TEXTILE & REVIEW LEATHER
3/2021 Volume 4 Issue 3 2021 textile-leather.com ISSN 2623-6257 (Print) ISSN 2623-6281 (Online)
TEXTILE & REVIEW LEATHER Editor-in-Chief
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Shahid Adeel, Government College University Faisalabad, Department of Chemistry, Pakistan Emriye Perrin Akçakoca Kumbasar, Ege University, Faculty of Engineering, Turkey Tuba Bedez Üte, Ege University, Faculty of Engineering, Turkey Mirela Blaga, Gheorghe Asachi Technical University of Iasi, Faculty of Textiles, Leather and Industrial Management, Romania Patrizia Calefato, University of Bari Aldo Moro, Department of Political Sciences, Italy Andrej Demšar, University of Ljubljana, Faculty of Natural Sciences and Engineering, Slovenia Krste Dimitrovski, University of Ljubljana, Faculty of Natural Sciences and Engineering, Slovenia Ante Gavranović, Economic Analyst, Croatia Ana Marija Grancarić, University of Zagreb, Faculty of Textile Technology, Croatia Huseyin Kadoglu, Ege University, Faculty of Engineering, Turkey Fatma Kalaoglu, Istanbul Technical University, Faculty of Textile Technologies and Design, Turkey Hüseyin Ata Karavana, Ege University, Faculty of Engineering, Turkey Ilda Kazani, Polytechnic University of Tirana, Department of Textile and Fashion, Albania Vladan Končar, Gemtex – Textile Research Laboratory, Ensait, France Stana Kovačević, University of Zagreb, Faculty of Textile Technology, Croatia Aura Mihai, Gheorghe Asachi Technical University of Iasi, Faculty of Textiles, Leather and Industrial Management, Romania Jacek Mlynarek, CTT Group – Textiles, Geosynthetics & Flexibles Materials, Canada Abhijit Mujumdar, Indian Institute of Technology Delhi, India Monika Rom, University of Bielsko-Biala, Institute of Textile Engineering and Polymer Materials, Poland Venkatasubramanian Sivakumar – CSIR – Central Leather Research Institute, Chemical Engineering Department, India Pavla Těšinová, Technical university of Liberec, Faculty of Textile Engineering, Czech Republic Savvas Vassiliadis, Piraeus University of Applied Sciences, Department of Electronics Engineering, Greece
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Textile & Leather Review ‒ ISSN 2623-6257 (Print), ISSN 2623-6281 (Online) UDC 677+675 DOI: https://doi.org/10.31881/TLR Frequency: 4 Times/Year The annual subscription (4 issues). Printed in 300 copies Published by Seniko studio d.o.o., Zagreb, Croatia Full-text available in open access at www.textile-leather.com
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TEXTILE & LEATHER REVIEW ISSN 2623-6257 (Print)
ISSN 2623-6281 (Online) CROATIA
VOLUME 4
ISSUE 3
2021
p. 133-204
CONTENT REVIEW 137-148
A Review of Natural Plants as Sources of Substances for Cleaner Leather Tanning Technologies Kallen Mulilo Nalyanya, Ronald K. Rop, Arthur S. Onyuka, Zephania Birech
ARTICLE 149-159
Biaxial Cyclic Loading of Woven Fabrics Snježana Brnada, Stana Kovačević, Irena Šabarić, Lovro Držaić
REVIEW 160-180
Textile Finishing Using Polymer Nanocomposites for Radiation Shielding, Flame Retardancy and Mechanical Strength Sorna Gowri, Mohammad Akram Khan, Avanish Kumar Srivastava
181-200
Solution Blow Spinning (SBS): A Promising Spinning System for Submicron/ Nanofibre Production Md. Khalilur Rahman Khan, Mohammad Naim Hassan
NALYANYA KM, et al. A Review of Natural Plants as Sources of Substances… TLR 4 (3) 2021 137-148.
A Review of Natural Plants as Sources of Substances for Cleaner Leather Tanning Technologies Kallen Mulilo NALYANYA1*, Ronald K. ROP2, Arthur S. ONYUKA3, Zephania BIRECH4 Department of Physics, Faculty of Science, Egerton University Department of Mathematics, Actuarial and Physical Science, School of science, University of Kabianga 3 Kenya Industrial Research and Development Institute, Nairobi 4 Department of Physics, College of Biological and Physical Sciences, University of Nairobi *kallenmulilo@ymail.com 1 2
Review UDC 675.024.3 DOI: 10.31881/TLR.2021.03 Received 30 January 2021; Accepted 23 March 2021; Published Online 31 March 2021; Published 7 September 2021
ABSTRACT The stringent environmental regulations and compliance regarding leather tanning has compelled leather industry to seek alternative cleaner ingredients that have the capacity to minimize or prevent pollution caused by hazardous chemicals. Practical measures have so far involved replacing the current use of synthetic chemicals such as chromium salts, dyes, fatliquors and surfactants or minimizing their usage by incorporating agrobased organic components. Numerous papers have documented the use of different plant extracts at different stages of leather processing such as tanning, retanning, dyeing and fatliquoring. This present article details the specific plants and the leather processing stage at which they are applied and eventually the quality of the resulting leather. This article attempts to compile a considerable number of investigations published on physical properties of leather that is processed using natural plants. It has been shown that there are striking similarities in leather properties of leather processed using natural plants and using synthetic chemicals. This could help in compiling a database that details works on natural plants, stages of application and the corresponding physical properties which could provide a crucial assistance to research focusing on environmental protection and physical properties of leather which would in turn improve the quality of the resulting leather. KEYWORDS Vegetable tanning, Leather, Hazardous, Environment
INTRODUCTION Leather industry, which thrives on a by-product of the meat industry, plays a critical role in the global economy and especially in the developing countries, by contributing towards the Gross Domestic Product (GDP), as a source of livelihoods, offering employment opportunities and supporting other downstream industries [1,2]. The potential of this industry is immense, owing to the demand for meat and leather products by the increasing world population. However, environmental concerns and the inferior quality of leather threaten the industry’s ability to penetrate the turbulent high market and comply with tough environmental regulations [2,3]. The last two decades have witnessed a growing consumer awareness leading towards the demand for quality leather products that meet the performance and durability criterion, in accordance with the occupational and safety footwear EC mark (Dir.89/686/EEC). Conversely, the growing awarewww.textile-leather.com 137
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ness among consumers towards human and environmental health crusaded by legislative policies such as UNEP and USEPA have compelled the industry to comply with the stringent environmental regulations [4]. Therefore, the appropriate strategy by the industry should be geared towards producing quality leather using environmental-friendly and cleaner manufacturing technologies to secure prospective markets for a viable and sustainable industry [5]. For leather products, the performance requirement is measured in terms of the functional property and the aesthetic values that the product should possess [6,7]. These include the physical (mechanical), hydrothermal and chemical stability, fastness, and organoleptic (tactile or sensorial character) properties of the resulting leather [7-9]. These properties are easily achievable by using the chromium tanning agent which, among the tanning technologies, is the most outstanding due to its superior performance characteristics it confers to leather [10,11]. Nevertheless, chromium is a limited natural resource, which when subjected to accelerated ageing conditions, oxidizes to form toxic and carcinogenic species that have an adverse impact on the environment and human health [12]. Consequently, much research has delved into cleaner tanning systems that are more eco-friendly and less hazardous to both the environment and human health [10, 12-14]. Many of the adopted technologies involve the use of eco-benign natural plant products either synergistically or using singular essence extracts [15-23]. Natural plant tannins contain polyphenols that can be categorized into hydrolysable or condensable tannins [13]. Hydrolysable phenols consist of glucose polyesters that have either gallic or ellagic tannins. On the other hand, condensable phenols consist of catechin monomers, also known as flavonoids [24]. The introduction of plant products into leather processing potentially contributes to the filling action of the leather structure, which alters the strength properties and uniformity of the properties. The interaction between the plant polyphenols and collagen molecules results with bond formation or crosslinking that resultantly modifies the quality of leather by affecting the physical and organoleptic properties of the final leather product [25,26]. The modification depends on the number of galloyl groups and the molecular size. The intergalloyl C-C bonds restrict the flexibility of the galloyl groups, thus hindering the collagen-polyphenol hydrophobic interactions hence affecting structural and physical properties [25]. Beside the phenolic antioxidants, which inhibit the oxidation of some tanning agents, the plant products have the potential to replace the synthetic tanning agents. In this present article, the authors have compiled research on some of the cleaner tanning systems that have used plant products and the corresponding quality impact on the final leather product. The aim is to further the previous work on the use of plant-based products to mitigate environmental challenges faced by the leather industry [12].
QUALITY PARAMETERS OF LEATHER Physical properties The strength properties of the manufactured leather determine the functionality of the final product, the routine quality and the serviceability assessment of the material [3,27,28]. Therefore, these properties form essential index of assessing the utility of the final leather product for various applications [29]. The strength properties include flex resistance, tear strength, elongation at break, tensile strength and colour fastness [27].
Tensile strength This is the maximum tensile stress leather can withstand without plastic deformation or breaking/rupturing the leather [30]. It is given in terms of force per unit area of cross section while applying force in linear direction. It determines the structural resistance of leather, and beyond it the material goes from being elastic to
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being plastically deformed [3]. Since the strength of the leather is determined by the fibrous structure and any modification of the structure, then any bond formation that occurs in the leather matrix affects these properties [10,11]. The acceptable standard minimum of tensile strength for upper leather, lining, furniture and goods is 15, 15, 10 and 10 N/mm2, respectively [31].
Elongation Elongation refers to the ability of leather to lengthen/stretch under tensile force without breaking (elasticity) [3]. Leather considered for garment should possess appropriate elongation since low elongation value results in easy tear while a high elongation value causes leather goods to become deformed very quickly or even become unusable [7]. Upper leather and footwear upper should possess high flexibility to prevent the appearance of cracks and tears in the ball area [32,33]. High elasticity allows the material to withstand the elongation stresses to which it is subjected during footwear lasting, especially on the toe area [34]. The recommended minimum percentage of elongation for quality chrome-tanned leather is 40-80% [31,35,36].
Resistance to tear Tear strength is the measure of the resistance of a material to tear forces, calculated by the maximum force or average of the peak forces in Newtons per unit of thickness of the material in mm [37]. Tear strength in bovine hide is dependent on the interweaving angle and crosslinking of the fibre bundles [28]. The recommended minimum value for tear strength of chrome-tanned shoe upper side leather is 40 N/mm.
Grain burst This parameter verifies if the grain layer of the leather breaks upon being folded. It indicates a level of elasticity derived from the specific processing step and determines the durability of leathers for footwear uppers as per ISO 3379:2015. The minimum grain burst requirement for the manufacture of footwear is 7 mm.
Flex resistance Bally flex or pliability is an indication of the finishing resistance to crack and crease when repeatedly flexed, emulating the flexing of the actual use of the shoe. Flex is an inevitable encounter for majority of leather applications such as footwear at the vamp, toe and heel bends, hence a prerequisite property for any leather meant for footwear upper to endure a predetermined number of flexes to gain qualification. The flexing endurance of leather measures the ability of leather and leather-cloth to withstand repeated flexing without cracking. The ISO 5402:2003 test method embarked the performance requirement for the ball flex/linear flex to be no significant damage at 150K cycle at dry stage [35].
Ball burst Shoe upper leather often shows slight crack in the toe area at the time of lasting operation despite the leather having good tensile and tear strength properties. The stipulated distension and the load at break/ burst are 7 mm and 20 N, respectively.
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Shrinkage temperature This is a parameter used to characterize the thermal stability of leather. It is the temperature at which the leather starts to shrink in water or over a heating media [29]. It determines the degree of crosslinking in leather by the tanning agents, since the higher the degree of crosslinking, the higher the shrinkage temperature. The threshold of the shrinkage for a quality leather is 75 °C. Due to this, the shrinkage temperature remains an important index, which reflects the quantity of new bonds formed in collagen and the quality of tanning and tanned leather. Usually, the users of leather, as raw material for shoes, garment or other, require the shrinkage temperature of leather to be not less than 100 °C [29,38].
Organoleptic properties These properties are also known as tactile and visual evaluation properties or sensory properties or bulk properties [39,40]. These properties include surface colour, texture like softness and roughness, structure fullness or compactness, grain tightness, smoothness, dye uniformity and general appearance [39].
NATURAL PLANT PRODUCTS IN LEATHER TANNING TECHNOLOGIES Tanning processes involving vegetable tannins, organic compounds and chromium salts Sirvaityte et al. investigated the possibility of using essential oils from Thymus vulgaris (thyme) as a natural alternative preservative in leather tanning technology [41]. The essential oil of thyme was the more active component in the mixture of essential oil and the synthetic biocide used for the preservation of chromed leather. The shrinkage temperature of the leather treated with essential oils was 113 °C. The tensile strength and elongation at break were 16.7 N/mm2 and 66.5%, respectively. Musa et al. investigated the possibility of using Lawsonia inermis (henna) leaves as a retanning agent for the wet blue leather and the physical properties of the resulting leather were compared with those of the leather retanned using wattle [42]. Henna-retanned leather recorded good tightness and their dyeing characteristics were better in comparison to the wattle-retanned leather. The shrinkage temperature of the wet blue leather was 109 °C while that of the henna-retanned and the wattle-retanned leather was 121 °C and 123 °C, respectively. The organoleptic properties of the henna crust leather, such as fullness, grain tightness, roundness, grain smoothness, softness and general appearance, were superior to those of the wattleretanned crusted leather. The tensile strength, elongation, tear strength, load at grain crack and distension at grain of the experimental leathers were 25.23 N/mm2, 60.15%, 39.93 N/mm, 24 kg and 10.64 mm, respectively, while those for control leathers were 25.09 N/mm2, 64.58%, 42.37 N/mm, 26 kg and 11.6 mm, respectively. In this case, the strength values of the leather retanned with henna met the standards stipulated by UNIDO [31]. The study also alluded to the possibility of using henna leaves as mordanting agents. Apart from the use of tannic acid as an explicit tanning agent, Colak et al. investigated the antioxidant effects of tannic acid on the formation of formaldehyde and Cr (VI) in leathers [43]. The wet blue sheepskins were treated with tannic acid of concentrations of 0.1, 0.5, 1, 2, and 3% during the retanning process. It was observed that increasing tannic acid concentration significantly improved the physical properties of the resulting leathers. The tensile strength, percentage elongation, tear load and shrinkage temperature at 3 wt. % tannic acids were 17.8 N/mm2, 49.5%, 35.9 N/cm, and 130.8 °C, respectively. Bitlisli et al. determined the physical properties of the split suede leather treated with Aloe barbadensis miller L. (Aloe vera) and chromium [44]. When compared with the physical properties of leather tanned
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with chromium only, the tear strength of the leather treated with Aloe vera 6% wt. weas comparatively higher. The Aloe vera concentrations improved the moisture content and the softness of the final leather. Affiang et al. developed a fatliquoring system by using seed oil extracted from the Aradirachta indica (neem) [45]. They sulphated the extracts by using sulphuric acid followed by the addition of sodium hydroxide in order to maintain the pH at 5.0. The physical properties of the chromed goatskins processed by this fatliquoring system were compared with those processed by using the imported palm oil fatliquor. The tensile strength, elongation at break and tear resistance of experimental leathers were 14.15 N/mm2, 49.0% and 61.01 N, respectively, while those of the control leathers were 19.03 N/mm2, 56% and 67 N, respectively. The organoleptic properties for the experimental leathers were comparable to the control leathers and the difference was insignificant. Sivakumar et al. used castor oil as a vegetable-based fatliquor and fatliquored the chromed leather [46]. The results indicated that the strength properties of the leather fatliquored by these oils were comparable to those of the leather fatliquored by using other imported fatliquors. The strength properties of the leathers were above the quality standards for tensile strength as per UNIDO [31]. Quadery et al. extracted fatliquor oils from Pongamia pinnata L. (Karanja) seed oil by sulphation process followed by the addition of sodium hydroxide to maintain the pH at 5.0 with concentrated sulphuric acid [47]. The prepared fatliquor was applied for the processing of chrome-tanned goatskins. The physical properties of skins were compared with those of the skins fatliquored by fatliquor from castor oil. The tensile strength, elongation and tear resistance of the leather fatliquored with experimental oils were comparable with those fatliquored by using imported fatliquors. Kusumawati et al. evaluated the effect of using different concentrations of Indigofera tinctoria L. (indigo), as a natural dye, to the quality of chrome-tanned milkfish skins [48]. The concentrations used were 20%, 25% and 30%. The results showed that different concentrations have significant effect (p < 0.05) on the rub resistance on wet and dry coating, fastness to perspiration, tensile strength and elongation at break of the resulting leather. The 25% concentration gave the best quality in terms of the physical properties and dyeing characteristics. The highest score for tensile strength was obtained when using 30% indigofera solution showing the score of 18.94 N/mm2. This value was higher in comparison to the value of the synthetic dyeing system; a fact attributed to the significant content in indigofera.
