Direct measurement of surface forces due to charging of solids immersed in a nonpolar liquid

Direct measurements of a long-range force between charged solid surfaces in a nonpolar liquid are presented for the first time. Measurements were made between mica surfaces in solutions of the anionic surfactant sodium di-2-ethylhexylsulfosuccinate (AOT) at millimolar concentrations in n-decane using a surface force apparatus which has been modified to improve its sensitivity for detecting a weak and long-range force. Modifications include a magnetic drive system, the use of a weak cantilever spring with the apparatus mounted in a vertical configuration, and a detailed consideration of the interference optics to allow accurate measurements of surface separations up to several micrometers. The results show a repulsion that is well fitted by theoretical curves based on a model in which only counterions enter the calculation, in other words, in the absence of a reservoir of ions in the solvent. Fitting the theory to the data allows an estimate of the mica surface charge density of ∼1 mC/m². A mechanism for surface charging of mica in this solution is proposed, which includes a role for trace amounts of water that are inevitably present and adsorbed surface aggregates of AOT. The relevance of the results to previously observed charge stabilization of colloids in nonaqueous solvents is discussed.

Sol-gel derived HA/TiO2 double coatings on Ti scaffolds for orthopaedic applications

Hydroxyapatite/titania (HA/TiO₂) double layers were coated onto Ti scaffolds throughout for orthopaedic applications by sol-gel method. Differential scanning calorimetry (DSC), thermogravimetric analysis (TG) and X-ray diffractometry (XRD) were used for the characterisation of the phase transformations of the dried gels and coated surface structures. Scanning electron microscope (SEM) equipped with energy dispersive spectrometry (EDS) was used for the observation and evaluation of the morphology and phases of the surface layers and for the assessment of the in vitro tests. The in vitro assessments were performed by soaking the HA/TiO₂ double coated samples into the simulated body fluid (SBF) for various periods. The TiO₂ layer was coated by a dipping-coating method at a speed of 12 cm/min, followed by a heat treatment at 600 °C for 20 min. The HA layer was subsequently dipping-coated on the outer surface at the same speed and then heat-treated at difference temperatures. The results indicat that the HA phase begins to crystallize after a heat treatment at 560 °C. The crystallinity increases obviously at 760 °C. SEM observations find no delamination or crack at the interfaces of HA/TiO₂ and TiO₂/Ti. The HA/TiO₂ coated Ti scaffolds displays excellent bone-like apatite forming ability when it is soaked into SBF. Ti scaffolds after HA/TiO₂ double coatings can be anticipated as promising implant materials for orthopaedic applications

Sol-gel derived hydroxyapatite/titania biocoatings on titanium substrate

A simple sol–gel method was successfully developed for a hydroxyapatite (HA)/TiO₂ double layer deposition on a pure titanium substrate. Phase formation, surface morphology, and interfacial microstructure were investigated by differential scanning calorimetry analysis (DSC), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The TiO₂ layer was coated by a spin coating method at a speed of 1500 rpm for 15 s, followed by a heat treatment at 560 °C for 20 min. The HA film was subsequently spin coated on the outer surface at the same speed and then heat-treated at difference temperatures. Results indicated that the HA phase began to crystallize after a heat treatment at 580 °C; and the crystallinity increased obviously at a temperature of 780 °C. The HA film showed a porous structure and a thickness of 5–7 μm after the heat treatment at 780 °C. SEM observations revealed no delamination and crack at the interfaces of HA/TiO₂ and TiO₂/Ti. The HA film with a porous structure is expected to be more susceptible to the natural remodeling processes when it is implanted in a living body.

Cellular localization of water soluble, allergenic proteins in rye-grass (Lolium perenne) pollen using monoclonal and specific IgE antibodies with immunogold probes

A postembedding method has been developed for localizing water soluble allergens in rye-grass pollen. This uses dry fixation in glutaraldehyde vapour, followed by 2,2-dimethoxypropane, prior to a 100% ethanol series leading into embedment in LR Gold. This has allowed the attachment of specific monoclonal antibodies to the allergen, which are themselves probed with specific immunogold labels to the antibodies. Wall and cytoplasmic sites have been identified, representing an improvement of fixation and localization of allergens over previous studies employing polyclonal, broad spectrum antibodies.

