ABOUT THE PROJECT
Project name: IP-11-2013 ADVANCED TEXTILE MATERIALS BY TARGETED SURFACE MODIFICATION
PI institution: University of Zagreb, Faculty of Textile Technology
PI: Prof Sandra Bischof, PhD
Duration: 48 months
Funding instrument: National Science Foundation
Project cost: 989.200,00 HRK
The demand for advanced textile materials has dramatically increased during the last few decades, in particular for engineering, medical and technical applications. A new sight proposed by this project is in the merging of so far separate research teams involved in the development of advanced textile materials, through targeted eco-driven surface modifications. Surface pre-treatments and modification will be carried out on selected sustainable textile materials, using environmentally friendly substances and processes, in order to attain antimicrobial, flame retardant, oil/hydrophobic, wellness or medical properties obtaining high added value textiles. Different environmentally friendly methods of microwave, ultrasound or plasma modification processes will be used to enhance targeted functionalities as well as to increase interfacial adhesion between fibres and polymer matrix in fibre reinforced composites. The other approach of the production of highly active surfaces which will have capability to block UV and microwave radiation, enhance oil and water repellence, antimicrobial, self-cleaning, and flame retardant properties is in the application of micro/nano-particles such as TiO2, ZnO, Cu, Ag and Au. These particles can be applied on the surface of fibers, textiles, clothing or inlayers for footwear. Detailed characterization of each treatment effectiveness, so as their effect on humans and the environment will be investigated. Laundering durability and maintenance properties are equally important as the effectiveness of developed advanced material. Introduction of novel eco-driven surface modification processes in textile production will be complemented by the risk analysis and sustainability issues, focusing onto production and product safety, usage and recyclability of newly developed product without significant environmental burden. Innovative textile products will be directed towards the needs of the textile, chemical, pharmaceutical or medical industries.
The demand for advanced textile materials (ATM) has dramatically increased during the last few decades, in particular for engineering, medical and technical applications. The development of materials has been acknowledged as one of the most important generators of the economic development since it is found in almost every industrial sector. For that reason was the European initiative Alliance for Materials (A4M)  initiated by six European Technological Platforms: EuMaT (Advanced Engineering Materials and Technologies) , Suschem (Sustainable Chemistry), Manufuture, FTC (Future of Textiles and Clothing), ESTEP (EU Steel Technology Platform) and SMR (Sustainable Mineral Resources). Development of materials in all domains, so as in textile one, is the imperative of the 21st century and the main reason for initiating ADVANCETEX project. Furthermore, the topic of advanced textile materials is recognized as one of the Key Enabling Technologies (KET) whose deployment by industry is a key factor in strengthening Europe¢s competitiveness [3-4].
Project is completely in compliance with the most important European, so as the Croatian initiatives [5-6]. Therefore, research of Croatian scientists within this ATM group, supported with the collaboration with international ones, definitively will be at the forefront of the science and will enhance the chances for the competitiveness of Croatian SMEs in the EU market.
MAIN OBJECTIVES of the project:
· conducting internationally competitive research in compliance with strategic needs and priorities of the Republic of Croatia and with the goals of the European strategies: Europe 2020, Horizon 2020, European Technological Platforms for the Future of Textile and Clothing (ETP-FTC) and European initiatives: NANOfutures and A4M.
· continuous promotion of Croatian Science, by increasing international visibility and recognition of the Croatian scientific community in the technical area and by transferring knowledge into education in the so called STEM area (Science, Technology, Engineering and Mathematics).
· strengthening of mentoring capacity in the area of advanced materials.
· enhancing the training of young scientists.
· acquisition of new knowledge and its transfer into economy with the goal of increasing competitiveness of Croatian economy (textile and defence sector) in an international environment and for the welfare of the social community.
Based on the experience of the leading industrial countries, the development of advanced materials requires interdisciplinary approach to research, which is especially highlighted in the development of textile materials and clothing, requiring:
· knowledge about fibres
· advanced process technologies (including biotechnology and nanotechnology ) in accordance with the Life Cycle Assessment (LCA) initiative
· knowledge about requirements posed on specific textile purposes (technical, medical and/or protective).
Figure 1: Development of Advanced Textile Materials (ATM) through the textile surface modifications
SPECIFIC OBJECTIVES of the project are:
· development of novel bio-innovated pre-treatment processes.