Tanning processes involving vegetable tannins, organic compounds and other non-chromium inorganic materials Haroun et al. investigated the interactions of Acacia nilotica spp. tomentosa pods (garad), used as a vegetable tanning agent, and aluminium sulphate, with collagens at pretannage and retannage stages [49]. In this tanning system, the authors evaluated two methodologies; the authors compared the vegetable pretannage followed by aluminium sulphate retannage with that of the reversed order, aluminium pretannage followed by vegetable retannage. Indeed, the former methodology resulted in superior leather with optimum results obtained when 10% and 2% of vegetable tannins and aluminium sulphate were used, respectively. The optimum concentrations of the garads improved the percentage elongation of the final leather to 60.5% and the shrinkage temperature, pretanned with different aluminium retanning, to 125 °C. This is probably due to the enhanced cross-links, stabilized complexes and new bond formation that eventually increased hydrothermal stability of the resulting leather. The tensile strength of leather using the former methodology similarly showed higher values compared to the latter methodology. This study unravels a chromefree tannage system that yields leathers of shrinkage temperature greater than 100 °C, elongation of 65.6%,
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and tensile and tear strengths of 38 N/mm2 and 98 N/cm, respectively. The study showed that a combination of vegetable tannage of garad followed by aluminium sulphate retannage effectively crosslinks collagens, resulting in good quality leather as evidenced by high strength properties and shrinkage temperatures. Musa and Gasmelseed developed a combination tanning system based on garad and aluminium [50]. Results showed that a combination system of 2% of Al2O3 followed by 20% of garad produces leathers of shrinkage temperature above 101 °C. Similarly, the physical properties were above the UNIDO-recommended minimum. The study attributed the excellent hydrothermal stability and physical properties to aluminium, which enhances amount of garad fixation as indicated by the increased garad exhaustion. Musa et al. and Musa et al. extended the research area by evaluating the combination tanning process based on Lawsonia inermis (henna) leaf extract and tetrakis hydroxymethyl phosphonium sulphate (THPS) and aluminium sulphate, respectively, for production of upper leather [51,52]. In the evaluation of this regime, two methodologies involved varying the order in the combination; henna extracts (20%) followed by tetrakis hydroxymethyl phosphonium sulphate (1.5%) and tetrakis hydroxymethyl phosphonium sulphate followed by henna extracts. The second permutation resulted with superior leathers, both in strength and organoleptic properties and the shrinkage temperature of 96 °C. Also compared with the leathers tanned with henna alone (control), the shrinkage temperature dropped to 84 °C. From this study, generally leathers tanned with henna and THPS showed better fullness, dye uniformity, softness, smoothness and general appearance. Similarly, the strength properties of the experimental leathers were above the minimum required standards. More so, the use of THPS increased henna fixation and exhaustion, which may explain the increased shrinkage temperature observed. Aravindhan et al. evaluated the Tara-THPS combination tannage system [53]. Pretannage with glutaraldehyde or THPS were employed in order to improve the tannin uptake/penetration. The resulting leathers recorded shrinkage temperature of 88 °C. The system was found versatile in tannage of both upper and garment leather since the strength and organoleptic properties were similar to those of the leather tanned with chromium. This combination is effective since it also has both scavenging effect of free formaldehyde and Cr (VI). The adjunct of THPS has additional importance. In the subsequent study by Plavan et al., the tanning process was based on using Tara and mimosa tannins with an aluminium adjunct as tanning agents [54]. Leathers tanned with Tara tannins have more stable properties than those not tanned with those tannins. The developed technology produced leathers with the shrinkage temperature of 98 °C, tensile strength of 18.2 N/mm2, and elongation at break of 42%. The shrinkage temperature was enhanced up to 106 °C as a result of treating the pelt with THPS in the place of chromium before tanning with Tara-aluminium. Tannic acid, as a precursor, has been used immensely in the leather tanning process as a green material. This is partly due to its low molecular weight compared to other vegetable tannins, which allows it to effectively penetrate the collagen fibres. Fathima et al. studied the tanning system combining tannic acid, aluminium and silica [55]. Apart from improving the hydrothermal stability, the presence of aluminium in the precursor of tannic forms an aluminium-tannic acid complex that gives the leather a pastel colour. The presence of silica in the system gives the leather softness and a fluffy feel. The shrinkage temperature was found to increase with sodium metasilicate and aluminium sulphate offers. It was shown that 5% of both sodium metasilicate and aluminium sulphate concentrations were optimum for better results. The strength and organoleptic properties were either comparable to or higher than those of the conventionally chrometanned leather. The optimum amount of tannic acid, aluminium sulfate and sodium metasilicate was found to be 10, 5, and 5 wt. %, respectively, which correspondingly yielded leathers with the shrinkage temperature of up to 95 °C. In a related study by Saravanabhavan et al., a combination tannage system based on tannic acid (10%), zinc (10%) and silica (5%) was used to tan garment leathers [13]. The physical strength and 142 www.textile-leather.com
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organoleptic properties of the leather from the experimental system were generally comparable to those of the leather tanned using chromium salts, while the shrinkage temperature was 85 °C. Later, Fathima et al. developed an organic tanning system using a vegetable tannin precursor of tannic acid and THPS as an alternative to the chrome tanning system [56]. There was no difference between the physical and organoleptic properties of the experimental leather and the chrome-tanned leather. Furthermore, the shrinkage temperature of the experimental leather increased to as high as 88 °C. Ding et al. used a combination of genipin and aluminium for the tanning process and evaluated the physical properties of the resulting leather against the aluminium-glutaraldehyde and mimosa-aluminium leathers prepared as controls [57]. In this system, bated pelts were pretanned with the 6%-aluminium and then tanned with the 6 wt. %-genipin. The shrinkage temperature of the leather produced by this technology was 89 °C (measured by DSC) and 92 °C when measured using traditional measurement. The physical-mechanical properties of the experimental leathers were similar to those of the leather used for the control in the experiment. Ali et al. used extracts from Faidherbia albida (Haraz) combined with aluminium as an alternative tanning system for the production of upper leathers [29]. The system involved altering the order of application commutatively i.e., applying Haraz followed by aluminium and applying aluminium followed by Haraz with the concentrations of 20% of Haraz and 2% of Al2O3 by weight. The shrinkage temperature in the Haraz-Al methodology was 100 °C, and 98 °C in the Al-Haraz methodology. Similarly, Haraz-Al combination system resulted in leathers with better organoleptic and strength properties that satisfy the standard of quality leather.
Tanning processes that involved using vegetable tannins and other organic materials Omur and Mutlu chemically modified the condensed tannins from mimosa and quebracho by applying sulphitation, sulpho methylation and novalac synthesis [58]. The aim was to enhance the colour fastness of mimosa- and quebracho-tanned leathers that usually change colour and darken upon exposure to light for a prolonged period. Leathers tanned with tannins from quebracho and sulpho-methylated mimosa exhibited improved colour fastness to light [10]. Incorporating UV stabilized groups into flavonoid structures of both quebracho and mimosa was done in order to inhibit bond rearrangements by oxidative free radical mechanism. The modification did not significantly alter the physical properties, which agreed closely with those tanned with standard tannins. The values of strength properties were within the recommended standard limits.
Tanning processes utilizing pure vegetable tannins Later Musa and Gasmelseed studied the possibility of using the garad as a vegetable tanning agent for upper leather [59]. In the study, they compared the physical properties of the leathers tanned with garad with those tanned with chromium. The difference between the tensile strength, tear strength, elongation at break, load at grain and distension at grain crack were not significant (p<0.05). In the same study, the researchers extended the tanning system by combining garads and Oxazolidine tannage for production of garment leathers. Investigating different concentrations of garad powder and oxazolidine, a combination of 20% of garad powder and 4% of oxazolidine provided a shrinkage temperature of 102 °C. The system also produced leathers with good organoleptic properties and physical properties comparable to the chromium tanning system. Later, Ozkan and co-workers investigated the prowess of vegetable tannins of Acacia nilotica L. for tannage and determined a spectrum of the resulting physical characteristics [40]. The lasto-
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meter tests were as follows: strength at grain crack - 30.5 N, grain distension at crack - 14.68 mm, strength at ball burst - 35.5 N, ball burst grain distension - 15.67 mm, tensile strength - 21.69 N/mm2, percentage elongation - 86.66%, and tear load - 70.06 N. In the subsequent study, Ali et al. combined 80% of Acacia nilotica pods (garads) and 20% of Azadirachta indica (neem) barks spray-dried powder mixture as a full vegetable tanning system to produce shoe upper leathers [58]. The parameters of the resulting leathers were as follows: tensile strength - 20 N/cm2, tear strength - 4.4 N/cm, percentage elongation - 40.5%, grain distension - 8.9 mm and shrinkage temperature > 82 °C. The results showed that the garad-neem blend enhances the quality of the final leather to almost double the magnitude of the leather tanned by conventional pure Acacia nilotica pods (garads). The blend also improved the fullness and fellness, quality parameters recommended for good leather. The complementing effect arises from the fact that Acacia nilotica contains hydrolysable tannin while Azadirachta indica bark contains condensed tannin. A comparative study done by Kuria et al. assessed the physical properties of leathers tanned Acacia xanthophloea, Acacia nilotica, standard mimosa and Hagenia abyssinica plants [62]. Leathers tanned with Acacia xanthophloea recorded the highest shrinkage temperature of 85 °C, while that of the leathers tanned with commercial mimosa, Acacia nilotica and Hagenia abyssinica was 83 °C, 82.5 °C and 80 °C, respectively. However, the leather tanned with Acacia xanthophloea recorded the lowest tensile strength of 20 N/mm2, while Hagenia abyssinica, commercial mimosa and Acacia nilotica had a tensile strength of 27.91 N/mm2, 28.8 N/mm2 and 29.22 N/mm2, respectively. Hussein [63] extracted the tannins from Acacia seyal bark (Taleh), whose content was determined to be 28.9%, and used them for retanning the upper and garment materials. With this content of tannins, Taleh forms a potential source of tannins for both vegetable tanning and retanning. Furthermore, the resulting leather exhibited competitive quality in terms of strength properties. For instance, the range of tensile strength was 21.5-31 N/mm2 and the percentage of elongation was 42-63.5%. Nasr et al. investigated vegetable tanning systems that involved quebracho and mimosa plant extracts [64]. They then compared the physical properties of the resulting tanned leather with those of chrome-tanned leather. From the results, chrome-tanned leather had the highest tensile and tear strengths, elongation and water permeability followed by quebracho-tanned leathers and then mimosa-tanned leathers. The superiority of quebracho over mimosa could be explained by higher tannin content (35%) against 18% of tannin content in mimosa. Huantian et al. used the 20%-quebracho solution as a vegetable tannin for the tanning process and leathers recorded a shrinkage temperature of 78.4 °C [65]. When the quebracho tanning was followed by posttreatment with transglutaminases (enzymes), the shrinkage temperature slightly improved by 2 °C. When quebracho was combined with transglutaminase and laccase (another enzyme) in a one-step treatment, the shrinkage temperature increased to 84 °C. Conclusively, enzymes assisted in the collagen crosslinking and the phenol oxidizing hinders the uptake or penetration of the tannins into the leather. The eucalyptus bark contains simple phenolics, such as gallic, ellagic and protocatechuic acid, as well as derivatives and flavonoids. It also contains complex polyphenolic compounds, such as ellagitannins (hydrolysable tannins) and proanthocyanidins (condensed tannins). Pinto et al. [66] characterized the eucalyptus globule bark as a source of tannin extracts and applied them for the retanning process. The results from the study showed that all the strength properties fulfilled the required minimum standards.
CONCLUSION This review compiles the papers on the use of natural plants in the leather tanning process and the way their use impacts the quality of the resulting leather. This lays the foundation for the possibility of their adoption in the leather tanning industry due to the adherence to standards. The reviewed literature focused 144 www.textile-leather.com
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on studies that employed natural plants or extracts or combinations of natural plant extracts and showed the physical properties of the final leathers. The natural plants have been demonstrated to be effective in improving several physical and organoleptic properties of interest to the quality of leather, mainly the tensile strength, tear strength, elongation, distension at grain crack and grain burst. Although most studies were conducted with physical and organoleptic properties in mind, the overall concerns of the leather industry need to be addressed. As much research delves into plant products that replace synthetic agents and producing leathers with greater variety of property profiles which can compete favourably with synthetic leather, the actual leather must adhere to both human and environmental health. The safety of these leathers for a direct contact with the foot must be achieved. The overall and specific plant products must be tested thoroughly to demonstrate the novelty in their use and meet the stringent requirements. The application of some plants may be limited due to their insufficient quality, safety and lifespan of their usage. More research is needed to unravel suitable extraction methods, possible synergy of plants and plants that can possibly reduce the toxicity of chromium use. Funding This research was funded by the National Research Fund-Kenya (NRF-KE) of 2016/2017. Conflicts of Interest The authors declare no conflict of interest.
