Chemical residue trends for Australian and New Zealand wool

Textile consumer trends towards improved product safety and high environmental standards have significantly influenced regulators in key consumer markets. The apparel wool industry sector has responded to regulators, and for three decades the Australia and New Zealand wool industries have managed advancements in ectoparasiticides and improved sheep treatments targeting high environmental, animal health and welfare standards leading to safe wool products. Australian and New Zealand chemical residue data from greasy wool have been consolidated and analysed for organophosphate, synthetic pyrethroid, insect growth regulator, neonicotinoid, macrocyclic lactone and spinosad active. Trend analysis has been applied to time domain data to evaluate advancements in ectoparasiticide technology after revising environmental, animal health and welfare standards. Analysis shows impacts from technology improvement, regulatory change and compliance by sheep farmers meeting or exceeding published European Union residue limits for regulated ectoparasiticides namely organochlorine, organophosphate, synthetic pyrethroid and insect growth regulators. Implications from advancements in ectoparasiticide technology, industry management and regulatory measures, include healthy sheep growing in clean pastoral environments with evidence of reduced wool residue levels which complement high and rising proportions of Australian and New Zealand wool fibre meeting European Union Ecolabel criteria.

Optimisation and Scale-up of the Synthesis of Gold Nanoparticle-Wool Fibre Composites

<p>Gold nanoparticles are known for their remarkable optical properties; they exhibit localised surface plasmon resonance bands in the visible region of the electromagnetic spectrum. This has led to their use as luxury dyes for the colouring of wool fibres. Gold is associated with wealth and desire, and as such, gold nanoparticle-wool fibre composites may be fabricated into high-quality garments, apparel, textiles and carpets for international markets. Novel proprietary approaches for the laboratory-scale synthesis of gold nanoparticle-wool fibre composites have previously been developed by Professor James Johnston and Dr Kerstin Lucas. The innovative nanotechnology utilises the affinity of gold for sulfur-containing cystine residues in wool fibres, to attract and bind the gold nanoparticles. One approach involves the absorption of gold ions by wool fibres and the nucleation of gold nanoparticles in-situ. In an alternative method, gold nanoparticle colloids are synthesised ex-situ, and are then used to colour wool fibres. The reaction conditions of the in-situ and ex-situ approaches were optimised with respect to cost-effectiveness and scalability. The gold content of the in-situ composites was minimised, and the range of possible colours widened, via the use of heat and external reducing agents. In the ex-situ process, the formation and stability of the gold nanoparticle colloids was studied, and the reaction conditions of the synthesis were optimised. The rate of uptake of gold nanoparticles to wool was controlled by manipulating the pH, concentration, volume, and wool to liquor ratio of the gold colloids, and by introducing auxiliary agents into the dyeing reactions. A range of chemical treatments and alternative stabilising agents were investigated to improve the washfastness properties of ex-situ gold nanoparticle-wool fibre composites. There are numerous size-controllable syntheses of gold nanoparticle colloids at the laboratory-scale. However, when the process is scaled-up, gold nanoparticle synthesis is no longer trivial. A barrel reactor with a high velocity mixer was utilised to achieve uniform mixing and heating in the synthesis of gold nanoparticle colloids of up to 90 L in volume. The ratios of gold to stabilising agents in the colloidal gold syntheses were optimised to result in more stable and reproducible gold colloids for subsequent dyeing reactions. The uniform colouring of small quantities of wool is easily achieved in the laboratory, but preventing colour variation across a kilogram of wool is a significant challenge. Initial kilogram-scale dyeing reactions in static tank reactors resulted in unevenly coloured gold nanoparticle-wool fibre composites. To overcome this, conventional hank dyeing equipment was used to colour felted merino yarn, in collaboration with the wool dyeing industry. Modified hank dyeing procedures were recreated in the laboratory, and composites with remarkable colour uniformity were produced. Industrial package dyeing reactors were then used to colour fine merino yarn with gold nanoparticle colloids. The uptake of gold nanoparticles was controlled by manipulating the owrates, ow direction and amounts of auxiliary agents that were employed in the dyeing reactions. Based upon the success of the industrial dyeing reactions, novel dyeing reactors were developed for the colouring of hanks of wool fibres and yarns in the laboratory. These reactors utilised rapid dye circulation and pressure to produce gold nanoparticle-wool fibre composites with remarkable colour uniformity. The composites were used to fabricate luxury apparel and carpets for international trade expositions. The pathway from synthesis in the laboratory to pilot-scale production of gold nanoparticle-wool fibre composites is presented. The PhD research was an integral step in the successful commercialisation of this innovative nanotechnology, and will assist in scaling-up the synthesis of metal nanoparticle colloids and nanocomposites in the future.</p>

