM images as well as the tensile properties of different formulations have confirmed the uniform distribution of organoclay in polymer matrix. At 3 phr organoclay addition, the UV-cured film exhibited the best mechanical performance due to the formation of both intercalated and exfoliated morphologies. Curing time was reduced and the initial thermal decomposition temperature shifted 50°C to higher temperature by the incorporation of small amount of organoclay. The nanocomposite coating was also found to be more resistant against scratching compared with clay-free coating

Morphological and Tribological Properties of PMMA/Halloysite Nanocomposites

From an environmental and cost-effective perspective, a number of research challenges can be found for electronics, household, but especially in the automotive polymer parts industry. Reducing synthesis steps, parts coating and painting, or other solvent-assisted processes, have been identified as major constrains for the existing technologies. Therefore, simple polymer processing routes (mixing, extrusion, injection moulding) were used for obtaining PMMA/HNT nanocomposites. By these techniques, an automotive-grade polymethylmethacrylate (PMMA) was modified with halloysite nanotubes (HNT) and an eco-friendly additive N,N′-ethylenebis(stearamide) (EBS) to improve nanomechanical properties involved in scratch resistance, mechanical properties (balance between tensile strength and impact resistance) without diminishing other properties. The relationship between morphological/structural (XRD, TEM, FTIR) and tribological (friction) properties of PMMA nanocomposites were investigated. A synergistic effect was found between HNT and EBS in the PMMA matrix. The synergy was attained by the phase distribution resulted from the selective interaction between partners and favourable processing conditions. Modification of HNT with EBS improved the dispersion of nanoparticles in the polymer matrix by increasing their interfacial compatibility through hydrogen bonding established by amide groups with aluminol groups. The increased interfacial adhesion further improved the nanocomposite scratch resistance. The PMMA/HNT-EBS nanocomposite had a lower coefficient of friction and lower scratch penetration depth than PMMA/HNT nanocomposite.Financial support by the EU Commission through Project H2020-686165-IZADINANO2INDUSTRY is gratefully acknowledged

Fire retardancy of bis[2-(methacryloyloxy)ethyl] phosphate modified poly(methyl methacrylate) nanocomposites containing layered double hydroxide and montmorillonite

Copolymer nanocomposites were prepared by suspension copolymerization of bis[2-(methacryloyloxy)ethyl] phosphate and methyl methacrylate, together with bis(2-ethylhexyl) phosphate layered double hydroxide and a montmorillonite, Cloisite 93A. X-ray diffraction and transmission electron microscopy were used to characterize the morphology of nanocomposites and the dispersion of additives in the polymer. The thermal stability of the nanocomposites has been assessed by thermogravimetric analysis and cone calorimetry has been used to study the fire properties. Bis[2-(methacryloyloxy)ethyl] phosphate not only copolymerized with MMA, but also aids in the dispersion of additives in PMMA. The copolymer nanocomposites have better dispersion and higher degradation temperature and more char mass than the corresponding PMMA nanocomposites. The largest peak reduction in the heat release rate of the copolymer nanocomposites are 52 and 65% for LDH and MMT additives, respectively

Tomographic imaging and scanning thermal microscopy: thermal impedance tomography

The application of tomographic imaging techniques developed for medical applications to the data provided by the scanning thermal microscope will give access to true three-dimensional information on the thermal properties of materials on a mm length scale. In principle, the technique involves calculating and inverting a sensitivity matrix for a uniform isotropic material, collecting ordered data at several modulation frequencies, and multiplying the inverse of the matrix with the data vector. In practice, inversion of the matrix in impractical, and a novel iterative technique is used. Examples from both simulated and real data are given

Modular polyoxometalate-layered double hydroxides as efficient heterogeneous sulfoxidation and epoxidation catalysts

Selective sulfoxidation of sulfides and epoxidation of olefins are two types of important organic reactions and the corresponding products of sulfoxides, sulfones and epoxides are widely used as raw materials in industrial processes. The fabrication of one efficient catalyst for both reactions, remains a challenging task. In this paper, we report the preparation of a highly efficient heterogeneous catalyst of Mg3Al-ILs-La(PW11)2 using an exfoliation/assembly approach. The catalyst was characterized by FT-IR, XRD, TG/DTA, BET, XPS, 29Si CP/MAS NMR, the 27Al-MAS NMR, SEM, HRTEM, EDX etc. The designed catalyst showed high efficiency and selectivity for sulfoxidation of sulphides and epoxidation of olefins under mild conditions at a production rate of 208 mmol g-1 h-1 and 31 mmol g-1 h-1, respectively. Moreover, the Mg3Al-ILs-La(PW11)2 can be recycled and reused at least 5 times without obvious decrease of its catalytic activity. The scaled-up experiments revealed that the catalyst retained its efficiency and robustness, demonstrating the catalyts' great potential for industrial applications

A transformative route to nanoporous manganese oxides of controlled oxidation states with identical textural properties

Nanoporous nanocrystalline metal oxides with tunable oxidation states are crucial for controlling their catalytic, electronic, and optical properties. However, previous approaches to modulate oxidation states in nanoporous metal oxides commonly lead to the breakdown of the nanoporous structure as well as involve concomitant changes in their morphology, pore size, surface area, and nanocrystalline size. Herein, we present a transformative route to nanoporous metal oxides with various oxidation states using manganese oxides as model systems. Thermal conversion of Mn-based metal-organic frameworks (Mn-MOFs) at controlled temperature and atmosphere yielded a series of nanoporous manganese oxides with continuously tuned oxidation states: MnO, Mn3O 4, Mn5O8, and Mn2O3. This transformation enabled the preparation of low-oxidation phase MnO and metastable intermediate phase Mn5O8 with nanoporous architectures, which were previously rarely accessible. Significantly, nanoporous MnO, Mn3O4, and Mn5O8 had a very similar morphology, surface area, and crystalline size. We investigated the electrocatalytic activity of nanoporous manganese oxides for oxygen reduction reaction (ORR) to identify the role of oxidation states, and observed oxidation state-dependent activity and kinetics for the ORR.close5

Solvent Exfoliation of Electronic-Grade, Two-Dimensional Black Phosphorus

Solution dispersions of two-dimensional (2D) black phosphorus (BP), often referred to as phosphorene, are achieved by solvent exfoliation. These pristine, electronic-grade BP dispersions are produced with anhydrous, organic solvents in a sealed tip ultrasonication system, which circumvents BP degradation that would otherwise occur via solvated oxygen or water. Among conventional solvents, n-methyl-pyrrolidone (NMP) is found to provide stable, highly concentrated (~0.4 mg/mL) BP dispersions. Atomic force microscopy, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy show that the structure and chemistry of solvent-exfoliated BP nanosheets are comparable to mechanically exfoliated BP flakes. Additionally, residual NMP from the liquid-phase processing suppresses the rate of BP oxidation in ambient conditions. Solvent-exfoliated BP nanosheet field-effect transistors (FETs) exhibit ambipolar behavior with current on/off ratios and mobilities up to ~10000 and ~50 cm^2/(V*s), respectively. Overall, this study shows that stable, highly concentrated, electronic-grade 2D BP dispersions can be realized by scalable solvent exfoliation, thereby presenting opportunities for large-area, high-performance BP device applications.Comment: 6 figures, 31 pages, including supporting informatio