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[27] Valeika V, Sirvaityte J, Beleska K. Estimation of Chrome-free Tanning Method Suitability in Conformity with Physical and Chemical Properties of Leather. Material Science. 2010; 16(4):330-336. [28] Basil-Jones MM, Edmonds RL, Cooper SM, et al. Collagen Fibril orientation and tear strength across ovine skins. Journal of Agricultural and Food Chemistry. 2013; 61(50):1227-1233. [29] Ali SB, Haroun HE, Musa AE. Haraz Bark Powder extract for manufacture of Nappa upper leather as alternative retanning agent. Journal of Forest Products and Industries. 2013; 2(5):25-29. [30] Liu CK, Latona NP, Taylor M, et al. Characterization of mechanical properties of leather with airborne Ultrasonics. Journal of the American Leather Chemists Association. 2015; 110(3):88-93. [31] UNIDO. Acceptable quality standards in the leather and footwear industries, United Nations Industrial Development Organization, Vienna. 1996. [32] SATRA. Shoe and allied trade research association. Testing Equipment Catalogue. 2011. [33] ESA (Ethiopian Standards Agency). The quality standards for leather and leather products, Addis Ababa, Ethiopia. 2012. [34] INESCOP (Center for Technology and Innovation). Available from: http://www.manual for Oxazolidine Tanned Leather: Environmentally Friendly Oxazolidine-Tanned Leather (LIFE08 ENV/E/000140).com. Accessed on June 21, 2013. [35] Ashebre M. Performance of leather uppers of local footwear products and the determinants. International Journal of Advancement in Technology. 2014; 3:26-30. [36] Inanc L, Gulumser G. Determination of the Effects of Splitting and Shaving Operations before Tanning at Shoe Upper Leathers on the Quality of Leather. Tekstil ve Konfeksiyon. 2015; 25(4):365-370. [37] Cloete SWP, van Schalkwyk SJ, Brand TS, et al. The effects of dietary energy and protein concentrations on ostrich skin quality. South African Journal of Animal Science. 2006; 36(1):40-44. 10.4314/ sajas.v36i1.3984 [38] Ibrahim AA, Youssef MSA, Nashy E-SHA, Eissa MM. Using of Hyperbranched Poly (amidoamine) as Pretanning Agent for Leather. International Journal of Polymer Science. 2013; 1-8. [39] Musa AE, Aravindhan R, Madhan B, et al. Henna–aluminium Combination tannage: a greener alternative tanning system. Journal of the American Leather Chemists Association. 2011; 106(6):190-199. [40] Musa AE, Gasmelseed GA et al. Eco-friendly Vegetable Combination Tanning System for production of hair-on shoe upper leather. Journal of Forest Products & Industries. 2013; 2(1): 5-12. [41] Sirvaityte J, Siugzdaite J, Valeika V, Dambrauskiene E. Application of essential oils of thyme as a natural preservative in leather tanning. Proceedings of the Estonian Academy of Sciences. 2012; 61(3): 220–227. [42] Musa AE, Madhan B, Madhulatha W, et al. Henna extract: Can it be an alternative retanning agent? Journal of the American Leather Chemists Association. 2008; 103(6):188-193. [43] Colak SM, Dandar U, Kilic E. Antioxidant Effect of Tannic Acid on Formation of Formaldehyde and Hexavalent Chromium Compounds in Leather. Tekstil ve Konfeksiyon. 2014; 24(1):105-110. [44] Bitlisli BO, Yasa I, Aslan A, et al. Physical and antimicrobial characteristics of Aloe vera treated split suede leather. Journal of the American Leather Chemists Association. 2010; 105(2):34–40. [45] Affiang SD, Ggamde G, Okolo VN, et. Synthesis of Sulphated-Fatliquor from Neem (Azadirachta Indica) Seed Oil for Leather Tannage. American Journal of Engineering Research (AJER). 2018; 7(4):215-221. [46] Sivakumar V, Prakash PR, Rao PG, et al. Power ultrasound in fatliquor preparation based on vegetable oil for leather application. Journal of Cleaner Production. 2008; 16(4): 549-553. [47] Quadery AH, Uddin MT, Azad MAK, et al. Fatliquor preparation from Karanja seed oil (Pongamia pinnata L.) and its application for leather processing. IOSR Journal of Applied Chemistry. 2015; 8(1):54-58. www.textile-leather.com 147
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[48] Kusumawati F, Riyadi PH Rianingsih L. Applications Indigo (Indigofera tinctoria L.) as Natural Dyeing in Milkfish [Chanos chanos (Forsskal, 1775)] Skin Tanning Process. Aquatic Procedia. 2016; 7:92–99. [49] Haroun M, Palmina K, Gurshi A, Covington D. Potential of Vegetable Tanning Materials and Basic Aluminium Sulphate in Sudanese Leather Industry. Journal of Engineering Science and Technology. 2009; 4(1):20-31. [50] Musa AE, Gasmelseed GA. Development of Eco-friendly Combination Tanning System for the Manufacture of Upper Leathers. International journal of advance industrial engineering. 2013; 1(1):9-15. [51] Musa AE, Madhan W, Rao JR, et al. Colouring of leather using henna-natural alternative material for dyeing. Journal of American Leather Chemists Association. 2009; 104(5):183-190. [52] Musa AE, Madhan B, Kanth SV, et al. Cleaner tanning process for the manufacture of upper leathers. Clean Technologies and Environmental Policy. 2010; 12:381–388. [53] Aravindhan R, Madhan B, Rao RJ. Studies on Tara-Phosphonium Combination Tannage: Approach towards a Metal Free Eco-Benign Tanning System. Journal of American Leather Chemists Association. 2015; 110(3):80-88. [54] Plavan V, Koliada M, Valeika V. Eco-benign semi-metal tanning system for cleaner leather production. Journal of society of leather technologists and chemists. 2017; 101(5):260-265. [55] Fathima NN, Saravanabhavan S, Rao RJ, Nair BU. An Eco-Benign Tanning System Using Aluminium, Tannic Acid, and Silica Combination. Journal of American Leather Chemists Association. 2004; 99(2):73-781. [56] Fathima NN, Aravindhan R, Rao JR, Nair BU. Tannic Acid-Phosphonium Combination: A Versatile Chrome-Free Organic Tanning. Journal of American Leather Chemists Association. 2006; 101(5): 161-168. [57] Ding K, Taylor MM, Brown EM. Tanning effects of aluminium- Genipin or vegetable tannin combinations. Journal of American Leather Chemists Association. 2008; 103(11):377-382. [58] Ali AEH, Gasmelseed GA, Ahmed AH. Utilization of Improved Indigenous Tannins of Grain Powder (Acacia Nilotica) in Eco Friendly Tannage. International Journal of Multidisciplinary and Current Research. 2016; 4:14-20. [59] Omur S, Mutlu MM. Modification of Mimosa and quebracho tannins and the lightfastness properties of the processed leathers. Tekstil ve Konfeksiyon. 2016; 26(2):230-235. [60] Ozkan CK, Zengin ACA, Dandar U, et al. A new vegetable tanning material for leather industry: Acacia nilotica L. XXXIII IULTCS Congress November 24th – 27th, 2015 Novo Hamburgo/Brazil, 169-174. [61] Kuria A, Ombui J, Onyuka A, et al. Quality Evaluation of Leathers Produced by Selected Vegetable Tanning Materials from Laikipia County, Kenya. IOSR Journal of Agriculture and Veterinary Science. 2016; 9(4):13-17. [62] Hussein SA. Utilization of Tannins Extract of Acacia seyal Bark (Taleh) in Tannages of Leather. Journal of Chemical Engineering & Process Technology. 2017; 8(3):1000334. [63] Nasr AI, Abdelsalam MM, Azzam AH. Effect of tanning method and region on physical and chemical properties of Barki sheep leather. Egyptian Journal of Sheep and Goat Sciences. 2013; 8(1):123-130. [64] Huantian C, Changqing W, Crescent S, Leslie S, Wenging X. Final report environmentally friendly leather tanning using enzymes. EPA Grant Number: SU835511. 2014. [65] Pinto PCR, Sousa G, Crispim F, et al. Eucalyptus globulus Bark as Source of Tannin Extracts for Application in Leather industry. ACS Sustainable Chemistry & Engineering. 2013; 1(8):950-955.
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BRNADA S, et al. Biaxial Cyclic Loading of Woven Fabrics. TLR 4 (3) 2021 149-159.
Biaxial Cyclic Loading of Woven Fabrics Snježana BRNADA1*, Stana Kovačević1, Irena ŠABARIĆ2, Lovro DRŽAIĆ3 University of Zagreb Faculty of textile technology, Department of Textile Design and Management, Prilaz baruna Filipovića 28a, Zagreb, Croatia 2 University of Zagreb Faculty of textile technology, Department of Fashion Design, Prilaz baruna Filipovića 28a, Zagreb, Croatia 3 AWT International d.o.o., Zagreb *snjezana.brnada@ttf.unizg.hr 1
Article UDC 677.024 DOI: 10.31881/TLR.2020.22 Received 18 December 2020; Accepted 31 March 2021; Published Online 14 April 2021; Published 7 September 2021
ABSTRACT For the purpose of this paper, investigations were carried out on specifically designed fabrics with different structural parameters. The biaxial cyclic loading of fabrics and its consequences were investigated. The weave structures with the smallest weave units (plain weave, basket weave 2/2, rib weave 1/1 (2+2) and rib weave 2/2 (1+1) with the same warp and weft density (24 ends/cm and 24 picks/cm) were selected. Biaxial cyclic loadings of fabrics were performed on a newly developed patented device. The influence of the low level of cyclic loadings of fabrics on the change of tensile properties in warp and weft direction was investigated. The results showed that the low level of biaxial cyclic loading can lead to a permanent linear deformation of fabrics. Despite the fact that the forces that cyclically strain the fabric in two directions amount to 10% of the breaking elongation, after a certain number of cycles there is an irreversible deformation and reduction of breaking forces, but sometimes they can result in an increase in breaking forces. It was found that the tensile elongation of fabrics is affected both by thread crimping and by the structural properties of fabrics resulting from changes in the weave. KEYWORDS Biaxial cyclic loading of fabrics, Fabric deformation, Weave structures of fabrics, Tensile elongation of fabrics
INTRODUCTION The market share of fabrics for technical purposes is increasing, as a substitute for many other materials such as steel, iron and generally components of massive constructions. In addition to their strength, resilience, durability and protection, they also feature other important properties, such as being the load-bearing component in composites, lightweight, pliable and breathable, all according to the targeted use. Fabrics used for technical purposes are exposed to extreme conditions, either weather conditions or various mechanical impacts. Multidirectional loading often occurs during the application of fabrics and can be long lasting and intense, such as in the application of fabrics in road construction, civil engineering, transport, industry, agriculture, protection, etc. Likewise, fabrics are often exposed to the low level of cyclical loading, such as in car seat covers, where deformation can occur after a certain time.
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BRNADA S, et al. Biaxial Cyclic Loading of Woven Fabrics. TLR 4 (3) 2021 149-159.
A fabric is an orthotropic material with two axes of symmetry (warp and weft direction) in which its mechanical properties are extreme (moduli, maximum breaking force, minimum elongation at break) [1,2]. The authors of the paper [3] performed an experiment on laminated fabric by subjecting it to uniaxial, uniaxial cyclic and biaxial cyclic loading to expose the detailed mechanical behaviours and determine proper elastic parameters for the laminated fabrics under specific stress states. They observed three degrees of tensile behaviour of the fabrics (crimp region, nonlinear transition region and yarn extension region). In order to be able to predict the behaviour of the fabric as a whole, more extensive research is needed regarding the low loads (up to 10% of the maximum breaking elongation) and a solution should be found when designing it. In their research [4], the authors divided the plain weave unit into small parts and applied a mechanical model to each of them in order to predict fatigue strength of a plain-woven fabric reinforced composite subjected to multiaxial cycling loads. They commented that the “agreement between the predicted and available experimental results is reasonable”. The properties of fabrics, which depend on fibres, yarns and structures and their mutual contractions, have been investigated and presented in the literature [5-8]. For woven materials, there is a rule that the warp and weft run in the direction of the highest loading [9-11]. Due to the action of the external forces, the fabric is subjected to tensile loading. From the perspective of material behaviour, loading is the internal distribution of forces that creates an equilibrium in response to the loads impacting the fabric. When the fabric is subjected to tensile and cyclic loading, its dimensional and mechanical properties change, and a material fatigue occurs [12,13]. Material fatigue should provide answers to very important questions, such as the expected number of cycles the material can withstand and that its mechanical properties are kept within the recommended areas of application. Most often these are low loads that occur in two or more directions. Fabrics exposed to these loads experience changes in properties, especially mechanical ones, which depend on two groups of factors: a) The internal factors relating to the structure and the material, including fibres, yarn, fabric density, the mass and the weave structure. b) The external factors relating to the test conditions, such as cycle duration, loading level and the number of cycles. In their review, the authors discussed the results of experimental investigations under monotonic and cyclic loadings [14]. They noted that composite materials could exhibit complicated behaviour in the biaxial loading conditions that often exist in engineering practice. In conclusion, they indicate, among other things, that flat cruciform specimens are appropriate for a biaxial test, if the ‘edge effects’ can be overcome by introducing a central notch or deep-cut edge notches in the specimens. They also point out the simplicity of performing the biaxial test and interpreting the results. In their paper [15], the authors investigated the fatigue of E-glass/polyester fabrics due to cyclic loading. They concluded that the fabric biaxial pre-stressing can extend the fatigue in the intermediate and lowstress regions of composites with woven fabric as reinforcement. Also, increased off-axis orientation is crucial for prolonging fatigue life. The aim of this paper is to examine the consequences of the low level of biaxial cyclic loading of fabrics of different structures, i.e., to investigate to what extent biaxial cyclic loading of fabrics affects tensile properties of fabrics. In the study [16], uniaxial and biaxial tests were performed to analyse the biaxial cyclic behaviours with different stress ratios. The tests were performed on coated woven fabrics. They found that the material’s tensile strength after cyclic loading remains almost unchanged, which may be related to the lower number of cycles and that the tensile behaviours under cyclic loading are mainly related to the stress amplitude, the temperature, and the structure of woven fabric. 150 www.textile-leather.com
BRNADA S, et al. Biaxial Cyclic Loading of Woven Fabrics. TLR 4 (3) 2021 149-159.
In the paper [17], the authors stated that, although the uniaxial strength was studied extensively, it cannot properly characterize the real strength of the woven fabric composite due to the normal biaxial tensile state in operation service. They found that the biaxial strength equals the lower uniaxial strength multiplied by an amplification factor of 1.1–1.3 under a 1:1 stress ratio.
EXPERIMENTAL Research was carried out on mechanical behaviour of fabrics that were subjected to conditions of biaxial cyclic loading in both warp and weft direction. The research was conducted on plain weave fabrics (P) and plain weave derivatives: basket weave 2/2 (B), rib weave 1/1 (2+2) (R1) and rib weave 2/2 (1+1) (R2). Due to their stable structure and loading resistance, these weaves are often used in the production of technical fabrics that will be subjected to cyclic loading during use (e.g., car covers, car seat covers, mobile buildings, road construction, civil engineering, etc.).