Rye-grass allergens are labelled in mature pollen grains in the exine (tectum, nexine and central chamber), and in the electron opaque areas of the cytoplasm, especially mitochondria. The allergens are absent from the intine, polysaccharide (P) particles, amyloplasts, Golgi bodies and endoplasmic reticulum. IgE antibodies derived from humans allergic to rye-grass pollen, bind to similar sites in the cytoplasm but only to the outer surface of the pollen grain wall. This method now provides a valuable tool for further developmental studies on the pollen grains, in order to establish the site/s of synthesis of the allergens.

Possible electrical double-layer contribution to the equilibrium thickness of intergranular Glass films in polycrystalline ceramics

The plausibility of the entropic repulsion of electrical double layers acting to stabilize an equilibrium thickness of intergranular glass films in polycrystalline ceramics is explored. Estimates of the screening length, surface potential, and surface charge required to provide a repulsive force sufficiently large to balance the attractive van der Waals and capillary forces for observable thicknesses of intergranular film are calculated and do not appear to be beyond possibility. However, it has yet to be established whether crystalline particles in a liquid-phase sintering medium possess an electrical double layer at high temperatures. If they do, such a surface charge layer may well have important consequences not only for liquid-phase sintering but also for high-frequency electrical properties and microwave sintering of ceramics containing a liquid phase.

Contact electrification and adhesion between dissimilar materials

Simultaneous measurements of surface force and surface charge demonstrate strong attraction due to the spontaneous transfer of electrical charge from one smooth insulator (mica) to another (silica) as a result of simple, nonsliding contact in dry nitrogen. The measured surface charge densities are 5 to 20 millicoulombs per square meter after contact. The work required to separate the charged surfaces is typically 6 to 9 joules per square meter, comparable to the fracture energies of ionic-covalent materials. Observation of partial gas discharges when the surfaces are approximately 1 micrometer apart gives valuable insight into the charge separation processes underlying static electrical phenomena in general.

Approach to improved dye sensitized solar cells by using plasma technology

The surface of TiO₂ working electrode in dye sensitized solar cells was modified using O₂ plasma. The cell efficiency was increased by 30%. Surface characterization revealed the changes in the surface charge state and the chemical composition after the plasma treatment.

Evolution of moisture management behavior of high-wicking 3D warp knitted spacer fabrics

Moisture management behavior is a vital factor in evaluating thermal and physiological comfort of functional textiles. This research work studies functional 3 dimensional (3D) warp knitted spacer fabrics containing high-wicking materials characterized by their profiled cross section. These spacer fabrics can be used for protective vest to absorb a user’s sweat, to reduce the humidity and improve user’s thermal comfort. For this reason, different 3D warp knitted spacer fabrics were produced with functional fiber yarns in the back layer of the fabric (close to the body) and polyester in the front and middle layers (outer surface). Comfort properties such as air and water vapor permeability and wicking and other moisture management properties (MMP) of different fabric samples were measured. It is demonstrated that by using profiled fibers such as Coolmax fiber, moisture management properties of spacer fabrics can be improved, enabling them to be use as a snug-fitting shirt worn under protective vests with improved comfort.

New approaches for adding value to paper and other substrates

This paper describes research into three different but interrelated technologies that can add value to commodity printing substrates by taking advantage of developments in synthetic chemistry, materials science and plasma physics. These investigations have been conducted in a Cooperative Research Centre (CRC) in Australia, called CRC Smartprint. Research into ink receptive coatings based on pigments possessing a positive surface charge has led to coatings that display improved resolution and colour saturation compared with silica based formulations. Although silica exhibits a high level of liquid absorption, it has relatively poor affinity for dye molecules contained in ink-jet ink. The second development involves the use of plasma enhanced chemical vapour deposition at atmospheric pressure to change surface functionality with particular emphasis on absorptive and printing properties. Thirdly, the development of a prototype labelling system based on the application of electrochromic conductive polymer to a flexible substrate that responds to electrical stimuli is discussed. Taken together, these three developments illustrate how both impact and non-impact printing technologies can be judiciously used to apply not only improved visual imagery to paper and paperboard, but also have the potential to enable printing of micro-electronic circuitry directly onto packaging materials, or onto labels that will enable a wide range of improved tracking, security and marketing functions to be incorporated cost-effectively into packaged goods in future.

