Gel electrolytes based on lithium modified silica nano-particles

In this work lithium modified silica (Li-SiO₂) nano-particles were synthesized and used as a single ion lithium conductor source in gel electrolytes. It was found that Li-SiO₂ exhibited good compatibility with DMSO, DMA/EC (a mixture of N,N-dimethyl acetamide and ethylene carbonate) and the ionic liquid, N-methyl-N-propyl pyrrolidinium bis(trifluoromethylsulfonyl) amide ([C₃mpyr][NTf₂]). Several gel electrolytes based on Li-SiO₂ were obtained. These gel electrolytes were investigated by DSC, solid state NMR, conductivity measurements and cyclic voltammetry. Conductivities as high as 10⁻³ S/cm at room temperature were observed in these nano-particle gel electrolytes. The results of electrochemical tests showed that some of these materials were promising for using as lithium conductive electrolytes in electrochemical devices, with high lithium cycling efficiency evident.

Robust, self-healing superamphiphobic fabrics prepared by two-step coating of fluoro-containing polymer, fluoroalkyl silane, and modified silica nanoparticles

A robust, superamphiphobic fabric with a novel self-healing ability to autorepair from chemical damage is prepared by a two-step wet-chemistry coating technique using an easily available material system consisting of poly(vinylidene fluoride-co-hexafluoropropylene), fluoroalkyl silane, and modified silica nanoparticles. The coated fabrics can withstand at least 600 cycles of standard laundry and 8000 cycles of abrasion without apparently changing the superamphiphobicity. The coating is also very stable to strong acid/base, ozone, and boiling treatments. After being damaged chemically, the coating can restore its super liquid-repellent properties by a short-time heating treatment or room temperature ageing. This simple but novel and effective coating system may be useful for the development of robust protective clothing for various applications.

Synthesis of an Al/MgAl2O4 in situ metal matrix composite from silica gel

An aluminum/MgAl2O4 in situ metal matrix composite has been synthesized using silica gel containing B98% SiO2 in an Al–5Mg alloy. The thermodynamics and kinetics of MgAl2O4 formation have been discussed in detail. A transition phase of composition between MgO and MgAl2O4 has been detected in the SEM-EDS analysis of the particles extracted from the composite by a 25% NaOH solution. This confirms the gradual transformation of MgO to MgAl2O4 by the reaction 3SiO2(s)12MgO(s)14Al(l)-2MgAl2O4(s)13Si(l). The stoichiometry, n, of MgAl2O4 has been found to sustain close to 1 and the crystallite growth of MgAl2O4 has been stopped at DB30 nm in the composites held at 7501C up to 10 h.

An investigation into the ion-exchange properties of chemically modified wool for use in water treatment and chromatography

This study was undertaken to investigate the suitability of natural and chemically treated wool fibres for use in water treatment and in the separation of constituents for monitoring contaminants in water.

Experimental work was carried out to determine the ability of natural and treated wool fibres to remove these constituents from water,

This study provided information on the characteristics of the wool fibre as a medium in water treatment.

Influence of emulsification on the properties of styrene-butadiene-styrene chemically modified bitumens

The effect of emulsification on the styrene-butadiene-styrene (SBS) chemically modified bitumens (CMBs) is studied by conventional tests, differential scanning calorimetry (DSC) and fourier transform infrared (FTIR) spectroscopy. Compared to CMBs, modified bitumen emulsion residues (MBERs) exhibit higher temperature susceptibility, inferior resistant to cracking and deformation, lower elastic recovery and storage stability whereas these properties are improved substantially relative to base bitumens. DSC results show that the thermostability of CMBs decreased slightly after emulsification which indicate the emulsification exerts very little effect on the thermal property of CMBs. The FTIR results do not indicate any chemical reaction exists on CMBs during the emulsification.

Aggregation, ageing and transport properties of surface modified fumed silica dispersions

We have investigated the aggregation, ageing and transport properties of surface modified silica dispersions in DMSO by photon correlation spectroscopy and conductivity measurements. The surface modification introduces Li+-ions that dissociate in the dispersion creating a single Li+-ion conducting electrolyte. We show that the surface modification changes the aggregation and ageing properties of the material. There is a pronounced ageing observed for the modified silica dispersions. At high concentrations of fumed silica a gel state is found, which in the case of the surface modified silica is a very weak gel that can be rejuvenated by ultrasonic treatment. The key parameter controlling the aggregation in this system is hydrogen bonding and the surface modification results in a very low number of sites for hydrogen bonding. In addition there is a contribution from repulsive electrostatic interactions in the surface modified silica dispersions due to the highly charged surfaces of these particles. Furthermore, the Li+-ion diffusion, at low silica concentration, is three orders of magnitude faster than that of the silica particles and in the gel state the silica particles are immobile. We also find that the Li+-ion diffusion is virtually independent of the silica concentration in the dispersions.