Materials The basic parameters of warp and weft yarn are: 100% cotton, yarn count 36 tex, number of twists 505 twists/m, breaking force 4.26 N, elongation at break 6.4%, strength 11.8 cN/tex. The tests were carried out on fabrics of the same density in warp and weft (24 threads/cm) in four weaves. The samples were woven from the same lot of warp and weft on a Picanol air-jet weaving machine in the textile factory Čateks, Čakovec. Further fabric properties related to weave structures are listed in Table 1, which presents the design parameters of fabrics and their structural properties. The breaking forces and elongation at break areThe shown Table 2.fabric has the highest mass per unit area, the smallest thickness, but also the plaininweave The plain weave fabric has the mass per unitper area, thearea, smallest but also thebut greatest weft The plain weave fabric hashighest the highest mass unit the thickness, smallest thickness, also the greatest crimp (Table 1).the highest mass per unit area, the smallest thickness, but also the The plainweft weave fabric has crimp (Table 1). crimp greatest (Table 1).the highest mass per unit area, the smallest thickness, but also the The plainweft weave fabric has greatest weft crimp (Table 1). greatest weft crimp (Table 1).1.1.Basic Table to weave weavestructures structures Table Basicproperties propertiesof offabrics fabrics related to Weave Weave Weave Plain Plain Weave Plain Plain
Plain Basket Basket Basket Basket Basket Rib 1/1 Rib 1/1 Rib 1/1 Rib 2/2 1/1 Rib Rib 2/2 Rib 2/2 Rib 2/2
Table 1. Basic properties of fabrics related to weave structures Density Mass per related to weave structures Table 1. Basic properties of fabrics Density Thickness Mass per unit Thickness (threads/cm) X // CV Designation CV unit area Designation (threads/cm) Table 1.XBasic properties of fabrics related to weave structures (mm) Density 2 2) area (g/m (mm) (g/m ) Mass per unit Thickness Warp Weft DensityWeft Warp Designation / CV (threads/cm) X Mass per unit Thickness 2 Designation area (g/m2) (mm) (threads/cm) X / CV DensityWeft Warp area (g/m ) (mm) 186,7 0,332 24,2 24,0 Mass per unit Thickness X 186,7 0,332 24,2 24,0 Warp Weft Designation (threads/cm) X /XCV 2 P area (g/m ) (mm) 186,7 0,332 24,2 24,0 P X Warp Weft CVX(%) 0,1 1,061 1,7 0 186,7 0,332 24,2 24,0 P CV (%) 0,1 1,061 1,7 0 P CVX(%) 0,1 1,061 1,7 0 186,7 0,332 24,2 24,0 178,8 0,379 24,3 23,7 CV (%) 0,1 1,061 1,7 0 X P B 178,8 0,379 24,3 23,7 178,8 0,379 24,3 23,7 CVXX(%) 0,1 1,061 1,7 0 CVX(%) 0,6 0,949 2,0 2,0 178,8 0,379 24,3 23,7 BB B CV 0,6 0,949 2,0 2,0 178,8 0,379 24,3 23,7 X(%) CVX (%) 0,6 0,949 2,0 2,0 177,1 0,377 24,5 24,0 CV (%) 0,6 0,949 2,0 2,0 B R1 177,1 0,377 24,5 24,0 CVX(%) 0,6 0,949 2,0 2,0 CVXX(%) 0,7 0,886 2,2 3,4 177,1 0,377 24,5 24,0 177,1 0,377 24,5 24,0 R1 R1 CV (%) 0,7 0,886 2,2 3,4 177,1 0,377 24,5 24,0 R1 X 178,1 0,376 24,4 24,3 CVX(%) 0,7 0,886 2,2 3,4 R1 CV (%) 0,7 0,886 2,2 3,4 R2 178,1 0,376 24,4 24,3 CVX(%) 0,7 0,886 2,2 3,4 CV (%) 0,9 1,152 2,1 2,0 178,1 0,376 24,4 24,3 X R2 R2 178,1 0,376 24,4 24,3 CVXX(%) 0,9 1,152 2,1 2,0 178,1 0,376 24,4 24,3 CV (%) 0,9 1,152 2,1 2,0 R2 R2 CV 0,9 1,152 2,1 2,0 CV(%) (%) 0,9 1,152 2,1 2,0
Crimp (%) Crimp (%) Crimp (%) Warp Weft Warp Weft Crimp (%) Warp Weft 7,9 8,2 Crimp (%) 7,9 8,2 Warp Weft 7,9 Warp 5,7 7,9 5,7 5,7 7,9 3,6 5,7 3,6 3,6 5,7 4,2 3,6
8,2 Weft 8,1 8,2 8,1 8,1 8,2 9,0 8,1 9,0 9,0 8,1 6,4 9,0
4,2 3,6 4,2 6,3 4,2
6,4 9,0 6,4 5,6 6,4
6,3 4,2 5,1 6,3 6,3 5,1 6,3 1,8 5,1 5,1 1,8 5,1 6,8 1,8
5,6 6,4 5,3 5,6 5,6 5,3 5,6 9,8 5,3 5,3 9,8 5,3 5,5 9,8
1,8 6,8 1,8 6,8
9,8 5,5 9,8 5,5
6,8 6,8
5,5 5,5
Working methods and test equipment Working methods and test equipment Working andof test The basicmethods parameters theequipment fabric structure were calculated as follows: determination of mass per Working methods and test equipment The basic parameters of the fabric structure were calculated as follows: determination of mass per unit basic area was determined accordance withwere the calculated ISO 3801:1977, thickness of the woven samples The parameters of thein fabric structure as follows: determination of mass per unit basic area was determined accordance withwere the calculated ISO 3801:1977, thickness of the woven samples The parameters of thein fabric as follows: of mass per was determined in accordance withstructure the ISO 5084:1996, number ofthickness warpdetermination andofweft per unit unit area was determined in accordance with the ISO 3801:1977, the threads woven samples www.textile-leather.com 151 was determined in accordance with the ISO 5084:1996, number ofthickness warp andofweft per unit unit area was determined in accordance with the ISO 3801:1977, the threads woven was determined in 1049-2:2003, and of thewarp determination of crimpsamples of yarn in accordance accordancewith withthe theHRN ISO EN 5084:1996, number and weft threads per unit was determined in with 1049-2:2003, and of thewarp determination of crimpper of yarn in accordance accordance withthe theHRN ISO EN 5084:1996, number and where weft threads unit in samples was conducted with the ISO 7211-3:1984, warp and waswoven determined in accordance with in theaccordance HRN EN 1049-2:2003, and the determination of crimp of weft yarn
BRNADA S, et al. Biaxial Cyclic Loading of Woven Fabrics. TLR 4 (3) 2021 149-159.
Working methods and test equipment The basic parameters of the fabric structure were calculated as follows: determination of mass per unit area was determined in accordance with the ISO 3801:1977, thickness of the woven samples was determined in accordance with the ISO 5084:1996, number of warp and weft threads per unit was determined in accordance with the HRN EN 1049-2:2003, and the determination of crimp of yarn in woven samples was conducted in accordance with the ISO 7211-3:1984, where warp and weft crimp are expressed in % as a length difference between the yarn woven in fabric and the straightened yarn in relation to the length of yarn in the fabric [18-21]. The testing of fabric tensile properties was carried out on the Textechno Statimat M tensile tester in accordance with the standard test method HRN EN ISO 13934-1:2008 [22]. The fabric samples were tested in warp and weft direction before and after cyclic loading. The device for samples preparation for measuring the resistance of technical textile materials to biaxial cyclic stress was patented under the patent number HR P20150735 A2. The number of loading cycles was 30,000 cycles and frequency was 80 cycles/min. The shape of the prepared sample is in a cross form (Figure 1b), with the dimensions of 500x500 mm, while the centre surface of the cruciform is 200×200 mm. The cyclic stress of the material is achieved by the vertical movement of a metal plate (floor), with the dimensions of 200×200 mm, with side rollers, which is acted upon by a force perpendicular to the surface of the sample from below. The force acting on the sample of moment. After the cyclic loading, the tensile properties of the fabrics were tested in accordance with the tested material is variable but could be calculated through the stiffness of the spring and the height of the modified ISO 13934 on three testing strips per sample direction. The dimensions of the monothe floor at the current moment. After the cyclic loading, the tensile properties of the fabrics were tested axial test specimens were 200x50 mm, wherein thetesting longer strips side was to the tensile in accordance with the modified ISO 13934 on three persubjected sample direction. Theloading. dimensions force at constant elongation the mm, maximum force elongation the samples were of theThe mono-axial test specimens wereand 200x50 wherein theand longer side wasofsubjected to the tensile loading. The force at constant elongation force and of the samples recorded. Elongation was calculated asand the the ratiomaximum of the elongation ofelongation the test specimen from thewere recorded. Elongation was calculated as the ratio of the elongation of the test specimen from the initial initial length, expressed as a percentage. length, expressed as a percentage.
a)
a)
b)
b)
Figure 1. (a) Biaxial loading apparatus for fabrics; (b) Sample dimension Figure 1. (a) Biaxial loading apparatus for fabrics; (b) Sample dimension
RESULTS Figures 2-5 show scattered diagrams of force-elongation point pairs for fabric samples. Point clouds
152 were www.textile-leather.com approximated by sigmoid curves, dose-response functions, and the area between the curves before and after cyclic preloading was calculated in order to determine the difference in mechanical
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RESULTS Figures 2-5 show scattered diagrams of force-elongation point pairs for fabric samples. Point clouds were approximated by sigmoid curves, dose-response functions, and the area between the curves before and after cyclic preloading was calculated in order to determine the difference in mechanical behaviour of fabrics. Sigmoid dose-response function, or S curve approximates the data (stress or force/strain) for tensile mechanical behaviour of the woven fabric with very high accuracy. The comparison of fabric breaking forces before and after cyclic loading with error intervals is shown in Figure 6, and regression lines and regression coefficients in Figure 7. By examining the fabrics before and after the cyclic loading depending on the weave structure, their differences can be determined, even though they are woven from the same yarn on the same loom and under the same conditions. Basket weave has the greatest thickness, transverse rib weave (R2) has the lowest warp crimp, but the highest weft crimp. Despite the fact that all samples were woven under the same conditions, there were large crimp differences in the warp direction (1.8% (R2) to 7.9% (P)) and in the weft direction (5.6% (R2) to 9.8% (R2)). The breaking forces before and after cyclic loading per specimens and test directions differ and do not follow the course of changes in other parameters, indicating that the breaking forces are mainly affected by the weave structure (Table 2). Rib weave (R2) has the highest breaking force in the warp direction before and after the cyclic testing (484/482 N), while plain weave has the highest breaking force in the weft direction (535/533 N). Basket weave (B) has mostly the lowest breaking force in warp and weft direction (warp 449/481, weft 440/431). Plain weave (P) has the highest elongation at break in the warp direction (16/14%), while basket and rib weaves have the highest elongation at break in the weft direction. Table 2. Basic properties of fabrics related to weave structures Test conditions
Weave designation
P B Before cyclic loading R1
R2
P
B After cyclic loading R1 R2
Breaking forces
Elongation at break
Test direction
X (N)
CV (%)
X (%)
CV (%)
Warp
476
3,2
16
2,7
Weft
535
8,0
18
1,9
Warp
449
5,9
9
3,4
Weft
440
4,1
19
3,0
Warp
478
2,2
14
3,1
Weft
449
1,8
13
3,0
Warp
484
1,9
9
1,4
Weft
490
2,9
19
0,2
Warp
452
8,0
14
15,7
Weft
533
1,9
15
4,0
Warp
481
0,9
7
5,8
Weft
431
8,4
14
1,0
Warp
467
1,6
11
6,3
Weft
444
2,6
10
2,3
Warp
482
1,8
8
1,5
Weft
484
1,9
13
3,6
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The difference in breaking forces of the specimens that are subjected to cyclic loading, compared to the ones that were not, is very small, although the consistency of slightly lower breaking forces for the samples that were subjected to cyclic loading is evident. The reason for the small deviations are the already mentioned relatively low cyclic loads at which the fabric slightly deforms (level of crimp straightening). An exception, however, is the basket weave in the warp direction, where the breaking forces in the cyclically loaded specimens are higher even after repeated measurements. The threads within the basket weave are looser, which allows them to interact, they are stretched at low loads, the fibres inside the yarn approach each other and are, therefore, more resistant. In materials with a fibrous structure, the load acts in the direction of the fibres, and if it isinside small it can such a way that is further adjusted the fibres the enough, yarn approach each act otherin and are, therefore, moreitresistant. In materials with aby stretching the fibrous the structure, thecloser load acts in the direction of the fibres, if it is small enough, it can act in structures, bringing fibres together in a yarn, whichand then becomes more compact and stronger. a way that it isreduced further adjusted by stretching thein structures, bringing the The elongationsuch at break was by cyclic loading all specimens in fibres bothcloser testtogether directions. The reason in a yarn, whichof then becomes compact and stronger. for this is the occurrence the linearmore deformation, i.e., an extremely small elongation in the elongation The elongation at break was reduced by cyclic loading in all specimens in both test directions. The direction, which could not be determined with statistical certainty. A comparison of crimp and mechanreason for this is the occurrence of the linear deformation, i.e., an extremely small elongation in the ical parameters shows the correlation between elongation at break and crimping, whereby higher thread elongation direction, which could not be determined with statistical certainty. A comparison of crimp crimping in the fabric leads to higher elongation at break. and mechanical parameters shows the correlation between elongation at break and crimping, Figures 2 to 5 show the tensile stress diagrams per weave structures in the warp and weft direction before whereby higher thread crimping in the fabric leads to higher elongation at break. and after cyclicFigures loading. 2 to 5 show the tensile stress diagrams per weave structures in the warp and weft direction before and after cyclic loading.
Figure 2. Tensile behaviour of the plain weave fabric before and after cyclic loading; where: warp_cycl – warp direction Figure 2. Tensile behaviour of the plain weave fabric before and after cyclic loading; where: warp_cycl – warp direction after cyclic loading, warp_non - warp direction before cyclic loading, weft_cycl – weft direction after cyclic loading, weft_ after cyclic loading, warp_non - warp direction before cyclic loading, weft_cycl – weft direction after cyclic loading, non – weft direction before cyclic loading weft_non – weft direction before cyclic loading
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Figure 3. Tensile behaviour of the basket weave fabric before and after cyclic loading
Figure 3. Tensile of the basket weave fabric after cyclic loading Figure behaviour 3. Tensile behaviour of the basket weave fabric beforebefore and after and cyclic loading
Figure 4. Tensile behaviour of theoflongitudinal ribweave weave fabric (R1)and before and after cyclic loading Figure 4. Tensile behaviour the longitudinal rib fabric (R1) before after cyclic loading Figure 4. Tensile behaviour of the longitudinal rib weave fabric (R1) before and after cyclic loading
Figure 5. Tensile behaviour of theoftransversal weave fabric (R2)and before and after cyclic loading Figure 5. Tensile behaviour the transversal rib rib weave fabric (R2) before after cyclic loading The results of the tensile test are shown by a scatter diagram, and the pairs of force-elongation
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points are approximated by the sigmoid curve, dose response. By integrating the curves in the tensile
area (until break) and adjusting the base curve of the unloaded specimen, the area under the curves
BRNADA S, et al. Biaxial Cyclic Loading of Woven Fabrics. TLR 4 (3) 2021 149-159.