Lessons from silkworm cocoons for future protective materials design

 Evolved over millions of years’ natural selection, very thin and lightweight wild silkworm cocoons can protect silkworms from environmental hazards and physical attacks from predators while supporting their metabolic activity. The knowledge of structure-property-function relationship of multi-layered composite silk cocoon shells gives insight into the design of next-generation protection materials. The mechanical and thermal insulation properties of both domestic (Bombyx mori, or B. moriand Samia. cynthia, or S. cynthia) and wild (Antheraea pernyi and Antheraea mylitta, or A. pernyi and A. mylitta) silkworm cocoons were investigated. The research findings are of relevance to the bio-inspired design of new protective materials and structures.
The 180 degree peel tests and needle penetration tests were used for examining the peel resistance and needle penetration resistance of both domestic and wild silkworm cocoon walls. The temperatures inside and outside of the whole silkworm cocoons under warm, cold and windy conditions were monitored for investigating the cocoon’s thermal insulation function. Computational fluid dynamics (CFD) models were created to simulate the heat transfer through the A. pernyi cocoon wall.
The wild cocoons experienced much higher peeling peak loads than the domestic cocoon. This transfers to a maximum work-of-fracture (WOF) of about 1000 J/m2 from the A. pernyi outer layer, which was 10 times of the B. mori cocoon. The A. pernyi wild cocoon exhibited a maximum penetration force (11 N) that is 70 % higher than a woven aramid fabric. Silk sericin is shown to play a critical role in providing needle penetration resistance of the non-woven composite cocoon structure by restricting the relative motion of fibres, which prevents the sharp tip of the needle from pushing aside fibres and penetrating between them. The wild A. pernyi cocoon exhibits superior thermal buffer over the domestic B. mori cocoon. The unique structure of the A. pernyi cocoon wall with mineral crystals deposited on the cocoon outer surface, can prohibit most of the air from flowing inside of the cocoon structure, which shows strong wind resistance under windy conditions.

Promoted water transport across graphene oxide-poly(amide) thin film composite membranes and their antibacterial activity

Hybrid composite membranes have great potential for desalination applications since water transport can be favorably promoted by selective diffusion at the interface between matrix and reinforcement materials. In this paper, graphene oxide nano-sheets were successfully incorporated across 200nm thick poly(amide) films by interfacial polymerization to form novel thin-film composite membranes. The impact of the graphene oxide on the morphology, chemistry, and surface charge of the ultra-thin poly(amide) layer, and the ability to desalinate seawater was investigated. The graphene oxide nano-sheets were found to be well dispersed across the composite membranes, leading to a lower membrane surface energy and an enhanced hydrophilicity. The iso-electric point of the samples, key to surface charge repulsion during desalination, was found to be consistently shifted to higher pH values with an increasing graphene oxide content. Compared to a pristine poly(amide) membrane, the pure water flux across the composite membranes with 0.12wt.% of graphene oxide was also found to increase by up to 80% from 0.122 to 0.219L·μm·m-2·h-1·bar-1 without significantly affecting salt selectivity. Furthermore, the inhibitory effects of the composite membrane on microbial growth were evaluated and the novel composite membranes exhibited superior anti-microbial activity and may act as a potential anti-fouling membrane material.

Functionalized mesoporous silica nanoparticles with redox-responsive short-chain gatekeepers for agrochemical delivery.

The controlled release of salicylic acid (SA), a key phytohormone, was mediated by using a novel decanethiol gatekeeper system grafted onto mesoporous silica nanoparticles (MSNs). The decanethiol was conjugated only to the external surfaces of the MSNs through glutathione (GSH)-cleavable disulfide linkages and the introduction of a process to assemble gatekeepers only on the outer surface so that the mesopore area can be maintained for high cargo loading. Raman and nitrogen sorption isotherm analyses confirmed the successful linkage of decanethiol to the surface of MSNs. The in vitro release of SA from decanethiol gated MSNs indicated that the release rate of SA in an environment with a certain amount of GSH was significantly higher than that without GSH. More importantly, in planta experiments showed the release of SA from decanethiol gated MSNs by GSH induced sustained expression of the plant defense gene PR-1 up to 7 days after introduction, while free SA caused an early peak in PR-1 expression which steadily decreased after 3 days. This study demonstrates the redox-responsive release of a phytohormone in vitro and also indicates the potential use of MSNs in planta as a controlled agrochemical delivery system.