· development of eco-friendly surface modification processes for technical, medical, cosmetic and protective purposes.
· achieving high safety level (non-harmfulness) of the developed materials.
Although the past decade has been marked by production decrease in the European textile industry and mass production of textiles , the technological level of their production increased, especially in the area of high added value textiles (functional textiles, composites and smart textiles), and so did the ecological awareness of the producers and society. The research conducted at TTF or in the cooperation with small and medium-sized enterprises (SMEs) within the framework of national or EU funded projects, made a significant contribution in this respect .
CHALLENGE 1: BIO-INNOVATED PRE-TREATMENT PROCESSES
The conventional pretreatment technology for cellulose based materials includes desizing, scouring, retting and bleaching. These operation sequences consume huge amounts of energy, water, and chemicals. The enzymatic pre-treatments of textiles have received much attention in the last decade due to their ecological benefits. The use of protease, lipase, pectinase, cutinase, cellulase, amylase, glucose oxidase and peroxidase enzymes can replace unsustainable conventional pre-treatment [9-16]. Enzymes can help in different stages of bast fibres processing like retting of flax, cottonization of bast fiber and/or hemp separation etc. The main enzymes acting in retting process are pectinases, xylanases and cellulases [17,18]. Besides being characterised as energy and water consuming processes retting can have negative influence on the environment. This is why scientists are focused on finding new, less expensive and environmentally friendlier processes, while at the same time fibre properties should be preserved or improved. According to some preliminary findings microwave, ultrasound or osmotic degumming can fulfil stated requirements [19-23].
Innovations beyond State-of-the-Art (SoA):
· application of enzymatic complexes in single bath processes for sustainable multifunctional properties of treated cellulose based materials.
· introduction of new pre-treatment activators for low temperature processes.
· development of novel, eco friendlier reting processes.
· development of procedures for recycling the raw material waste in composite manufacturing process. with the purpose of obtaining environmentally friendly fuel.
CHALLENGE 2: ECO-DRIVEN SURFACE MODIFICATIONS
Considering the strict EU regulation (Registration, Evaluation, Authorisation and Restriction of Chemicals - REACH) regarding the application of eco-friendly chemicals that may not have a negative effect on people or the environment, a series of chemicals which are still in the usage will be forbidden in the near future) . In this sense, one of the main challenges of this project is to develop innovative surface modifications whose application on textiles meets all standards, while at the same time ensuring safety for people and the environment, taking into the consideration Life Cycle Assessments [25,26].
In addition to the use and development of various organic compounds scientists are showing great interest in applying nanoparticles in/on textile and in interpretation of their structural complexity and chemical diversity [27-34]. One approach to the production of highly active surfaces which have capability to block UV and microwave radiation, enhance oil and water repellence, antimicrobial, self-cleaning, and/or flame retardant properties is the usage of nano-metal or nano-metal oxides particles such as TiO2, ZnO, Cu, Ag and Au. These particles can be applied on the surface of fibres, textiles, clothing or inlayers for footwear. However, durability of developed functional coatings is a huge and still not solved issue which needs to be addressed.
In order to achieve better durability of applied agents to textile materials ecologically and economically favourable surface modification processes with non-invasive ultrasounds, plasma and microwave technology will be used.
Innovations beyond State-of-the-Art (SoA):
· development of innovative layer (incorporating nano-metal or nano-metal oxydes for the purpose of their targeted functionalization and/or achieving optimal protective properties for medical and protective textiles).
· application of new manufacturing routes: in-situ synthesis where nanoparticles are grown in the matrix.
· application of novel eco-friendly microwave treatments (for drying and thermofixation).
· improvement of the durability to laundering obtained by the usage of ultrasound and plasma treatments.
· development of recipes and procedures for maintenance and care, with the purpose of obtaining consistent multifunctional textiles with minimum or no burden to the environment.
CHALLENGE 2.1: SURFACE MODIFICATIONS FOR TECHNICAL APPLICATIONS
The technical textile sector is undergoing significant industrial change with the growing importance of new applications (automotive, aeronautics, buildings, environment, medicine, sport and leisure) and a radical move from traditional technologies (knitting, weaving, etc.) to more recent ones like composites .