The results of the tensile test are shown by a scatter diagram, and the pairs of force-elongation points are approximated by the sigmoid curve, dose response. By integrating the curves in the tensile area (until break) and adjusting the base curve of the unloaded specimen, the area under the curves of the cyclically loaded and unloaded specimen is highlighted for each weave and direction. The obtained surfaces represent the difference in the work of rupture, i.e., the energy required to break the material. From the resulting curves it is apparent that the biggest difference in energy required to break the material was in the transverse rib weave, in both directions (warp direction 542.96x10 -5J and weft direction 773.93x10 -5J). In other samples, the differences in the warp direction were greater than in the weft direction. The reason for this is a greater elongation of the samples in the weft direction relative to the direction of the warp, which has a higher tensile stiffness, i.e., higher stress. In all cases, the non-linear behaviour of the stress-strain curves graphically displayed in the coordinate system, which were subjected to tensile loading until they break, is obvious. At the beginning of the elongation process, the yarn system was elongated for a longer period of time at low loads, especially in the weft direction. Thus, in the first part of the curve the length of the nonlinear part of the stress curve depended on the crimping of the longitudinal thread system. Higher crimping resulted in a longer length of the nonlinear part of the curve. During the tensile elongation of the fabric on the tensile strength tester, the longitudinal threads were stressed and lied close to each other, while the transverse threads were free and wrapped more and more around the longitudinal threads. In this part of the diagram, energy differences are visible for all the samples, which increase as the elongation progresses. The resistance created by the longitudinal threads directly affects the breaking force (Fig. 6). The percentage of change was calculated as the difference of the breaking force of the samples before and after the cyclic load in relation to the breaking force of the samples before the cyclic load. The percentage of change was more significant in the direction of the warp, with smaller values of crimp, especially in the case of the samples of plain and basket weave.
Figure 6. Breaking forces of the fabrics before and after cyclic loading with error intervals
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Figure 7. Regression lines and regression coefficients for the forces at break before and after cyclic loading; F1 – breaking forces before cyclic loading (N), F2 – breaking forces after cyclic loading (N)
Scattering points are significantly different between warp and weft (Fig. 7). The scattering values of the breaking forces before and after cyclic loading in the warp direction are significantly lower than in the weft direction, but further away from the approximate regression line, resulting in a lower regression coefficient (R2=0.0911). The weft direction has more scattered values, but closer to the approximated line, so the regression coefficient is higher and amounts to R2=0.9988.
CONCLUSION The following conclusions can be drawn from the analysis of the results obtained: • Fabric weave has a considerable influence on the mechanical properties of a fabric, especially the breaking forces before and after cyclic loading in warp and weft direction. • Lower crimp leads to greater changes in the tensile mechanical behaviour of woven fabrics subjected to cyclic preload in the observed direction, due to higher tensile stiffness. • Biaxial cyclic preloading at low loads has different effects on the deformation of the fabrics in warp and weft direction, which depends on the crimp that affects the rate of change of tensile stiffness during stretching. In all the samples, the values of elongation at break is lower after cyclic loads compared to before, which results in an increase in the tensile stiffness. The percentage of changes of elongation at break for the samples subjected to the cyclic load relative to the ones before, in warp directions, ranges from 11,1 to 22,2%, and in the weft direction from 16,7 to 31,6%. • Biaxial cyclic loading at low loads compensates for forces in the threads, which can sometimes lead to an increase in the breaking forces (e.g., basket weave in the warp direction), but at the same time to a lower elongation of the fabric. • Woven fabric in plain weave has the highest values of the breaking force, but it is simultaneously the one most affected by the cyclic loading. Due to the compactness of the structure, the resistance to tensile deformation (tensile stiffness) of the plain weave fabric is the highest (in relation to its derivatives), which is why it endures the greatest stress. In these conditions, the cyclic stress causes greater fatigue of the material, which is manifested in reduced mechanical properties.
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This paper makes contribution to the study of fabrics woven in different weaves at the low level of biaxial cyclic loads (less than 10% of elongation at break). Author Contributions Conceptualization – S.K. and S.B.; methodology – S.B.; formal analysis – S.K., L.D. and S.B; investigation – L.D. and S.B; resources – L.D. and S.B; writing-original draft preparation – S.K. and S.B; writing-review and editing – S.B.; visualization – S.K., S.B. and I.S.; supervision – S.K. and S.B. All authors have read and agreed to the published version of the manuscript. Funding „This work has been fully supported by the Croatian Science Foundation under the project number IP-201801-3170” Conflicts of Interest The authors declare no conflict of interest.
REFERENCES [1] Kovar R. Anisotropy in woven fabric stress and elongation at break. Rijeka: Sciyo publisher, 2010. In Woven fabric engineering; p. 1-24. [2] Šomođi Ž, Šajatović Hursa A, Brnada S. A Complete Nonlinear Anisotropic Incremental Deformational Model of Woven Fabric in Plane Stress. In: Dragčević Z, Hursa Šajatović A, Vujasinović E, editor. Book of Proceedings of 7th International Textile, Clothing & Design Conference - Magic World of Textiles; 05.-08.10.2014; Dubrovnik, Croatia. Zagreb: University of Zagreb; Faculty of Textile Technology; 2014. p. 159-164. [3] Chen J, Chen W, Wang M, Ding Y, Zhou H, Zhao B, Fan J. Mechanical behaviours and elastic parameters of laminated fabric URETEK3216LV subjected to uniaxial and biaxial loading. Applied Composite Materials. 2017; 24(5):1107-1136. [4] Huang ZM. Fatigue life prediction of a woven fabric composite subjected to biaxial cyclic loads. Composites Part A: Applied Science and Manufacturing. 2002; 33(2):253-266. [5] Nosraty H, Asgharian Jeddi AA, Saremi R. Investigation of fatigue behaviour of polyester filament woven fabrics under cyclic loading. Journal of Textiles and Polymers, 2013; 1(1):43-52. [6] Kovačević S, et al. Procesi tkanja. Sveučilište u Zagrebu. Zagreb: Tekstilno-tehnološki fakultet; 2008. [7] Plain weave and its characteristics. TextileSchool4U.Blogspot.com. 2013. [accessed 9.5.2019.]. Available from: https://textileschool4u.blogspot.com/2013/11/plain-weave-and-its-characteristics.html. [8] Gokarneshan N. Fabric structure and design. New Delhi: New Age International Limited Publisher, 2004. [9] Brnada S. Deformacije tkanina uvjetovane anizotropnošću. Zagreb: Sveučilište u Zagrebu Tekstilnotehnološki fakultet; 2017. 215 [10] Šomođi Ž, Kovačević S, Dimitrovski K. Fabric distortion after weaving an approximate theoretical model. In: Dragčević Z, Hursa Šajatović A, Vujasinović E, editor. Book of Proceedings of 5th International Textile, Clothing & Design Conference - Magic World of Textiles; 03.-06.10.2010; Dubrovnik, Croatia. Zagreb: University of Zagreb; Faculty of Textile Technology; 2010. p. 729-734.
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[11] Šomođi Ž, Brnada S, Kovačević S. Elements of Anisotropy in Woven Fabrics and Composites. In: Dragčević Z, Hursa Šajatović A, Vujasinović E, editor. Book of Proceedings of 8th International Textile, Clothing & Design Conference - Magic World of Textiles; 02.-05.10.2016; Dubrovnik, Croatia. Zagreb: University of Zagreb; Faculty of Textile Technology; 2016. p. 138-143. [12] Hu J, Xin B. Structure and Mechanics of Textile Fibre Assemblies. Cambridge England: Woodhead Publishing; 2008. 3, Structure and mechanics of woven fabrics; p. 48-83. https://doi.org/10.1533/9781845695231.48 [13] Šomođi Ž. Osnove tehničke mehanike. Zagreb: Sveučilište u Zagrebu, Tekstilno-tehnološki fakultet; 2011. [14] Chen AS, Matthews FL. A review of multiaxial/biaxial loading tests for composite materials. Composites. 1993; 24(5):395-406. [15] Mostafa NH, Ismarrubie ZN, Sapuan SM, Sultan MTH. Effect of fabric biaxial prestress on the fatigue of woven E-glass/polyester composites. Materials & Design. 2016; 92:579-589. [16] Yingying Z, Qilin Z, Ke L, Bei-lei K. Experimental analysis of tensile behaviours of polytetrafluoroethylenecoated fabrics subjected to monotonous and cyclic loading. Textile Research Journal. 2014: 84(3):231245. [17] Shi T, Chen W, Gao C, Hu J, Zhao B, Wang M. Biaxial strength determination of woven fabric composite for airship structural envelope based on novel specimens. Composite Structures. 2018: 184:1126-1136. [18] ISO 3801:1977 Textiles - Woven fabrics - Determination of mass per unit length and mass per unit area [19] ISO 5084:1996 Textiles - Determination of thickness of textiles and textile products [20] HRN EN 1049-2:2003 Textiles - Woven fabrics - Construction - Methods of analysis - Part 2: Determination of number of threads per unit length (ISO 7211-2:1984 modified; EN 1049-2:1993) [21] ISO 7211-3:1984 Textiles - Woven fabrics - Construction — Methods of analysis - Part 3: Determination of crimp of yarn in fabric [22] HRN EN ISO 13934-1:2008 Textiles - Tensile properties of fabrics - Part 1: Determination of maximum force and elongation at maximum force using the strip method (ISO 13934-1:1999; EN ISO 139341:1999)
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Textile Finishing Using Polymer Nanocomposites for Radiation Shielding, Flame Retardancy and Mechanical Strength Sorna GOWRI*, Mohammad Akram KHAN, Avanish Kumar SRIVASTAVA CSIR-Advanced Materials and Processes Research Institute, Bhopal, Madhya Pradesh, India *gowrisorna@yahoo.com Review UDC 677.027.6:620.3 DOI: 10.31881/TLR.2021.07 Received 12 February 2021; Accepted 8 April 2021; Published Online 28 April 2021; Published 7 September 2021
ABSTRACT The uses of nanotechnologies in textiles are strategic and allow textiles to become multifunctional. There is an ever-increasing demand for new functionalities, like flame retardancy, radiation shielding, improved mechanical strength etc., for highly specific applications. There is no industrial supply for the above-mentioned functionalities. Keeping in view of this background, surface treatment becomes one of the most important methods to create new textile properties. Polymer nanocomposites based on coatings for textiles have a huge potential for innovative modifications of surface properties like flame retardancy, radiation shielding and improved mechanical properties, which can be applied with a comparatively low technical effort and at moderate temperatures. This review compiles recent research on polymer nanocomposites for functional finishing of textiles to understand the theoretical and experimental tools on polymer nanocomposites and their applications in textiles. KEYWORDS Textile finishing, Polymer nanocomposites, Radiation shielding, Flame retardancy, Mechanical strength
INTRODUCTION Functionalization of textiles is very important in view of improving their properties. The first commercial application of nanofinishing materials is found in textiles in the form of nanoparticles through finishing processes. But these finishes do not withstand subsequent washing due to poor fixing of these nanoparticles on the textile surface. Polymer nanocomposites are materials with high potential for developing a new class of coating system for textiles to overcome the above problem. Polymer nanocomposites are polymers usually filled with less than 10% of nanometre sized inorganic particles. They are superior in properties when compared to the conventional polymer composites [1-4]. The current research on textiles is focused on exploitation of the unique characteristics of polymer nanocomposites in textile industry. There are many synthetic methods followed to prepare polymer nanocomposites [5-7]. But the common theme of these approaches is intermingling the nanometre scale inorganic particles with properties not available from either of the pure component materials integrated in nanocomposites.
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Multifunctional finishing of textiles The uses of nanotechnologies in textiles are strategic and allow textiles to become multifunctional. The application of polymer nanocomposite coatings on textiles imparts various functionalities, like UV protection, antibacterial properties, flame retardancy, antistatic properties and radiation shielding. The addition of nanoparticles to the hydrophobic/hydrophilic functional polymers will improve the properties of the polymer with the additional incorporation of the functional properties of nanoparticles. Hydrophilic finishes on textiles are very important to impart absorbency in the applications of sportswear. The inorganic UV blockers are non-toxic compared to the organic UV blockers and they are chemically stable at a high temperature and exposure to UV. TiO2, SiO2, ZnO and Al2O3 are the certain inorganic oxides used as UV blockers [8,9]. In another work, zinc oxide nanoparticles were prepared by a wet chemical method and ZnO–PMMA nanocomposites were prepared by dispersing the ZnO nanoparticles in the solution of poly (methyl methacrylate) (PMMA) and applied on polyamide fabrics by padding. The results also showed that the impregnation of fabrics with ZnO–PMMA nanofinishings also enhanced the protection of polyamide fabrics against the UV radiation [10]. For imparting antibacterial properties, nanosilver, titanium dioxide and zinc oxide are used [11-14]. Textiles treated with nano TiO2 could provide effective protection against bacteria and discoloration or stains due to the photo catalysis effect [15,16]. Nano ZnO has photo catalytic properties when illuminated by light and it imparts antibacterial properties to textiles [17-19]. Raza et al. studied the fabrication of chitosan/zinc oxide nanocomposites (CZNCs) by using a facile preparation method. The nanocomposite-coated cotton fabric exhibited durable antibacterial, UV-blocking and textile properties with a fair whiteness index [20]. Ulfiqar et al. developed an antibacterial viscose fabric via a clean, easy and reproducible approach. Silver nanoparticles (SNPs) were prepared using chitosan both as a reducing and as well as a stabilizing agent to promote a green synthesis of SNPs. The developed treated viscose fabric showed good antibacterial properties, with fair textile characteristics. This is the first report on in situ fabrication and the impregnation of SNPs using chitosan as both a reducing and a stabilizing agent on a regenerated cellulose fabric like viscose [21]. Xiaoning et al. produced a knit polyester fabric simultaneously with remarkable electrical conductivity, waterrepelling and photocatalytic activity properties through the aid of chitosan and polyaniline nanocomposite polymer. A facile fabrication of multifunctional knit polyester fabric was based on chitosan and polyaniline polymer nanocomposite [22]. For almost two decades, the nanofinishing of cellulose textile material while using copper and copper oxide nanoparticles has been in the focus of science and textile industries [23]. Textile surfaces need to be pre-treated making certain functional groups available for bonding with the polymer nanocomposite finishing. Hydroxylamine treatment and plasma discharges are the treatments used for the fabric surface pre-treatment of [24,25]. Studies on plasma treatment of cotton and linen, wool and synthetic fibres proved that this treatment improves the whiteness degree, removal of waxes and sizing agents, absorption and fixation of dyes and finishing agents, increases the durability of functional effects and is able to provide certain functional groups available to bind with polymer nanocomposites [26-30]. Multi-functional finishing of cotton fabrics by plasma with nano TiO2/SiO2 via pad dry method was studied by Palaskar et al. and it was observed that the textile surface modification by the plasma treatment reduced the concentration of chemicals by 20-25%, thereby reducing environmental pollution and proving to be cost effective in comparison to the conventional finishing technique [31]. Research work has been carried out on atmospheric pressure dielectric barrier discharge plasma treatment for fabric surface activation to facilitate deposition of nano silicon oxide and nano-titanium dioxide onto cotton fabric. It has been found
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that the flame retardancy, UPF, antibacterial activity, wash fastness and thermal stability of the treated samples were improved compared to the untreated samples [32].
APPLICATION OF POLYMER NANOCOMPOSITES FOR DESIRED FUNCTIONAL PROPERTIES IN TEXTILES Out of the many possible applications of polymer nanocomposites for functional properties other than surface properties (Figure1) some of the most successful ones are antimicrobial, UV protection, flame retardancy, radiation shielding and improvement of mechanical properties of textiles. Our earlier review paper on polymer nanocomposite-based multifunctional coatings on textile, covered various properties like UV resistance, hydrophilicity, hydrophobicity and antimicrobial properties [33]. Focus of this review will be on the application of polymer nanocomposite finishings on textiles to impart fire retardancy, enhanced mechanical properties and radiation shielding properties.
