Anne Ammala

Degradation Studies of Polyolefins Incorporating Transparent Nanoparticulate Zinc Oxide UV Stabilizers

Coated and dispersed nanoparticulate zinc oxide is shown to improve ultra violet (UV) stability of polypropylene and high-density polyethylene without changing its characteristic absorption spectrum in the visible region (400–800-nm). The performance of these nanoparticulate UV stabilizers is compared to conventional hindered amine light stabilizers (HALS). QUV accelerated weathering is used to simulate long-term exposure. Positron annihilation lifetime spectroscopy (PALS) is used to provide an indication of physical and chemical changes due to accelerated weathering and is shown to have potential for detecting changes well before other techniques. Visual observation, optical microscopy, carbonyl index, yellowness index and PALS indicate that nanoparticulate zinc oxide gives superior resistance to UV degradation compared to organic HALS at appropriate loading levels.

Electrical conductivity and space charge in LDPE containing TiO/sub 2/ nanoparticles

Electrical conductivity (DC) and space charge accumulation were studied in samples of low density polyethylene to which nano-sized and micro-sized TiO/sub 2/ (anatase) particles and a dispersant had been added. Sample thicknesses were in the range 150-200 /spl mu/m. At applied field strengths of 10 and 20 kV/mm, the conductivity at 30 /spl deg/C, measured in vacuum in samples containing 10 % w/w nano-sized TiO/sub 2/, decreased by 1-2 orders of magnitude relative to samples with dispersant but without TiO/sub 2/, and by three orders of magnitude at 70 /spl deg/C. In air at 30 /spl deg/C the corresponding decrease was an order of magnitude at 10 kV/mm, and a factor of four at 20 kV/mm. In samples containing 10 % w/w micro-sized TiO/sub 2/ the conductivity increased in air and in vacuum, but only by factors in the range 2-10 depending on temperature and field. Space charge profiles were obtained using the laser-intensity-modulation-method (LIIMM), irradiating both surfaces of the sample. The micro-sized TiO/sub 2/ particles are associated with increased charge injection from the electrodes and increased charge trapping in the sample bulk, increasing the conductivity overall. The nano-sized particles generate very little charge in the sample bulk, but render the electrodes partially-blocking and so lower the conductivity.

Conductivity and space charge in LDPE containing nano- and micro-sized ZnO particles

DC conductivity and ac impedance measurements were made in air and in vacuum on samples of low density polyethylene to which nano-sized and micro-sized ZnO particles and a dispersant had been added. The samples were 150-200 mum thick. The temperature range was 30-70degC. The temperature dependence of the vacuum dc conductivity in samples containing the dispersant and 10% w/w nanosized ZnO followed an Arrhenius relationship closely, the conductivity being 1-2 orders of magnitude lower than that of a sample containing dispersant only. The addition of 10% w/w microsized ZnO had very little effect on the dc conductivity. The ac measurements were made in the frequency range 10 mHz-1 MHz. Addition of nanoparticles increased the ac conductivity at higher frequencies but decreased it at lower frequencies, the cross-over frequency increasing with increasing temperature. The real part of the relative permittivity of samples with nanoparticles was increased relative to that of samples containing dispersant only, at all temperatures, but the corresponding values in samples with microparticles were unchanged, within experimental error. Space charge profiles were obtained using the laser-intensity-modulation-method (LIMM). Space charge densities of order 300 Cm-3 were measured in the bulk near the electrodes, several hours after poling at field strengths around 30 kV/mm.

Biodegradable polymers as encapsulation materials for cosmetics and personal care markets.

The topical and transdermal delivery of active cosmetic ingredients requires safe and non‐toxic means of reaching the target sites without causing any irritation. Preservation of the active ingredients is also essential during formulation, storage and application of the final product. As many biologically active substances are not stable and sensitive to temperature, pH, light and oxidation, they require encapsulation to protect against unwanted degradation and also to target specific and controlled release of the active substance. The use of biodegradable polymers as encapsulation materials offers several advantages over other carrier materials. Encapsulation of active ingredients using biodegradable polymeric carriers can facilitate increased efficacy and bioavailability and they are also removed from the body via normal metabolic pathways. This article reviews current research on biodegradable polymers as carrier or encapsulation materials for cosmetic and personal care applications. Some of the challenges and limitations are also discussed. Examples of biodegradable polymers reviewed include polysaccharides, poly α‐esters, polyalkylcyanoacrylates and polyamidoamine dendrimers.

Poly(m-xylene adipamide)-montmorillonite nanocomposites: effect of organo-modifier structure on free volume and oxygen barrier properties

It was shown that nanoparticle–polymer interactions that affect the free volume and oxygen barrier properties of poly(m-xylene adipamide)/clay nanocomposites can be tailored by the choice of organic modifier of montmorillonite clay. Three different organo-modified clay compounds based on montmorillonite (Cloisite 30B, 10A and 93A) were dispersed in the resin poly(m-xylene adipamide) at loading levels of 2 wt% clay. Samples were melt compounded and extruded using a laboratory scale twin screw micro compounder. Positron annihilation lifetime spectroscopy (PALS) was used to examine the free volume of the polymer nanocomposites. PALS results suggested that the Cloisite 10A additive should give the higher reduction in gas permeability as it results in the lowest free volume for the nylon resin when compared to all of the clay additives examined. Oxygen transmission rates (OTR) were measured on nanocomposite films and the Cloisite 10A additive was found to give the best oxygen barrier, showing a reduction of OTR of 66% compared to the neat resin. In all cases examined, PALS free volume data was found to have excellent correlation to the measured oxygen transmission rates. The addition of Cloisite 10A resulted in the highest crystallinity and an increase in glass transition temperature when compared to the neat resin. Results indicate that the improved barrier properties of the clay compounds is primarily due to an increase in the degree of crystallinity of the polymer, with the nanoparticles being more effective nucleating agents when favourable nanoparticle–polymer interactions are present.

Electrical conductivity in LDPE containing nano- and micro-sized ZnO particles

Dc conductivity and ac impedance measurements were made in air and in vacuum on samples of low density polyethylene to which nano-sized and micro-sized ZnO particles and a dispersant had been added. The samples were 150-200 mum thick. The temperature range was 30-70degC. The temperature dependence of the vacuum dc conductivity in samples containing the dispersant and 10% w/w nanosized ZnO followed an Arrhenius relationship closely, the conductivity being 1-2 orders of magnitude lower than that of a sample containing dispersant only. The addition of 10% w/w microsized ZnO also reduced the dc conductivity, but to a much lesser extent. The ac impedance measurements were made in the frequency range 10 mHz - 1 MHz. Addition of nanoparticles increased the ac conductivity at higher frequencies but decreased it at lower frequencies, the cross-over frequency increasing with increasing temperature. The real part of the relative permittivity of the nanosamples was increased relative to that of samples containing dispersant only, at all temperatures, but the values in the microsamples were equal to those in samples with dispersant only, within experimental error.