Thermodynamics and kinetics of the formation of Al2 O3/ MgAl2O4/MgO in Al-Silica metal matrix composite

The formation of Al₂O₃, MgAl₂O₄, and MgO has been widely studied in different Al base metal matrix composites, but the studies on thermodynamic aspects of the Al₂O₃/ MgAl₂O₄/MgO phase equilibria have been limited to few systems such as Al/Al₂O₃ and Al/SiC. The present study analyzes the Al₂O₃/MgAl₂O₄ and MgAl₂O₄/MgO equilibria with respect to the temperature and the Mg content in Al/SiO2 system using an extended Miedema model. There is a linear and parabolic variation in Mg with respect to the temperature for MgAl₂O₄/MgO and Al₂O₃/MgAl₂O₄ equilibria, respectively, and the influence of Si and Cu in the two equilibria is not appreciable. The experimental verification has been limited to MgAl₂O₄/MgO equilibria due to the high Mg content (≥0.5 wt pct) required for composite processing. The study has been carried out on two varieties of Al/SiO₂ composites, i.e., Al/Silica gel and Al/Micro silica processed by liquid metallurgy route (stir casting route). MgO is found to be more stable compared to MgAl₂O₄ at Mg levels ≥5 and 1 wt pct in Al/Silica gel and Al/Micro silica composites, respectively, at 1073 K. MgO is also found to be more stable at lower Mg content (3 wt pct) in Al/Silica gel composite with decreasing particle size of silica gel from 180 micron to submicron and nanolevels. The MgO to MgAl₂O₄ transformation has taken place through a series of transition phases influenced by the different thermodynamic and kinetic parameters such as holding temperature, Mg concentration in the alloy, holding time, and silica particle size.

Analysis of self-assembled monolayer interfaces by electrospray mass spectrometry : a gentle approach

A general mass spectrometry technique for the characterization of alkanethiol-modified surfaces is presented. Alkanethiol self-assembled onto a gold surface (in this case, peptides were attached to the gold surface via a thiolate bond) was reductively desorbed in 0.05 M KOH in the presence of octadecyl-derivatized silica gel. The peptide adsorbed onto the silica gel, whereupon it could be filtered, washed to remove any salts, and then eluted using a mixture of 4:1 v/v methanol/water. The eluant containing the peptide was injected into a Fourier transform ion-cyclotron resonance mass spectrometer (FTICR/MS) via electrospray ionization. The spectrum showed no fragmentation of the peptide, demonstrating the gentleness of the technique. This simple procedure is not limited to FTICR/MS and could be adapted to other mass spectrometers.

The boundary lubrication of chemically grafted and cross-linked hyaluronic acid in phosphate buffered saline and lipid solutions measured by the surface forces apparatus

High molecular weight hyaluronic acid (HA) is present in articular joints and synovial fluid at high concentrations; yet despite numerous studies, the role of HA in joint lubrication is still not clear. Free HA in solution does not appear to be a good lubricant, being negatively charged and therefore repelled from most biological, including cartilage, surfaces. Recent enzymatic experiments suggested that mechanically or physically (rather than chemically) trapped HA could function as an “adaptive” or “emergency” boundary lubricant to eliminate wear damage in shearing cartilage surfaces. In this work, HA was chemically grafted to a layer of self-assembled amino-propyl-triethoxy-silane (APTES) on mica and then cross-linked. The boundary lubrication behavior of APTES and of chemically grafted and cross-linked HA in both electrolyte and lipid 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) solutions was tested with a surface forces apparatus (SFA). Despite the high coefficient of friction (COF) of μ ≈ 0.50, the chemically grafted HA gel significantly improved the lubrication behavior of HA, particularly the wear resistance, in comparison to free HA. Adding more DOPC lipid to the solution did not improve the lubrication of the chemically grafted and cross-linked HA layer. Damage of the underlying mica surface became visible at higher loads (pressure >2 MPa) after prolonged sliding times. It has generally been assumed that damage caused by or during sliding, also known as “abrasive friction”, which is the main biomedical/clinical/morphological manifestation of arthritis, is due to a high friction force and, therefore, a large COF, and that to prevent surface damage or wear (abrasion) one should therefore aim to reduce the COF, which has been the traditional focus of basic research in biolubrication, particularly in cartilage and joint lubrication. Here we combine our results with previous ones on grafted and cross-linked HA on lipid bilayers, and lubricin-mediated lubrication, and conclude that for cartilage surfaces, a high COF can be associated with good wear protection, while a low COF can have poor wear resistance. Both of these properties depend on how the lubricating molecules are attached to and organized at the surfaces, as well as the structure and mechanical, viscoelastic, elastic, and physical properties of the surfaces, but the two phenomena are not directly or simply related. We also conclude that to provide both the low COF and good wear protection of joints under physiological conditions, some or all of the four major components of joints—HA, lubricin, lipids, and the cartilage fibrils—must act synergistically in ways (physisorbed, chemisorbed, grafted and/or cross-linked) that are still to be determined.