Figure 1. Some possibilities of textile functionalization using PNC
Dispersion of nanoparticles to get a homogeneous solution is very difficult, since there is a strong tendency of the nanoparticles to aggregate. However, in polymer nanocomposites the polymers inhibit the aggregation and significantly increase the stability of the composite making their application in many fields easier. Sorna Gowri et al. [34] synthesized a new copolymer epoxy poly (dimethyl acrylamide) to disperse the SiO2 nanoparticles and developed a new method for the dispersion of nanoparticles. The results showed that the nanoparticles are well dispersed in epoxy poly (dimethyl acrylamide) as evidenced by the SEM analysis. Our recent unpublished results on polyvinyl alcohol-based polymer nanocomposites show that it is a good functional polymer system, which can be used for the dispersion of many inorganic nanoparticles (Figures 2, 3, 4, 5) since it is compatible with a number of inorganic nanoparticles.
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Figure 2. SEM image of PVA film with Al2O3
Figure 3. SEM image of PVA film with SiO2
Figure 4. SEM image of PVA film with TiO2
Figure 5. SEM image of PVA film with Fe2O3
There are two principal ways for the application of polymer nanocomposites on textiles. One is melt spinning of PA-6 yarns, which can be knitted or woven [7]. Another approach is coating the textile surface by polymer nanocomposites formulations. Application of these polymer nanocomposites coatings can be done by simple techniques such as pad application dip coating, spray coating, or exhaust process. One interesting method of polymer nanocomposite synthesis is in situ polymerization in which polymer nanocomposites are developed from nanoparticles.
Application of Polymer Nanocomposites as Flame Retardants in Textiles To inhibit or suppress the combustion of fabrics, flame retardants are applied to fabrics. Many flameretardant approaches have been developed and are used today by the textile industry [35]. If typical flame retardant finish is applied to the fabric, it adversely affects the fabric properties, such as drape and hand [36]. Also, some of the flame-retardant additives release toxic products during combustion, which is of concern regarding the environment [37]. Polymer nanocomposites are a new class of organic/inorganic hybrid material showing impressive performance for fire retardant application. Polymer-layered silicate nanocomposites are being investigated widely for their flame retardant effect. It is found that the addition of 2-5 wt% of layered silicates like montmorillonite (MMT) reduce the peak heat release rate (PHRR) during the burning of polymers by about 50-60% [38-44]. While the addition of conventional flame retardants deteriorates the mechanical properties of www.textile-leather.com 163
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polymers in most cases, tensile strength and the modulus of nano components with above 5 wt% of nanofillers are enhanced by 30-40% when compared with neat polymers [45-48]. Kadhiravan et al. investigated the flame-retardant properties of nylon 6/organically modified montmorillonite (DMMT) fibres and fabrics, and they found that with a higher concentration level of 8-10% DMMT, the fabrics burned without any dripping [49]. The flame spread rate was reduced by 30-40% compared to the nylon 6 films and the peak heatrelease rate of nylon 6 was reduced by 65-67% with this content. Devaux et al. studied the addition of two kinds of additives to PU in order to provide flame retardancy to the coated textile structure, namely montmorillonite clay and polyhedral oligomeric silsesquioxanes (POSS) [50]. Polypropylene (PP) is one of the most widely used thermoplastic polymers for application in textiles and plastics. This is attributed to its low density, low cost, easy processing, high tensile strength and excellent chemical stability [51-54]. Consequently, similar to other polymeric materials, the properties such as flame retardancy, UV resistance, crystallization behaviour, strength, hygienic behaviour and electrical resistance of PP fibres have been modified by compounding them with very small amounts of nanoparticles. Some examples of these attempts are observed in products like PP/silver [55], PP/SiO2 [53,56-59], PP/ Ba Fe[60-62], PP/TiO2 [63,64]. Nilufer et al. produced slow burning or flame-retardant polypropylene filaments for carpet pile yarns by incorporating SiO2 nanoparticles into polypropylene [65]. The oxygen index test was used in their studies to evaluate the flammability of polymers, because this test is a useful method to get single numerical value of relative flammability of polymeric fibres. Materials between the thresholds 20.95% < LOI <28% can be considered as slow burning materials in the oxygen index test. It has been found that filaments containing 1 and 3% of SiO2 nanoparticles reach the limit value of slow burning materials in the oxygen index test, thus obtaining a fire-resistant filament for the carpet pile yarn. Gillain et al. reported the burning behaviour of knitted fabrics produced from PP fibres comprising of several dispersed nanoclays and compatibilizing copolymers in the presence of ammonium polyphosphate (APP) as a model conventional fire retardant with regard to flammability when present alone [66]. Polylactic acid (PLA) is a biodegradable polymer which can be spun to produce textile fibres. In order to disperse the clay in PLA, two techniques are used: the solution-intercalation process [67,68] and the melt-blending process [69-73]. The interaction between the carbonyl functions of PLA chains and hydroxyl functions of alkyl ammonium surfactants surface–covering MMT nano platelets seem to improve the dispersion of this organoclayin a PLA matrix contrary to the other kinds of MMT without hydroxyl functions on the surfactants. [67,6972]. An original way to obtain a good dispersion of clay in PLA matrix is the in-situ coordination–insertion polymerization [74]. The PLA nanocomposites are characterized by an increase of the crystallization rate but also by a decrease of the activity to crystallize, so by a lower melting enthalpy compared to pristine PLA [67,70,74]. But the clay does not seem to influence the glass transition temperature of second order of PLA [67,70,74]. An improvement of the thermal stability of PLA can be obtained, especially when MMT Cloisite is used [67,75].The above studies show that the flame retardancy of neat polymers like poly urethane, polypropylene and PLA, can be improved by the addition of inert nanoparticles to the polymer system. In2002, for the first time, Bourbigot et al. described the use of a polymer matrix to produce a nanocomposite multifilament yarn [76].The matrix they used was a polyamide 6 polymer (PA6) reinforced with commercial MMT Cloisite 30B (C30B). The flammability of a knitted structure made with PA6 and PA6/C30B yarns was compared using a cone calorimeter and a strong decrease of the heat release was observed in the last case. A method to produce PLA organoclay nanocomposites was proposed by Samuel et al. [77]. They prepared PLA organoclay nanocomposites by melt-blending and particularly by twin-screw co-rotating extrusion. It was shown that C30B increases the crystallization rate and improves the thermal stability, especially for PLA/4%C30B. 164 www.textile-leather.com
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These polymer nanocomposite-coated textile fabrics showed excellent fire-retardant property evaluated by 45° flame test as per ASTM D1230-94 [78]. The flame-retardant cotton fabric was also developed by electrospinning polyamide/boric acid nanocomposites [79]. A one–pot approach base on coatings of sodium carboxymethylcellulose (CMC)/montmorillonite (MTM) polymer nanocomposites of bio-inspired brick-wall nanostructure on textiles was demonstrated by Paramita Das et al. Fire retardancy tests of these textile coatings elucidated the increasing fire barrier and the retardancy properties with the increasing coating thickness [80]. Yu-Chui Li et al. demonstrated a layer-by-layer assembly of branched polyethylenimine (BPEI) and sodium montmorillonite (MMT) clay nanocomposite coatings on cotton fabrics for imparting flame retardant properties. The treatments showed that all coated fabrics reduced the total heat releasing capacity of the fabric. These coatings are expected to be useful on a variety of substrates, like foam, fibre etc., as flame retardants [81]. In a research work, cotton fabric was coated with polypyrrole–zinc oxide–carbon nanotube (PPY-ZnOCNT) composites prepared by an in situ chemical polymerization method. The composite-coated cotton was found to have better flame retardant properties than the uncoated cotton [82]. A polymer nanocomposite was developed from carbon nanotubes and different phosphorous flame retardants, like ammonium phosphate, or melamine phosphate resin. The fabrics were coated by these composites. The fabric flammability tests were carried out and it was found that the coatings effectively reduced flammability and improved the thermal stability of the fabric. It has been observed that there was a synergistic effect between carbon nanotubes and phosphorous compounds [83]. A facile coating method for imparting flame retardancy to a silk fabric was developed, which involved montmorillonite (MMT) and graphene oxide (GO) hydrosol being added to polyvinyl alcohol, which was then coated onto the silk fabric by a simple coating machine. The analysis of the coated silk fabric showed excellent flame retardancy, thermal stability and smoke suspension properties [84]. Ihor et al. studied the effect of styrene acrylate and urethane polymer coatings filled with titanium dioxide on the thermophysical properties of a cotton fabric surface and found that the presence of polymer nanocomposite coating leads to the formation of coke residue on the fabric under the influence of the flame, which allows the fabric surface structure to be preserved after ignition [85]. The above results show that treating various fabrics, like cotton, nylon and silk, by various polymer nanocomposite finishings, dramatically improves their fire resistance.
Influence of Polymer Nanocomposites Finishes on Mechanical Properties of Textiles The application of polymer nanocomposites may affect fabric properties, like strength and bending rigidity. The addition of certain nanoparticles to neat polymers imparts improved mechanical strength to polymer nanocomposites and these polymer nanocomposites, applied as finishings on textiles, influence the mechanical strength of textiles. Polypropylene (PP)/organic-layered silica nanocomposites are attractive systems which impart improved mechanical properties, while simultaneously increasing dimensional stability, stiffness, strength and impact resistance [86-88]. By preparing PP nanocomposites in situ, with in situ formation of silicate nanoparticles by using an interlayer silicate modified by n-alkyl primary amine and PP-g-MA compatibilizer, an improved exfoliation of uniformly dispersed anisotropic nanoparticles was achieved [89]. The exfoliation of organoclay affords the in situ nano filler, which behaves as clay building bricks, to be uniformly dispersed into the PP matrix. The storage modulus was found to be three times that of the pure PP [88]. The improved mechanical properties of PP nanocomposites were attained by using SiO2-g-PS nanoparticles, obtained by the modification of SiO2 through the irradiation-grafting polymerization of styrene[90]. The elastic modulus of the syndiotactic polypropylene (SPP) nanocomposites, based on organophilic layered
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silicates and grafted PP as compatibilizer, was higher over a wider temperature range than that of the unfilled SPP [91]. Zita Mlynarcikova et al. studied the influence of the spinning process on the properties and morphology of the SPP nanocomposite fibres [92]. From the mechanical and morphological study of the above nanocomposites, it has been found that the filler and the compatibilizer highly influenced the spinning process. In their work, the extruded sPP nanocomposite fibres were drawn on a vertical elongation device (at 708⁰C). The values obtained from the measurement of the tensile strength of the fibres of both the non-filled sPP and the sPP nanocomposite fibres showed that the non-filled sPP fibres have relatively high tensile strength values in comparison with the iPP nanocomposite fibres at the same drawing ratio. It is known that porous materials are better assimilated by living organisms, considering their similar structure to that of hard tissues [93]. Therefore, it is important that the precursor fibres for biomedical applications should be characterized by an increased porosity [94]. On the other hand, typical, highly porous precursor fibres are characterized by having an inadequate level of tensile strength. It is also known that the tensile strength of carbon fibres directly depends on the strength of the precursor fibres [95]. Therefore, in the case of manufacturing PAN fibres dedicated for the production of carbon fibres for medical applications, it is important to select process parameters in such ways that the fibres obtained would have a relatively high porosity and, at the same time, tensile strength that would allow for carrying out the carbonization process without any problems. The tensile strength of textile fibres also significantly depends on the type and the amounts of nano additives added to the fibre matrix which in term influences the interactions with the polymer matrix [96-98]. If carbon nanotubes are added to the fibre matrix, an increase in the fibre tensile strength is observed depending on the nanotube type and amount [99,100]. T. Mikolajczyk et al. examined how the addition of silver nanoparticles to polyacrylonitrile spinning solutions influences their rheological properties as well as the structure and properties of the fibres produced [101]. Consequently, tensile strength properties were only a little lower than those of the fibres without silver nanoparticles, although there was a significant increase in porosity. Ceyhan Celik et al. studied the mechanical and electrical properties of the polymer blend of a tactic polystyrene and poly(phenylene ether) containing 5.0 wt% of graphite nanoparticles [102]. It was observed that the lack of bonding between the polymer and the nanoparticles resulted in reduced extrinsic mechanical properties. Both the tensile strength and elongation of the fibre were 20-25% less than those of the neat fibres. The modulus of the oriented fibre was unchanged by the addition of the graphite nanoparticles. The dip coating of the nanocomposite solution of organosilanes was done on textiles and it has been found that these super hydrophobic coatings showed good mechanical properties in terms of abrasion, scratch resistance and adhesion on the textiles. In addition to these properties, the coatings improved the tensile strength and elongation at break of the textiles [103]. Yadav et al. prepared ZnO nanoparticles and applied them on cotton fabrics using acrylic polymer as a matrix [104]. Along with the UV-blocking property, they studied and evaluated the friction and the mechanical properties of the treated fabrics. The friction was significantly lower in the case of nano ZnO-coated fabric than in bulk ZnO-coated fabric, due to the nano size and distribution. CNT–polyacrylate composites and CNT polybutacrylate composites were applied onto cotton fabrics using a simple surface coating method. The coated cotton textiles exhibited enhanced mechanical properties, flame retardancy, improved UV blocking and super hydrophobic properties [105]. A novel polyester fabric, with enhanced mechanical properties and photo-, bio- and magneto-activated by the in situ synthesis of TiO2/Fe3O4/Ag nanocomposites, which were coated onto the fabric surface, was developed by Tina et al. It has been shown that the tensile strength properties of the treated sample were enhanced when compared to the untreated fabric. The bending rigidity of the treated sample was reduced 166 www.textile-leather.com
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by 76% in comparison to the untreated fabric, indicating a softer handle of the fabric [106]. The cotton fabric was finished with the PPMACC-AGE/MMT composite prepared by the polymer intercalation method. The tensile strength of the treated fabric was superior to that of the untreated fabric. It has been observed that the presence of montmorillonite in the composite was responsible for the improvement of thermal and flammability properties of the treated fabric [107]. In another research work, polymer nanocomposites were prepared from mixers of resin / clay, with various percentages of clay, and applied onto cotton fabrics. The mechanical properties were enhanced by the coatings and the maximum clay percentage to enhance the mechanical performance was from 4% to 5% [108]. The tensile strength of the woven fabric coated with the MWCNTPP polymer composite showed optimum increase in tensile strength at 2 wt% of MWCNT added to the composite. The tensile strength of knitted fabric is higher in the wale direction than along the course direction [109]. Preetam et al. [110] prepared cotton fabric coated with graphite nano platelets filled polyaniline-gum Arabic nanocomposites and analysed the mechanical properties of the coated fabric. It has been observed that fabric coated with 3wt% Gnp/PANI-GA nanocomposites showed enhanced tensile strength of 145 N in the weft direction. The effect of polymer nanocomposite finishings on various types of textiles is indicated in Table 1. Table 1. Effect of the polymer nanocomposite finishing on mechanical properties of some of the textile samples S.No.
Textile sample
Nanofiller
Polymer
Impact on the mechanical properties of textiles
1.
Cotton
Zinc Oxide
Acrylic polymer
The nano-ZnO coating was found to reduce the tensile (Yadav strength of the fabric in the warp direction, with no et al. 2006) significant change in the weft direction. The strain reduced 104 significantly in both warp and weft directions.
2.
Cotton
CNT
Polybutacrylate
The tensile strength improvement of the CNTs-coated cotton fabrics along the warp direction, indicating that after being coated with the CNTs both the loading capability and flexibility (displacement) have been improved.
3.