Optimisation and Scale-up of the Synthesis of Gold Nanoparticle-Wool Fibre Composites

<p>Gold nanoparticles are known for their remarkable optical properties; they exhibit localised surface plasmon resonance bands in the visible region of the electromagnetic spectrum. This has led to their use as luxury dyes for the colouring of wool fibres. Gold is associated with wealth and desire, and as such, gold nanoparticle-wool fibre composites may be fabricated into high-quality garments, apparel, textiles and carpets for international markets. Novel proprietary approaches for the laboratory-scale synthesis of gold nanoparticle-wool fibre composites have previously been developed by Professor James Johnston and Dr Kerstin Lucas. The innovative nanotechnology utilises the affinity of gold for sulfur-containing cystine residues in wool fibres, to attract and bind the gold nanoparticles. One approach involves the absorption of gold ions by wool fibres and the nucleation of gold nanoparticles in-situ. In an alternative method, gold nanoparticle colloids are synthesised ex-situ, and are then used to colour wool fibres. The reaction conditions of the in-situ and ex-situ approaches were optimised with respect to cost-effectiveness and scalability. The gold content of the in-situ composites was minimised, and the range of possible colours widened, via the use of heat and external reducing agents. In the ex-situ process, the formation and stability of the gold nanoparticle colloids was studied, and the reaction conditions of the synthesis were optimised. The rate of uptake of gold nanoparticles to wool was controlled by manipulating the pH, concentration, volume, and wool to liquor ratio of the gold colloids, and by introducing auxiliary agents into the dyeing reactions. A range of chemical treatments and alternative stabilising agents were investigated to improve the washfastness properties of ex-situ gold nanoparticle-wool fibre composites. There are numerous size-controllable syntheses of gold nanoparticle colloids at the laboratory-scale. However, when the process is scaled-up, gold nanoparticle synthesis is no longer trivial. A barrel reactor with a high velocity mixer was utilised to achieve uniform mixing and heating in the synthesis of gold nanoparticle colloids of up to 90 L in volume. The ratios of gold to stabilising agents in the colloidal gold syntheses were optimised to result in more stable and reproducible gold colloids for subsequent dyeing reactions. The uniform colouring of small quantities of wool is easily achieved in the laboratory, but preventing colour variation across a kilogram of wool is a significant challenge. Initial kilogram-scale dyeing reactions in static tank reactors resulted in unevenly coloured gold nanoparticle-wool fibre composites. To overcome this, conventional hank dyeing equipment was used to colour felted merino yarn, in collaboration with the wool dyeing industry. Modified hank dyeing procedures were recreated in the laboratory, and composites with remarkable colour uniformity were produced. Industrial package dyeing reactors were then used to colour fine merino yarn with gold nanoparticle colloids. The uptake of gold nanoparticles was controlled by manipulating the owrates, ow direction and amounts of auxiliary agents that were employed in the dyeing reactions. Based upon the success of the industrial dyeing reactions, novel dyeing reactors were developed for the colouring of hanks of wool fibres and yarns in the laboratory. These reactors utilised rapid dye circulation and pressure to produce gold nanoparticle-wool fibre composites with remarkable colour uniformity. The composites were used to fabricate luxury apparel and carpets for international trade expositions. The pathway from synthesis in the laboratory to pilot-scale production of gold nanoparticle-wool fibre composites is presented. The PhD research was an integral step in the successful commercialisation of this innovative nanotechnology, and will assist in scaling-up the synthesis of metal nanoparticle colloids and nanocomposites in the future.</p>

Effect of Granular Silica Aerogel as Filler on Tensile and Flexural Strengths and Moduli of Stone-Wool-Fibre-Reinforced Composite as Rigid Board Roof Insulation Material