Flexural characteristics of coir fiber reinforced cementitious composites

This study has examined the flexural properties of natural and chemically modified coir fiber reinforced cementitious composites (CFRCC). Coir fibers of two different average lengths were used, and the longer coir fibers were also treated with a 1 % NaOH solution for comparison. The fibers were combined with cementitious materials and chemical agents (dispersant, defoamer or wetting agent) to form CFRCC. The flexural properties of the composites, including elastic stress, flexural strength, toughness and toughness index, were measured. The effects of fiber treatments, addition of chemical agents and accelerated ageing of composites on the composites’ flexural properties were examined. The results showed that the CFRCC samples were 5–12 % lighter than the conventional mortar, and that the addition of coir fibers improved the flexural strength of the CFRCC materials. Toughness and toughness index, which were associated with the work of fracture, were increased more than ten times. For the alkalized long coir fiber composites, a higher immediate and long-term toughness index was achieved. SEM microstructure images revealed improved physicochemical bonding in the treated CFRCC.

Developing a stakeholder analysis to aid bio-based product innovation

Purpose – The results which that study seeks to report are the first part of a larger research programme funded by the New Zealand Foundation for Research, Science & Technology (FRST) aimed at gaining a better understanding of stakeholder perceptions in relation to bio-based products.

Design/methodology/approach – Utilising three chemically modified wood products, data were collected from focus groups and questionnaires and centred primarily on perceptions surrounding the acceptability of building materials that have been bio-modified. Irrespective of the type of chemical modification, family health and durability were the most important factors identified.

Findings – The study finds that product cost rated lower in the 16 factors evaluated, and energy used in production was of little concern. When comparing the three products to one another, two distinct groups with quite differing purchasing philosophies were identified and these perspectives significantly influenced perceptions of product acceptability and willingness to purchase. Utilising a paired comparison technique, an investigation of trade-offs indicated preference for performance over cost and product familiarity. Similarly, low chemical emissions were also preferred over cost considerations. Among the findings, there was scepticism regarding trust in manufacturers to adequately safeguard health and safety and to have a minimum impact on the environment. Low levels of trust were expressed in regard to manufacturers' concern for future generations.

Originality/value – The paper develops an investigative framework which could be applied to the evaluation of products arising from bio-material technology innovation and recommendations for future research directions.

Critical assessment of various techniques for the extraction of carotenoids and co-enzyme Q10 from the Thraustochytrid strain ONC-T18

A variety of techniques for extracting carotenoids from the marine Thraustochytrium sp. ONC-T18 was compared. Specifically, the organic solvents acetone, ethyl acetate, and petroleum ether were tested, along with direct and indirect ultrasonic assisted extraction (probe vs bath) methods. Techniques that used petroleum ether/acetone/water (15:75:10, v/v/v) with 3 h of agitation, or 5 min in an ultrasonic bath, produced the highest extraction yields of total carotenoids (29−30.5 μg g^-1). Concentrations up to 11.5 μg g^-1 of canthaxanthin and 17.5 μg g^-1 of β-carotene were detected in extracts stored for 6 weeks. Astaxanthin and echinenone were also detected as minor compounds. Extracts with and without antioxidants showed similar carotenoid concentration profiles. However, total carotenoid concentrations were approximately 8% higher when antioxidants were used. Finally, an easy-to-perform and inexpensive method to detect co-enzymes in ONC-T18 was also developed using silica gel TLC plates. Five percent methanol in toluene as a mobile phase consistently eluted co-enzyme Q10 standards and could separate the co-enzyme fractions present in ONC-T18.