Nowadays, there is an increasing trend for the use of natural fibres as reinforcements in composite materials production . Within the project several sustainable fibres from domestic sources will be used – wool, flax and Spartium Junceum L. fibre . Their potential use as a reinforcement is greatly reduced because of their hydrophilic (water absorbing) nature, and the lack of sufficient adhesion between untreated fibres and the polymer matrix [38-40]. One of the aims of this project is development of bio composite material reinforced with natural fibres which will represent innovative technical textiles with broad application possibilities. The issue of poor interfacial adhesion between fibres and polymer matrix will be solved by the development of effective surface and chemical treatments in accordance with the EU legislation on environmental issues for composite industry and REACH regulation. This work will be done in the collaboration with UK partner, Brunel University (Prof. Mizi Fan will be co-mentoring PhD of Zorana Kovacevic).
Innovations beyond State-of-the-Art (SoA):
· application of newly synthesized nano-particles of the tailored characteristics on the textile fibres or material applicable for nanobiocomposites.
· fulfilment of required interfacial interaction and compatibility of nano-particles with biobased polymer matrixes to be utilised in the nanobiocomposite.
· enhancement of interfacial adhesion between fibres and polymer matrix
· selection of different processing techniques and optimization of process parameters in composite manufacturing to reduce its cost and time to market.
· better product and process design through better understanding of nanocomposite structure and property relationship.
· development of procedures for fibre reinforced composites (FRC) recycling.
CHALLENGE 2.2: SURFACE MODIFICATIONS FOR MEDICAL APPLICATIONS
Medical textiles is one of the most rapidly expanding sectors in the technical textile. The use of textile materials for medical and healthcare products ranges from simple gauze or bandage materials to scaffolds for tissue culturing and a large variety of prostheses for permanent body implants [41-43]. Major concern is to apply eco-friendly antimicrobial substances, in particular for the textiles in direct contact with the skin. The current protocols and initiatives in infection control could be improved by the use of antimicrobial agents applied on cellulose based materials.
The most frequently used agent for textiles is silver, although some other metals such as: copper, zinc, cadmium, mercury and cobalt have attracted scientist’s attraction . Metallic compounds work by inhibiting the active enzyme centres in microorganisms. Our previous work included deposition of nano-silver layers on the surface of PLA material using Direct current (DC) magnetron sputtering with 99.99% pure Ag target . Promising research will be continued in collaboration with Swiss research centre EMPA. Further possibility is usage of environmentally friendly agents, e.g. citric acid [46,47] or peroxyacids. A large group of environmentally safe antimicrobial agents is based on natural zeolites. On the other hand, synthetic zeolites are more flexible due to their homogenous chemical composition that enables different incorporation methods of metal ions. In addition to the ion exchange technique, microwave and sonication assisted methods have been claimed to produce high-quality antibacterial materials [48-50].
Innovations beyond State-of-the-Art (SoA):
· application of new environmentally friendly agents (citric acid, peroxyacids, mikro/nano-metal compounds) and catalysts for antimicrobial finishing.
· potential negative dermatological effectiveness will be diminished using agents with minimal or no impact on human skin.
· improvement of the current protocols and initiatives in infection control by the use of developed antimicrobial agents on cellulose based materials.
CHALLENGE 2.3: COSMETOTEXTILES
Introduction of cosmetotextiles was driven by the needs of the customer to combine health and wellness with appearance in everyday consumption. Cosmetotextiles are garments designed to contact the skin with the aim of transferring active substances useful for cosmetic purposes, particularly to combat ageing effects. Latest prediction of the cosmetotextiles market value for 2013 is around € 500 million .
Liposomes as biocompatible, biodegradable, and nontoxic artificial vesicles formed by lipids which can encapsulate many compounds (hydrophilic, hydrophobic, and amphiphilic) for application to textiles, drug delivery, cosmetics etc. have been the subject of intensive research . Moreover, liposomes have been the subject of intensive research because of their importance as microencapsulation devices for drug delivery and their applications in cosmetics .
Further functionality can be achieved with cyclodextrins (CDs) which can complex and release fragrances or “skin-care-active” substances like vitamins, caffeine and menthol as well as bioactive substances such as biocides, insecticides and drugs. Furthermore, various textile materials treated with CDs could be used for adsorption of small pollutants from waste waters – for filtration, purification, and/or separation treatments of waste waters .