Installation of stone wool as thermal insulation in the roof assembly can be adopted to store heat in the living space, if the building is exposed to cold weather, and, inversely, to retard heat from entering the living space, if it is exposed to hot weather. In spite of the effectiveness of stone wool as a roof insulation material, during installation, it can cause irritation to the skin and can be hazardous to the lungs. Therefore, incorporation of stone wool with other materials to form a rigid board, without compromising its effectiveness as a roof insulation material, is imperative. Strength properties of a stone-wool-fibre-reinforced high-density polyethylene (HDPE) composite roof insulation material were studied. Granular silica aerogel, which possesses an ultra-low thermal conductivity, was added as filler to reduce the thermal conductivity of the composite. Hot compression moulding was performed to prepare samples of the composite with varying silica aerogel content of 0, 1, 2, 3, 4, and 5 wt. %. Findings suggest that 2 wt.% is the optimum silica aerogel content as it resulted in the highest flexural strength and modulus, which is 24.4 MPa and 845.85 MPa, respectively, even though it reduced the tensile strength and modulus by 10% and 4.45% respectively, relative to 0 wt. %, which can be considered as inconsequential. Higher silica aerogel content above 2 wt. % may result in poor interfacial adhesion and low compatibility to the stone wool fibre and HDPE, which further reduces the tensile and flexural strengths and moduli of the composite.

Multifunctional Textiles from New Zealand Wool Coloured with Silver or Silver Halide Nanoparticles

<p>Significant opportunities exist for the development of innovative multifunctional textiles for high value market applications. Composites that combine the inherent properties of their all precursor components in a synergistic manner in particular are sought after. Thus the unique chemical and physical properties of silver or silver halide nanoparticles are combined with the traditional properties of wool, thereby producing an innovative multifunctional composite. The prepared wool - silver or - silver halide nanoparticle composites retain the elasticity, thermal insulation and softness of the wool, whilst the colour, conductivity and antimicrobial properties owing to the nanoparticles are also incorporated. Due to the multi functions of silver the resulting high quality, high value product has numerous applications within the fashion and interior furnishings industries. The wools employed for the preparation of wool - silver or - silver chloride nanoparticle composites are merino wool and crossbred wool. Merino wool provides the main focus of the research. The experimental approach for the colouring of merino by silver or silver halide nanoparticles follows a novel and proprietary approach. The preparation of wool - silver nanoparticle composites includes two different procedures: 1) the synthesis of nanoparticles in the presence of wool fibres, using an external reducing agent/stabilising agent (trisodium citrate (TSC)), with the in situ binding of nanoparticles to the surface of the fibre; and 2) the synthesis of nanoparticles in the presence of the merino wool substrate, using the reducing nature of wool, with the in situ binding of nanoparticles within the fibre. Merino wool - silver nanoparticle composites range in colour from very pale yellow, through gold to tan and brown. The successful preparation of wool - silver halide nanoparticle composites includes the in situ precipitation of nanoparticles within the wool fibre. This is accomplished by doping the wool, with one of the halides, Cl⁻, Br⁻ or I⁻, prior to treatment with a silver containing solution. The colour of merino wool - silver halide nanoparticle composites can be tuned from pink to peach to purple. The colour of the wool - silver or - silver halide nanoparticle composites is due to surface plasmon resonances, i.e. the interaction of electromagnetic radiation of visible light with the nanoparticles. The reflected colour is dependent upon the size and shape of the nanoparticle, in addition