Cotton
MMT
PPMACC-AGE
The breaking strength of the fabrics finished with PDMDAAC-AGE/ MMT was superior to those of the unfinished fabric and the fabric finished with PDMDAACAGE. The bending length of finished fabrics was slightly higher than that of unfinished fabrics.
4.
Cotton
Clay
PU & PAC
The mechanical performance of the fabric is globally (Elamin increased versus the amount of clay in the two used resins. et al. 2015) The maximum clay percentage to enhance the mechanical 108 performance of a fabric is between 4% and 5%.
5.
Woven fabric
MWCNT
Polypropylene
The maximum tensile strength along the weft direction of (Zheng-Ian conductive woven fabrics is present when 2 wt% MWCNT et al. 2017) is added. When the MWCNT content exceeds 2 wt% the 109 tensile strength along the weft direction decreases,the agglomerated MWCNT forms stress concentration sites, thereby decreasing the tensile strength of conductive woven fabrics at higher concentration of3 wt% of MWCNT.
6.
Cotton
Graphite Polyamide-gum nanoplatelets Arabic
In another study the authors carried out In –situ polymerization to prepare GnP (Graphene nanoparticles) filled polyaniline–gum arabic (GnP/PANI–GA) nanocomposites. It has been observed that cotton fabric coated with 3 wt% GnP/PANI–GA nanocomposite showed enriched tensile strength of (145 N) in weft direction
Reference
(Liu et al. 2008) 105
(Gao et al.2016) 107
(Preetam et al. 2019) 110
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Polymer Nanocomposites for Radiation Shielding Fabrics X-Ray Shielding Textiles Lead-based material is generally used as a radiation-shielding material but due to its toxicity and severe health concerns its use poses, it is advisable to avoid these materials for such applications. Recently, X-ray protective materials based on lightweight nanoparticles have been gaining in importance. Nanoparticles can be successfully included in polymer matrices of X-ray and gamma ray shielding materials. Polymer nanocomposites proved to be an alternate solution for lead-based materials due to the properties like light weight, cost-effectiveness and a high potential for significantly attenuating X-rays. To shield from the high energy radiation, high density of the polymer is the main criteria. The following Table 2 gives density and theoretical value of linear attenuation coefficient of some commercially available polymers. Table 2. Polymers and their density and linear attenuation coefficient at 276 keV [111] Density (in g/cc)
Linear attenuation coefficient (cm-1)
Polyamide (Nylon 6) (PA-6)
1.13
0.1362
2.
Polyacrylonitrile (PAN)
1.18
0.1370
3.
Polyvinylidene chloride (PVDC)
1.63
0.1819
4.
Polyaniline (PANI)
1.36
0.1576
5.
Polyethylene terephthalate (PET)
1.38
0.1581
6.
Polyphenylenesulfide (PPS)
1.35
0.1550
7.
Polypyrrole (PPy)
1.48
0.1701
8.
Polytetrafluoroethylene (PTFE)
2.20
0.2330
S.No.
Polymer
1.
The radiation-barrier effects of polymer nanocomposites are attributable to the increased number of particles dispersed per unit of mass and also to the size effects at the nanometric dimension. Therefore, the use of polymer nanocomposites as a finishing on textiles with the purpose of radiation protection may have important advantages in terms of effective radiation shielding, lightweight and to replace the toxic lead and lead composites. A lot of work has been carried outon the use of polymer nanocomposites for X-ray and gamma ray shielding applications [112-114]. PDMS nanocomposites containing different weight (%) of bismuth oxide were studied by Nambiar et al. for the radiation attenuating properties, and they concluded that PDMS composites can be used as protective coatings [115]. To avoid lead aprons, Huda Ahmad et al. explored the suitability of bismuth oxide coating on textiles as an alternative to lead. It is evident from their study that bismuth oxide in a suitable resin matrix can be coated onto fabrics and that it is an effective method of providing flexible, wearable and lead-free aprons [116]. Aprons made of lead are being widely used to protect X-ray technicians and patients from harmful radiations, with lead oxide being widely used as a protective material since the beginning of making protective aprons, but the weight and toxicity of lead are important limitations [116,117]. In all these aprons, nylon/polyester fabrics are used as the casing for lead sheets [118]. There are some examples of radiation shielding materials without lead as well as those lighter than lead-based materials that are available. [119122]. Polymer nanocomposites used for fabricating radiation shielding fabrics have been tested by many researchers [123,124]. An exploratory research was carried out at CSIR-AMPRI, Bhopal to develop X- ray shielding cotton fabrics based on the MWCNT (multi wall carbon nanotubes) nanocomposites. The cotton fabric was treated with plasma and the MWCNT coating in sodium dodecyl sulfate (SDS) was applied by dip 168 www.textile-leather.com
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coating. The SDS-treated MWCNT and the coated fabric were studied under SEM (Figures 6(a), 6(b), 7(a) and 7(b)). As seen from Figure 6(a), the raw MWCNTs are in the form of agglomerated bundles and have a more fibre-like structure. These bundles were broken down into separate tubes and became shorter due to the sonication during the SDS (surfactant) treatment (Figure 6 (b)), since the treatment of MWCNTs with surfactants shortens the length of the MWCNTs. The FE (field emission)-SEM microscopy image of the MWCNT-coated fabric at different magnifications shows a microfibril structure. The FE-SEM figures show the pores of cotton fabric without the coating, being the pore walls formed from fibre bundles, and thus feature an interstice structure as shown in Figure 7(a). Figures 7(a) and 7(b) show that the MWCNT coating can effectively fill the pores and enwrap the walls of the pores i.e., the interstices of fibre bundles, thereby forming a shielding layer on the cotton fabric. Studies on evaluation of these MWCNT-coated cotton fabrics for X-ray shielding are in progress.
a)
b)
Figure 6. (a) SEM image of untreated MWCNT and (b) SEM image of MWCNT treated with SDS
a)
b)
Figure 7. (a) Uncoated cotton fabric (b) MWCNT-coated cotton fabric
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EMI/Microwave Shielding Fabrics In recent years there has been a demand for using treated textiles for electromagnetic shielding applications. Textiles can be used for EMI shielding in protective garments [125,126]. EM shielding depends on electrical conductivity of the material, but textile materials are insulators and they can be made conductive by being treated with electrically conductive materials [127-130]. Shalu et al. synthesized the electrically conductive polypropylene (PP) and jute nonwoven fabrics by a chemical oxidative polymerization process [131]. The surface resistivity of PPy-coated PP nonwoven fabric was found to be superior to that of the jute nonwoven fabric. Carbon nanotubes are potential materials for EMI shielding due to their electrical properties, high surface area, lightweight and mechanical properties. Carbon nanotubes have cylindrical nanostructure and they are allotropes of carbon. The cylindrical carbon molecules have unique electrical, thermal and mechanical properties, which are valuable for nanotechnology and other fields of material science and technology. Due to the simplicity of process and ease of handling, coating the textile surface with polymer nanocomposites is a suitable method among various textile treatment methods [132-134]. Electrically conductive polymer composites have received much attention recently compared to the conventional metal-based EMI shielding materials [135]. They are corrosion resistant, flexible and easy to process due to their lightweight. Carbon nanotubes are one of the effective candidates for EMI shielding as the filler in polymer composites [136,137]. Nargis and Ismail have investigated cotton fabrics coated withpolyamide 6 (PA6)/multiwalled carbon nanotubes with varying amount of MWCNT for electromagnetic shielding properties and the effects of MWCNT loading on electrical resistivity, shielding effectiveness, shielding mechanism and also electromagnetic interference. They found that the highest electromagnetic shielding effectiveness value was obtained at 20wt%MWCNT [138]. Durable electromagnetic interference-shielding cotton fabric was prepared by Lihua Zou et al. with NafionMWCNT coatings. It has been shown that, in addition to the satisfactory shielding ability, the treated fabric exhibited good durability and superhydrophobicity [139]. Personal protective garments with high performance in EMI-shielding properties were prepared by Mingweietet al. via layer-by-layer self-assembly approach. In this work poly(sodium 4-styrene sulphonate) PSS was used as a polyanion and chitosan was adopted as a polycation with graphene added by solution mixing. The resultant fabric exhibited EMI-shielding ability with the maximum SE value of 30.04 dB [140]. In a study by Sundaramoorthy et al. different conducting and non-conducting fabrics were taken for an analysis of the EMI-shielding ability. It was found that the surface resistivity can be used to predict the EMI shielding ability of the fabric due to a string inverse relationship between these parameters [141]. Tellakula et al. carried out the fabrication of impedance-graded composites containing polyurethane, carbon nanotubes, carbon fibres, and micro balloons. Polypyrrole (PPy) fabrics with different surface resistances were used along with these composites, and experiments were carried out to find the effect of the PPy fabric. It was found that both the surface resistance of the fabric and its location in the composite are critical for the reflection property of the electromagnetic absorber [142]. A methodology and a material for the production of flexible, lightweight and porous conductive fabric for EMI shielding was reported by Renata et al. These novel shielding fabrics were fabricated by coating with the carbon-nanotube composite consisting of polymers and metal nanoparticles. The EMI shielding of the fabric was 95-99.99% (40 dB) and CNT was found to be the most effective shielding material [143]. It has been shown by MazeyarGashtiet al. that nano zircon can be used in various polymer nanocomposites and textile coatings to increase the EM reflection properties. In this work, nano ZrO2 particles were stabilized
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on wool surface by using citric acid as a cross-linking agent and sodium hypo phosphate (SHP) as a catalyst under the UV radiation. The results indicated that stabilized nano zirconia enhanced the flame retardancy and electromagnetic reflection of wool [144]. It has been reported that the fabric preforms made from multiwalled carbon nanotubes and carbon fibres, which were reinforced in epoxy resin to make composites, produced significant electromagnetic shielding effectiveness of -51.1 dB for CF-MWCNT/epoxy composites with the thickness of 2 mm [145]. Mazeyar Gashti et al. developed a method for the production of polypyrrole-based nanocomposites which can be applied as high electromagnetic shielding on textiles. In this methodpolypyrrole was prepared by a one-step UV-inducing polymerization by using AgNo3 as a catalyst for the oxidation of pyrrole monomers [146]. A simple and convenient approach for the fabrication of EMI-shielding textiles was developed by Lihua et al. In their work polyaniline-coated (PANI) carbon nanotube (CNTs) coating has been deposited onto a commercial fabric. The coated fabric had an exception EMI SE of 23.0dB. Simultaneously, the polymer nanocompositecoated fabric exhibited a high adsorption ratio of the incident electromagnetic energy with distinguished EMI-shielding performance [147]. In a recent research work, phase separated PEDDT-PSS, ornamented with reduced graphene oxide (rGo) nano sheets, was deposited on the newly fabricated ultra-lightweight superhydrophobic merino wool/ nylon (W-N) composite textile by a dipping and drying method. The coated textile showed electromagnetic shielding efficiency of 73.8dB (in the X-band) and the hydrophobicity of the coating lead to an excellent EMI-protective cloth, combined with an excellent performance under high mechanical or chemical tolerance [148]. Recently Shivam et al. reported zinc oxide and reduced graphene oxide-coated cotton fabric for the application of EMI shielding in the X-band (8.2-12.4GHZ). The coated cotton achieved highest total EMIshielding effectiveness of - 99.999%. Such high EMI shielding is attributed to highly dielectric ZnO nanoparticles, highly conductive rGo sheets and the core shell structure of the coated cotton fabric [149]. Mengwei et al. reported a facile approach with excellent EMI-shielding performance using polyurethane and a filler consisting of 80% of CNT and 20% of graphene nanoparticles applied onto the textile by a dipping method. The electromagnetic interference shielding effectiveness (EMISE) of the coated textile could achieve 35dB with the thickness of 0.35mm and the reflectivity of ca.41.4% [150]. The comparison of the above results show that the EM properties and the EM absorption properties of polymer nanocomposites are increased with the increase in percentage by weight (wt%) of nanofiller materials like CNT, carbon fibres and graphene oxide. Polypyrrole PPY/Al2O3 nanocomposites were prepared by the polymerization of pyrrole by using iron trichloride (FeCl3) as an oxidant in the presence of Al2O3 nanoparticles. The obtained nanocomposites absorbed more than 53% of the incident microwave radiation after passing through a thick composite-coated textile [151]. Research work has been carried out to load amine functionalized multiwalled carbon nanotubes (NH2-MWCNT) onto the polyester-fabric surface to obtain microwave shielding fabrics. The best microwave shielding properties were obtained from the fabric treated with plasma, which was then coated with 10% of NH2-MWCNT in the presence of acrylic acid [152].
CONCLUSION Polymer nanocomposites are a promising material with a potential for various applications in the textile industry, with regard to imparting various functional properties to textiles. In this review we have discussed radiation shielding, flame retardancy and enhanced mechanical properties of the textiles treated with polymer nanocomposites. It is evident from the earlier extensive research work that polymer nanocompos-
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ites are a new class of organic/inorganic hybrid material showing impressive performance for fire retardant application. Earlier research studies also show it is possible to improve some of the mechanical properties such as tensile strength and stiffness of the textiles by the application of certain polymer nanocomposite finishings. Recent research works on radiation shielding textiles suggest carbon nanotubes are a good candidate for imparting radiation-shielding property to the polymer nanocomposite finishing. Polymer nanocomposite finishings open up a new area of textile finishing by which a wide range of technical textiles can be produced. Multifunctional textiles finished with polymer nanocomposites, which are manufactured by environmentally friendly processes, are highly efficient. Textile products finished with polymer nanocomposites have wide applications in the handloom industry, the manufacturing industry and textile industries. Keeping in view the industrial application of polymer nanocomposites the further research work must be carried out to develop simple techniques which can be easily adopted by the industries. Acknowledgements The authors are thankful to Nano mission DST, India for providing financial support to the project on multifunctional coatings on textiles. Conflicts of Interest The authors declare no conflict of interest.