Cerium acetylacetonates—new aspects, including the lamellar clathrate [Ce(acac)4]·10H2O

Reactions of CeCl₃·7H₂O and Ce(NO₃)₃·6H₂O with Naacac or NH₄acac in aqueous solution at 21 and 45 °C yielded the trihydrate [Ce(acac)₃(H₂O)₂]·H₂O and the dihydrate [Ce(acac)₃(H₂O)₂], respectively, whereas similar treatment of (NH₄)₂[Ce(NO₃)₆] gave the trihydrate at both temperatures. Desiccation of the hydrates over silica gel left the dihydrate unchanged, whereas the trihydrate underwent decomposition rather than dehydration. Aerial oxidation of [Ce(acac)₃(H₂O)₂] in CH₂Cl₂ and toluene yielded α-[Ce(acac)₄] and β-[Ce(acac)₄], respectively, the structure of the former being re-determined with improved precision. Careful treatment of aqueous (NH₄)₄[Ce(SO₄)₄] and Hacac (initially pH 1–2) with aqueous ammonia to pH 5 precipitated hydrated [Ce(acac)₄], from which [Ce(acac)₄]·10H₂O was isolated as unstable, light-sensitive single crystals, and the structure was determined. The complex is a laminar clathrate containing layers of Ce(acac)₄ molecules sandwiched between extensive hydrogen-bonded layers of water molecules which do not interact with the metal. Electrochemical experiments confirmed the unstable nature of hydrated Ce^III(acac)₃, while the reduction of [Ce(acac)₄] yielded well-defined cyclic voltammograms in acetonitrile and acetone, corresponding to a quasi-reversible process. For the [Ce^IV(acac)₄]/[Ce^III(acac)₄]⁻redox couple, a calculated reversible potential of 0.22±0.02 V versus SHE was obtained in acetone or acetonitrile (0.1 M Bu₄NPF₆) at both gold and glassy carbon electrodes. This potential is consistent with the ease of both oxidation and reduction of cerium acetylacetonate complexes as found in the synthetic studies.

Identification of surface heterogeneity effects in cyclic voltammograms derived from analysis of an individually addressable gold array electrode

Voltammetric behavior at gold electrodes in aqueous media is known to be strongly dependent on electrode polishing and history. In this study, an electrode array consisting of 100 nominally identical and individually addressable gold disks electrodes, each with a radius of 127 µm, has been fabricated. The ability to analyze both individual electrode and total array performance enables microscopic aspects of the overall voltammetric response arising from variable levels of inhomogeneity in each electrode to be identified. The array configuration was initially employed with the reversible and hence relatively surface insensitive [Ru(NH₃)₆]^3+/2+ reaction and then with the more highly surface sensitive quasi-reversible [Fe(CN)₆]^3−/4− process. In both these cases, the reactants and products are solution soluble and, at a scan rate of 50 mV s⁻¹, each electrode in the array is assumed to behave independently, since no evidence of overlapping of the diffusion layers was detected. As would be expected, the variability of the individual electrodesʼ responses was significantly larger than found for the summed electrode behavior. In the case of cytochrome c voltammetry at a 4,4′-dipyridyl disulfide modified electrode, a far greater dependence on electrode history and electrode heterogeneity was detected. In this case, voltammograms derived from individual electrodes in the gold array electrode exhibit shape variations ranging from peak to sigmoidal. However, again the total response was always found to be well-defined. This voltammetry is consistent with a microscopic model of heterogeneity where some parts of each chemically modified electrode surface are electroactive while other parts are less active. The findings are consistent with the common existence of electrode heterogeneity in cyclic voltammetric responses at gold electrodes, that are normally difficult to detect, but fundamentally important, as electrode nonuniformity can give rise to subtle forms of kinetic and other forms of dispersion.

Experimental investigation of the dissolution of quartz by a muscovite mica surface : implications for pressure solution

Using the surface forces apparatus, which can measure small changes in thickness occurring even at essentially geological timescales, we have measured dissolution of quartz sheets when pressed against muscovite mica surfaces in aqueous electrolyte solution, but no dissolution is observed under dry conditions. It is postulated that the dissolved quartz may reprecipitate outside the contact junction as a fragile silica gel, which could be the main factor limiting the rate of further dissolution.