to the refractive index of the stabilising agent surround the particle. The refractive index of silver chloride or silver bromide differs to that of the reducing/stabilising agent implemented, TSC, or merino, and thus the reflected colour is altered. The colour of silver iodide nanoparticles appears to be due to the interaction of light with the formed nanoparticles themselves and not due to the formation of silver nanoparticles within the silver iodide nanoparticles. In addition to the colour being measured by UV-vis in reflectance mode, the characterisation of the hues of the prepared composites were monitored by obtaining CIE L*, a*, b* values via the HunterLab Colourquest. The morphological characterisation of merino wool coloured by silver or silver chloride nanoparticles was undertaken using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). When merino wool - silver nanoparticle composites are prepared using an external reducing agent, the formed nanoparticles predominantly bind to the wool fibres surfaces only. When the reducing nature of wool is used for composite preparation, nanoparticles are formed within the fibre and are dispersed throughout the fibres core, with few being present on the surface. Comparable studies of merino wool - silver halide nanoparticle composites showed that silver halide nanoparticles are formed and stabilised just below the fibres surface. The confirmation of silver or silver halide species within the prepared composites was undertaken using energy dispersive spectroscopy (EDS), scanning transmission spectroscopy (STEM), x-ray diffraction (XRD) and x-ray absorption near edge spectroscopy (XANES). Colourfastness tests to washing, rubbing and exposure to chlorinated swimming pool water were undertaken to assess the robustness of the prepared composites in terms of their colour. These tests indicate that the colours of both merino wool - silver and - silver chloride nanoparticle composites are very stable. The leaching of silver during the washing process was noted to be insignificant, suggesting a strong and stable bond between the fibre substrate and the nanoparticles. X-ray photoelectron spectroscopy (XPS) was used to elucidate the chemical bonding between the wool fibre substrate and the silver or silver halide nanoparticles. The colourfastness of merino wool - silver or - silver halide nanoparticle composites to light however, was not observed. When exposed to UV light for extended periods, a distinct change in colour occurs. Silver nanoparticle composites lighten considerably, whereas their silver chloride nanoparticle counterparts are noted to become grey in their colour. XPS was used in an attempt to determine what leads to the discolouration of the composites. Further research is required however, in order to reduce or halt the colour degradation of merino wool - silver or - silver chloride nanoparticle composites. Silver iodide nanoparticles, on the other hand, show great potential as colourants for wool, exhibiting stable colours over a long time period to light. A range of desirable colours are obtained through the colouring of wool by silver or silver halide nanoparticles. These nanoparticles are strongly bound to the fibres and thus the colours are stable to washing and rubbing, exhibiting insignificant leaching of silver during such processes. Additionally, the prepared silver and silver halide nanoparticle composites tested positive for their antistatic properties, and their antimicrobial activity, providing a high value multifunctional material. Numerous applications within fashion and interior furnishing industries are therefore apparent. However, the evident setback for applications in these fields is the colour instability to light of silver, silver chloride and silver bromide nanoparticles, and thus further studies are required to eliminate this problem. Alternative options exist for the exploitation of the photosensitivity of silver halide nanoparticles within the merino wool composites, or the possibility of using silver or silver halide nanoparticles in combination with other strong dyes for the production of coloured woollen fabrics.</p>