Different active substances, such as liposome, cyclodextrins (CD), Vitamin E, proteins, natural extracts of plants (aromatic oils, rosemary, lavandula, chestnut, marigold, nut, menthol) can be applied on cellulose based materials and polyamide by padding, spraying, coating, impregnation as textile finishes which can be transferred to skin. The goal is selection of best available technology (BAT) which can enable a slow release of „skin active substances“ with product long life.
Innovations beyond State-of-the-Art (SoA):
· application of natural active substances of Croatian origin (rosemary, lavandula, chestnut, marigold and Spartium junceum L. extracts) for cosmetic purposes.
· incorporation of eco-friendly cosmetic agents into textiles functionalized for both medical and wellness purposes.
· in-depth study of adsorption/desorption mechanism of active substances in different conditions
· re-loading techniques for active substances recovery.
CHALLENGE 2.4: PROTECTIVE TEXTILES
Rising health and safety concerns for those exposed to dangerous environments or high risk professions has increased the demand for improved protective apparel and accessories. Protective textiles are part of the Personal Protective Equipments (PPE) family and represent a specific area of the advanced technical textiles sector, a strongly growing market for the textile industry, satisfying an increasing demand for high performance requirements. Protective textiles are produced with the aim of eliminating or minimising the risk of injuries, accidents and infections, acting as shields against chemical, biological and nuclear hazards, radiation, high temperatures and fire, sharp objects, so as the ballistic projectiles, etc. .
Within the project accent will be laid on development of flame retardant surface treatments. Halogenated products and halogen-antimony systems tend to be flame inhibitors, but due to the environment concerns they are banned. Boron systems tend to enhance charring and formation of surface barrier layers while the metal hydroxides tend to be endothermic water-releasing systems .
Many nanomaterials (including titanium dioxide, silicon dioxide, clays and layered double hydroxide) have shown promise as flame retardant additives, enhancers of flame retardant coatings - effectively providing the flame resistance  and this research path will be further investigated, together with the application of layer-by-layer technique [58, 59].
Innovations beyond State-of-the-Art (SoA):
· improved environmental profile obtained by application of new agents and catalysts for flame retardant (FR) finishing.
· the introduction of new technologies with dramatically reduced resource consumption which will enable cost effective production of advanced FR materials with improved ecological footprint.
· in-situ synthesis where Cu and Zn nanoparticles are grown on cellulose based material in order to enhance FR and antimicrobial effectiveness.
· layer-by-layer deposition for enhancement of FR properties
· faster and more flexible design changes towards targeted functionality.
CHALLENGE 3: SAFETY ISSUES OF DEVELOPED PRODUCTS
Nano-technology based applications will substantially improve the performance of many products through their unique properties. These properties, on the other hand, give rise to concerns with regard to potential health and safety risks. Risk management will be integral part of the proposed research with the objective to support methods, techniques and equipment for material characterisation, hazard identification, occupational exposure assessment and risk reduction and/or mitigation.
Due to the huge water consumption, and equally huge burden posed on textile waste waters accent will be laid on quantification of the release of potentially harmful substances (e.g. Ag, Au) used for the surface modification. About 15 % of total silver release into water in the EU derives from silver containing plastics and textiles . So, textiles are one of the most important sources of Ag nanoparticles in the environment [61,62].
Significant amounts of silver are lost in the effluents discharged and due to the toxicity of silver to living organisms, the removal of this metal from wastewaters is an important concern. The main technologies used for silver removal wastewaters include precipitation, ion exchange, membrane processes, solvent extraction, cementation, electro coagulation, coagulation–flocculation, adsorption, reductive exchange and electrolytic recovery. Adsorption has attracted attention because of new material types available for the recovery process. Natural zeolites are cost-effective materials that have been investigated for their potential use as adsorbents for silver and copper uptake .
The zeolites (consisting mainly of clinoptilolite) used in our previous work are natural clay mineral from Croatian large sedimentary. Clinoptilolites could be successfully used for removal of silver, gold or copper ions from aqueous solutions after finishing or laundering. Furthermore, synthetic zeolites are more suitable since their exact chemical composition results in adsorbents with improved performances in different metal uptakes .
Innovations beyond State-of-the-Aart (SoA):
· better understanding of nanomaterial and nanotechnology intrinsic properties, through lab testing under simulated real conditions in use (wear and wash).
· application of sustainable natural/synthetic zeolites for nano-metal particles removal.
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