Multifunctional Textiles from New Zealand Wool Coloured with Silver or Silver Halide Nanoparticles

<p>Significant opportunities exist for the development of innovative multifunctional textiles for high value market applications. Composites that combine the inherent properties of their all precursor components in a synergistic manner in particular are sought after. Thus the unique chemical and physical properties of silver or silver halide nanoparticles are combined with the traditional properties of wool, thereby producing an innovative multifunctional composite. The prepared wool - silver or - silver halide nanoparticle composites retain the elasticity, thermal insulation and softness of the wool, whilst the colour, conductivity and antimicrobial properties owing to the nanoparticles are also incorporated. Due to the multi functions of silver the resulting high quality, high value product has numerous applications within the fashion and interior furnishings industries. The wools employed for the preparation of wool - silver or - silver chloride nanoparticle composites are merino wool and crossbred wool. Merino wool provides the main focus of the research. The experimental approach for the colouring of merino by silver or silver halide nanoparticles follows a novel and proprietary approach. The preparation of wool - silver nanoparticle composites includes two different procedures: 1) the synthesis of nanoparticles in the presence of wool fibres, using an external reducing agent/stabilising agent (trisodium citrate (TSC)), with the in situ binding of nanoparticles to the surface of the fibre; and 2) the synthesis of nanoparticles in the presence of the merino wool substrate, using the reducing nature of wool, with the in situ binding of nanoparticles within the fibre. Merino wool - silver nanoparticle composites range in colour from very pale yellow, through gold to tan and brown. The successful preparation of wool - silver halide nanoparticle composites includes the in situ precipitation of nanoparticles within the wool fibre. This is accomplished by doping the wool, with one of the halides, Cl⁻, Br⁻ or I⁻, prior to treatment with a silver containing solution. The colour of merino wool - silver halide nanoparticle composites can be tuned from pink to peach to purple. The colour of the wool - silver or - silver halide nanoparticle composites is due to surface plasmon resonances, i.e. the interaction of electromagnetic radiation of visible light with the nanoparticles. The reflected colour is dependent upon the size and shape of the nanoparticle, in addition to the refractive index of the stabilising agent surround the particle. The refractive index of silver chloride or silver bromide differs to that of the reducing/stabilising agent implemented, TSC, or merino, and thus the reflected colour is altered. The colour of silver iodide nanoparticles appears to be due to the interaction of light with the formed nanoparticles themselves and not due to the formation of silver nanoparticles within the silver iodide nanoparticles. In addition to the colour being measured by UV-vis in reflectance mode, the characterisation of the hues of the prepared composites were monitored by obtaining CIE L*, a*, b* values via the HunterLab Colourquest. The morphological characterisation of merino wool coloured by silver or silver chloride nanoparticles was undertaken using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). When merino wool - silver nanoparticle composites are prepared using an external reducing agent, the formed nanoparticles predominantly bind to the wool fibres surfaces only. When the reducing nature of wool is used for composite preparation, nanoparticles are formed within the fibre and are dispersed throughout the fibres core, with few being present on the surface. Comparable studies of merino wool - silver halide nanoparticle composites showed that silver halide nanoparticles are formed and stabilised just below the fibres surface. The confirmation of silver or silver halide species within the prepared composites was undertaken using energy dispersive spectroscopy (EDS), scanning transmission spectroscopy (STEM), x-ray diffraction (XRD) and x-ray absorption near edge spectroscopy (XANES). Colourfastness tests to washing, rubbing and exposure to chlorinated swimming pool water were undertaken to assess the robustness of the prepared composites in terms of their colour. These tests indicate that the colours of both merino wool - silver and - silver chloride nanoparticle composites are very stable. The leaching of silver during the washing process was noted to be insignificant, suggesting a strong and stable bond between the fibre substrate and the nanoparticles. X-ray photoelectron spectroscopy (XPS) was used to elucidate the chemical bonding between the wool fibre substrate and the silver or silver halide nanoparticles. The colourfastness of merino wool - silver or - silver halide nanoparticle composites to light however, was not observed. When exposed to UV light for extended periods, a distinct change in colour occurs. Silver nanoparticle composites lighten considerably, whereas their silver chloride nanoparticle counterparts are noted to become grey in their colour. XPS was used in an attempt to determine what leads to the discolouration of the composites. Further research is required however, in order to reduce or halt the colour degradation of merino wool - silver or - silver chloride nanoparticle composites. Silver iodide nanoparticles, on the other hand, show great potential as colourants for wool, exhibiting stable colours over a long time period to light. A range of desirable colours are obtained through the colouring of wool by silver or silver halide nanoparticles. These nanoparticles are strongly bound to the fibres and thus the colours are stable to washing and rubbing, exhibiting insignificant leaching of silver during such processes. Additionally, the prepared silver and silver halide nanoparticle composites tested positive for their antistatic properties, and their antimicrobial activity, providing a high value multifunctional material. Numerous applications within fashion and interior furnishing industries are therefore apparent. However, the evident setback for applications in these fields is the colour instability to light of silver, silver chloride and silver bromide nanoparticles, and thus further studies are required to eliminate this problem. Alternative options exist for the exploitation of the photosensitivity of silver halide nanoparticles within the merino wool composites, or the possibility of using silver or silver halide nanoparticles in combination with other strong dyes for the production of coloured woollen fabrics.</p>

Some Uptake Studies of Metal Ions and the Formation of Cu₂0 Particles in Wool

<p>This research programme is concerned with the uptake studies of Cu2+, Zn2+ and Mn2+ at different conditions, by merino wool fibres and also uptake studies of Cu2+ ions by chemically modified wool fibres. Cu2O particles and Cu complexes are formed within merino wool by an in situ reaction with sodium borohydride and thioglycoloic acid respectively. The d-block elements have the ability to bind chemically to certain functional groups present within the keratin protein of wool. The absorption of the Cu2+, Mn2+ and Zn2+ from solution by wool fibres under different conditions notably, time, temperature and initial concentration have been studied. The optimum temperature and reaction time to give highest absorption of the Cu2+ by the wool fibre was found to be 90 oC and one hour without modifying the nature of the wool, from a solution of Cu2+ concentration of 450 mg L-1. Cu2+ was found to give the greatest absorption by the wool fibres, whereas Zn2+ and Mn2+ were found to be absorbed the least. The absorption of Cu2+ ions increases with increasing temperature. At the higher temperature of 90 oC, the -S-S- bonds in the cystine amino acids break more readily, generating thiol and cysteic acid groups to bind with copper ions. The uptake of Cu2+ by ethylenediaminetetraacetic dianhydride (14 mg g-1 of wool) or thioglycolic acid (42.5 mg g-1 of wool) or sodium borohydride (41.8 mg g-1 of wool) treated merino wool fibres increases with respect to unmodified wool (8 mg g-1 of wool). NaBH4 treated merino wool reduces Cu2+ ions to Cu2O particles which form within the wool fibres by an in situ reaction. TGA treated merino wool provides additional functional groups to bind with copper ions and Cu2O particles also likely to be formed within TGA treated wool composites. The metal ions were absorbed into the fibres under various conditions and the extent of absorption was quantified. The form and binding of the Cu2O particles or Cu2+ ions onto the wool fibres are studied using UV-Visible, FTIR, XRD, SEM, EDS and TEM methods.</p>

Some Uptake Studies of Metal Ions and the Formation of Cu₂0 Particles in Wool

<p>This research programme is concerned with the uptake studies of Cu2+, Zn2+ and Mn2+ at different conditions, by merino wool fibres and also uptake studies of Cu2+ ions by chemically modified wool fibres. Cu2O particles and Cu complexes are formed within merino wool by an in situ reaction with sodium borohydride and thioglycoloic acid respectively. The d-block elements have the ability to bind chemically to certain functional groups present within the keratin protein of wool. The absorption of the Cu2+, Mn2+ and Zn2+ from solution by wool fibres under different conditions notably, time, temperature and initial concentration have been studied. The optimum temperature and reaction time to give highest absorption of the Cu2+ by the wool fibre was found to be 90 oC and one hour without modifying the nature of the wool, from a solution of Cu2+ concentration of 450 mg L-1. Cu2+ was found to give the greatest absorption by the wool fibres, whereas Zn2+ and Mn2+ were found to be absorbed the least. The absorption of Cu2+ ions increases with increasing temperature. At the higher temperature of 90 oC, the -S-S- bonds in the cystine amino acids break more readily, generating thiol and cysteic acid groups to bind with copper ions. The uptake of Cu2+ by ethylenediaminetetraacetic dianhydride (14 mg g-1 of wool) or thioglycolic acid (42.5 mg g-1 of wool) or sodium borohydride (41.8 mg g-1 of wool) treated merino wool fibres increases with respect to unmodified wool (8 mg g-1 of wool). NaBH4 treated merino wool reduces Cu2+ ions to Cu2O particles which form within the wool fibres by an in situ reaction. TGA treated merino wool provides additional functional groups to bind with copper ions and Cu2O particles also likely to be formed within TGA treated wool composites. The metal ions were absorbed into the fibres under various conditions and the extent of absorption was quantified. The form and binding of the Cu2O particles or Cu2+ ions onto the wool fibres are studied using UV-Visible, FTIR, XRD, SEM, EDS and TEM methods.</p>

From tools to production: recent research on textile economies in Greece

The aim of this report is to provide a summary of the latest developments in the textile archaeology of Greece and the broader Aegean from the Neolithic through to the Roman period, focusing in particular on recent research on textile tools. Spindle-whorls and loomweights appeared in the Aegean during the Neolithic and by the Early Bronze Age weaving on the warp-weighted loom was well established across the region. Recent methodological advances allow the use of the physical characteristics of tools to estimate the quality of the yarns and textiles produced, even in the absence of extant fabrics. The shapes of spindle-whorls evolved with the introduction of wool fibre, which by the Middle Bronze Age had become the dominant textile raw material in the region. The spread of discoid loomweights from Crete to the wider Aegean has been linked to the wider Minoanization of the area during the Middle Bronze Age, as well as the mobility of weavers. Broader issues discussed in connection with textile production include urbanization, the spread of different textile cultures and the identification of specific practices (sealing) and previously unrecognized technologies (splicing), as well as the value of textiles enhanced by a variety of decorative techniques and purple dyeing.