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Solution Blow Spinning (SBS): A Promising Spinning System for Submicron/Nanofibre Production Md. Khalilur Rahman KHAN1*, Mohammad Naim HASSAN2 Department of Textile Engineering, Bangladesh University of Business and Technology, Dhaka-1216, Bangladesh Department of Textile Engineering, Khulna University of Engineering and Technology, Khulna-9203, Bangladesh *khalilbutex@gmail.com 1 2
Review UDC 677.021.125.26 DOI: 10.31881/TLR.2021.04 Received 31 January 2021; Accepted 28 March 2021; Published Online 29 April 2021; Published 7 September 2021
ABSTRACT Submicron/nanofibres possess great potential for application in different areas because of their amazingly high surface area-to-weight ratio. The demand for fabrication of such fibres on a huge scale is increasing with the fast improvement of nanotechnology. Traditionally, nanofibre fabrication methods have intrinsic faults, limiting their application in industry. Solution blow spinning (SBS) is a viable option for producing adaptable and conformable submicron/nanofibre mats on a variety of surfaces. The technique can be employed to produce submicron/ nanofibres with only a simple commercial airbrush, a concentrated polymer solution, and a compressed gas source. It depends on the high velocity of decompressed air that allows the rapid stretching and evaporation of the solvent from a polymeric solution jet at the outlet of the concentric nozzles system. Along with recent advancements, the importance and drawbacks of the solution blow spinning system in comparison to other methods, such as electrospinning and melt blowing, are briefly discussed. Furthermore, the mechanisms of co-axial SBS spinning and micro SBS spinning system for submicron/nanofibre fabrication are also described. Drawbacks and research challenges of SBS are also addressed in this paper. KEYWORDS Submicron/nanofibre, Solution blow spinning (SBS), Airbrushing, Co-axial spinning
INTRODUCTION At present, the focus of engineers and scientists is on nanomaterials because of their potential to improve material efficiency and capabilities in a variety of commercial sectors [1]. The greatest significance of the nanotechnology is its aspect ratio that is related to the enormous surface area-to-volume ratio and their quantum effects [2]. Some advantageous features offered by the nano size of the materials enhance the properties of the material [3]. Thereby, nanostructured materials are used in numerous applications, such as catalysis, electronics, separation technologies, sensors, information storage, drug delivery systems, diagnostics, energy batteries, fuel cells, solar cells and more [4]. Researchers and industries have a considerable interest in the advanced functional nanostructured materials that use one-dimensional (1-D) nanostructures for their development [5]. Due to their distinctive physical and chemical characteristics, one-dimensional (1D) nanostructured materials, such as nanofibres (NFs), nanowires (NWs), nanotubes (NTs) and nanorods (NRs), have drawn substantial interest [6]. Fibrous materials are very intriguing structures with distinc-
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tive properties among other materials. They have a high porosity, a large specific surface area and good breathability [7]. For a wide variety of research and commercial utilization, nanofibres have appeared as a promising single-dimensional nanomaterial [8]. Typically, nanofibres are known as fibres with the diameter of less than 100 nm in the fibre science literature [9]. The nanofibre technology includes synthesis, processing, manufacturing, and application of fibres with the nanoscale dimension [10]. Unlike traditional rigid porous structures, a porous structure made of nanofibres is a dynamic device where the pore size and shape can change [11]. Nanofibres have a great variety of applications since they have high applicability in the fabrication of composites with other materials [12]. Besides, nanofibre scaffolds emulate the fibrous nanostructure of native extracellular matrix (ECM) and can be used effectively for tissue engineering [13]. The offering of nanofibres to the growth of the market for nonwovens will be dependent on the advancement of modern, affordable technologies, especially those that can scale up to manage large commercial volumes [14]. In view of the future opportunities presented by nanofibres, a growing interest in nanofibre technologies has emerged in the last decade to scale up the production of nanofibres [10]. SBS has the significance to be easily scaled-up in its in-situ use for different applications [15]. However, different procedures, such as template synthesis [16], phase inversion/separation, freeze/drying synthesis [17], drawing [18], bi-component extrusion [19], electrospinning [20], melt blowing [21], force spinning [22] and so on; can be used to produce nanofibres. While electrospinning is the most common spinning method used to produce nanofibres, it has drawbacks such that it can only be used in electrically conductive systems to conduct voltages applied during the electrospinning process and involves skilled personnel [23-24]. Electrospinning has advanced from very slow single-jet spinning to multi-jet or needleless spinning systems, which has permitted an improvement in the production rate, yet the rates are still much below than what is expected for it to be economical [25]. The throughput of SBS can be several times larger than that of electrospinning [26]. In the endeavour of creating micro- and nanoscale fibres, solution blow spinning comes as a hopeful prospect in recent times. Over the decade, due to its simplicity and high efficiency, solution blow spinning (SBS) has attracted a great deal of interest. A strong knowledge of technology and engineering is the driving force behind creativity and growth in the textile industry. This suggests that a yarn producer must also be technologically competent, effective, versatile, and cost-conscious. From this viewpoint, a description of the solution blow spinning (SBS) is being pursued regarding the advantages of this spinning device for the processing of submicron/nanofibre. Along with the influencing parameters, some examples of applications and challenges of SBS system are also addressed briefly in this article. However, the basic principles of the co-axial and micro SBS systems are also briefly mentioned.
SOLUTION BLOW SPINNING (SBS) Solution blow spinning (SBS) is a neoteric process for the preparation of high-efficiency and secure nanofibre mats, and SBS is a mature fibre-forming technique (shown in Figure 1) that provides several advantages over traditional electrospinning methods [27]. Centred on the concepts of ES and melt-blowing technologies, SBS offers the possibility to process nanofibre with a variety of diameters comparable to the ES system [28]. In 2009 Medeiros et al. first reported on the SBS spinning system.
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Figure 1. The nozzle geometry creates a region of low pressure around the inner nozzle (P2) compared to high pressure (P1) stream of gas that passes through the outer nozzle, which helps draw the polymer solution into a cone [Courtesy: Medeiros ES et al. Journal of Applied Polymer Science. 2009; 113(4):2322-2330. https://doi.org/10.1002/app.30275 © 2009 Wiley Periodicals, Inc.]
Basic Mechanism of the SBS System It is similar to the dry spinning process because the solution made of a polymer dissolved in a volatile solvent needs to be dried rapidly. It also corresponds similarly to the electrospinning process as there is a stretching induced by an external force prior to the deposition [28]. Solution blowing, however, is a system for spinning submicron and nanofibres from polymer solutions where high-velocity gas flow is used as a fibre-forming driving force [29]. In SBS, a polymer is dissolved into an appropriate solvent to reduce its viscosity [24]. A basic SBS system consists of a compressed gas supply, a pressure regulator, a syringe, a pump for the syringe, a concentric nozzle spray apparatus, and a collector as shown in Figure 2 [30,31]. A needle inserted concentrically inside the air nozzle is a more common configuration. The needle size can be changed accordingly. Usually, 0.2-0.7 mm is the inner diameter of the orifice [29]. SBS uses pressurized gas to create submicron and nanofibre from polymer solution. Parallel streams of polymer solution and pressurized gas are blown through the concentric nozzle chambers during fibre production. The polymer solution is contained in the inner chamber, while the pressure gas is located in the outer chamber [30]. Gas velocity increases due to the accelerated decompression of air based on the Bernoulli principle [28]. The pressurized high-speed gas induces a decrease in pressure and then the shearing at the gas/solution interface occurs and the polymer solution is stretched towards a fixed collector when the critical air pressure is surpassed [30,32]. In other words, the solvent went into a droplet out of the inner nozzle. The solution interface of the droplet was then deformed into a conical shape by the high-speed air flow coming from the outer nozzle. The solution droplet is ejected into several fine streams immediately after the surface tension is overcome because of the forces of air flow [33]. When these jets fly over the working distance towards the collector, they are stretched by the pressure drop. If the solvent evaporates, streams of extended polymers then easily form into fibres [30,32]. Highly viscous liquid jets experience lateral distributed force when it travels at a high-speed relative to the surrounding gas, resulting in enhanced bending perturbations [34]. However, within the working distance (typically 10-20 cm but differs depending on solvent volatility) the solvent evaporates, and polymer fibres are deposited with no further drying, cooling, or washing necessary [35]. Polymer fibres can be spun with a wide surface area for various future applications such as membranes for biological and chemical sensors, drug distribution, filtration media, and tissue engineering by varying polymer architecture and processing environments in the SBS system [32]. For example, Bonan et al. performed fibre processing by using poly (lactic acid) (PLA) polymer that is the most widely used biocompatible and non-toxic polymer in general. Solutions were pumped at a rate
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of 120 μL/min through the inner nozzle and a pressurized gas stream was delivered at 2.4 kPa through the outer nozzle. Fibre mats were directly deposited at 200 rpm on a revolving cylindrical collector, located at a working distance of 20 cm [36]. Wojasiński carried out the SBS procedure in atmospheric conditions with a RH of 45% -50% during the processing of PLA fibre [28]. The successfully fabricated polymers by the SBS system include PLGA, PEO, PLA, polyimide, SPEEK, poly (caprolactone), poly (styrene), poly (vinyl acetate), poly (methyl methacrylate), PVDF, and poly (acrylonitrile). However, Aerospinner (SBS) for lab and industrial scale production is provided by the Areka Group [37].
Influencing Parameters of SBS Many studies have been conducted to determine the effect of process parameters on the morphology of the fibre, such as concentration of polymer solution, air pressure, feed rate, work distance, and distance between nozzles. The nozzle diameter has to be small enough to facilitate the generation of fibres within the nanoscale range. The initial diameter of the free jet is dictated by the cross-sectional area of the inner orifice where the solution is extruded before jet experiences the stretching stage. Greater resistance is offered by a thicker jet to the stretching and bending instability which results in a thicker fibre. The most important parameters influencing fibre diameter have been found to be polymer solution concentration and air pressure. The entanglement of polymer chains is linked to the formation of fibres from the polymer solution, and it requires a specific concentration (overlap concentration) of polymer in the solution. The entanglement of polymer chains leads to the increase in viscosity that overcomes the surface tension. The lower concentration of polymers creates fibres of smaller diameters. The low concentration rate of the solution lowers the viscosity of the solution. Therefore, the solution jet is more refined by high-pressure airflow which leads to the production of thinner fibres. An increase in polymer concentration increases the difficulties in nanofibre production. In addition, the polymer-solvent system is also very critical since the viscosity of the solution and the surface tension have a direct effect on the SBS system [15,29,34,38-40]. In addition, the molecular weight of the polymer and the evaporation rate of polymer solutions influence the diameter of the fibre [32]. For instance, scaffold qualities are improved by low molecular weight polymers because of acting as plasticizers and it leads to generating longer fibres [41]. Properties such as the average fibre diameter and morphology of nanofibrous sheets derived from SBS can be adjusted [28]. SBS fabricated fibres have a diameter ranging from 100 nm to greater than 1 μm [35]. When the air pressure is increased, the fibre diameter is reduced and fibre mats become more uniform. The airflow field distribution, air velocity and morphology of the final product greatly depend on the nozzle design which is a very critical parameter in the SBS system. Although a smaller orifice can generate thinner fibres, it decreases the throughput rate [24]. For producing fibres, the air pressure higher than 30 psi is required in general. Otherwise, it will not be able to provide adequate driving force to overcome the surface tension. The air pressure working range is reported to be between 30 and 90 psi [42]. Providing extra gas pressure produces smaller and thinner fibres, which is due to the greater level of fibre stretching as well as the shearing force [29]. Fibre formation is also influenced by the working distance but has a low effect on the fibre diameter. The distance required for the fibres to dry before collection is called minimum working distance and the distance that avoids the excessive loss of the jettisoned fibres is considered as maximum working distance [42]. A higher stretching of fibre and a better dissipation of the solvent is obtained at a higher working distance [29]. The temperature ameliorates the drying and spinnability of the SBS nanofibres when a spinning line is arranged with a heating environment. For example, once the configuration of the nozzle, the feed rate, the air pressure, the solvent and the polymer concentration are being optimized, the yield can be further
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improved by the combination of several nozzles and the solution is injected into each nozzle at the same time [24]. The polymer blending improves the process ability and it can be utilized to adjust the polymer degradation rates [29]. More research should focus on optimizing the process parameters of the SBS system to fabricate the mats based on the characteristics of the polymer and the requirements for final products.
Figure 2. Schematic of solution blow spinning process [Courtesy: Atif et al. Polymers. 2020; 12(5):1140. https://doi.org/10.3390/polym12051140 © 2020 by Atif et al.]
AIRBRUSHING SYSTEM The commercial airbrush is the most commonly used device for the SBS process [43]. Commercial airbrushes (a gravity-fed brush) have been successfully used as an alternative to the traditional SBS apparatus to produce polymer fibres based on the same principles [34]. It is often referred to as airbrushing [44] or solution spraying [45]. It is estimated that the set-up is ten times quicker and 100 times less costly than the traditional electrospinning techniques [46]. The polymer solution is sprayed at a predetermined temperature and relative humidity by using an airbrush (shown in Figure 3) atomization unit. With an internal mixing capability, the atomization nozzle used has a double action. For atomizing the polymer solution, the air pressure is applied and the distance between the tip of the nozzle and the collector plate is set typically at the range of 30-40 cm [47]. The reduced cost and instant availability are the benefits of airbrushing; there are less parameters in the airbrushing method that obstruct reproducibility [48,49]. Dias et al. found the optimum working conditions during fabricating SBS spun PVDF nanofibres as follows: the pressure at 5 bar, a working distance of 20 cm, and a polymer concentration of 20% (w/v) [49]. The porosity of the airbrushed material ranged from 77% to 95%, while the porosity of the nanofibres produced by electrospinning was 67%, and the airbrushed nanofibres were more commercially viable, easier to handle and safer [49]. Costs are decreased and deposition rates are in the order 10 times higher than electrospinning when a gravityfed or siphon-fed airbrush is used [35]. The process is environmentally friendly and simple [46]. Cell adhesion, proliferation and differentiation are also supported by the airbrushing system [13]. It could promote the deposition of nanofibres directly onto living tissues at a higher rate, form three-dimensional biomimetic scaffolds with enhanced cell penetration and could be deposited in different chemical and structural configurations [46]. This technique has been mentioned by many researchers [13,43,50-53] as a viable and alternative nanofibre production spinning system for 3D tissue engineering scaffolds. Nevertheless, one downside of the airbrush is that this approach is unable to generate nonwovens consisting of long indi-
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vidual fibres. Instead, they create entangled fibres or fibre strands [52]. However, Hell AF et al. developed a semi-automatic SBS system to produce poly (ε-caprolactone) (PCL) fibrous mats for tissue engineering and compared its merits and demerits to the airbrushing system. They mentioned that the airbrushing tended to create more fibre bundles than SBS and produced more beads as well. Diameter ranges were similar, but airbrushing gave a narrower distribution than that of SBS (i.e., 132-1607 nm for airbrushing and 132-1268 nm for semi-automatic SBS) [48].
Figure 3. Schematic illustration of the Airbrush Spinning System [Courtesy: Bhullar SK et al. Journal of Nanoscience and Nanotechnology. 2018; 18(4):2951–2955. https://doi.org/10.1166/jnn.2018.14376, Copyright © 2018 American Scientific Publishers, ref. 46]
COAXIAL SOLUTION BLOWING METHOD (CSB) Over the last decade, core-shore nanofibres have become popular based on their special features and their biomedicine application [54,55]. Core–shell bi-component nanofibres are emerging for tissue engineering and wound healing applications as they mimic the natural extracellular matrix (ECM). They can serve as conduits for the delivery of the growth factors such as proteins, antibiotics, and other agents, while remaining bioactive [56]. A novel co-axial airbrushing technique successfully created the core-shell nanofibre mat. There are three detachable components in the coaxial solution blowing process (shown in Figure 4). The process of co-axial airbrushing can be explained as follows: The core-shell polymer drop at the tip of the needle elongates due to the stress generated and the shell polymer solution causes the core solution to be sheared through viscous drag and contact friction. This phenomenon allows the conical structure of the central polymer fluid and a compound co-axial jet forms at the tip of the cones, and further progression leads to the creation of core-shell fibres [44]. Polymer nanofibres are dragged out of the cone by the viscous forces of the moving air that overpower the surface tension forces [28]. Pressurized air confines the polymer solution to generate a fine liquid jet [57]. Fine polymer nanofibres are collected on rotating drums [28]. However, Lei Li et al. produced the three-dimensional hollow PAN nanofibre mat (CSB-HPAN) successfully using a coaxial solution blowing process [58]. Higher molecular weight PDLLA (Mw ≈ 100 000 g mol−1 ) and lower molecular weight carboxylic acid terminated PDLLA (PDLLA-COOH, Mw ≈ 25 000 g mol−1 ) were blended to produce nanofibre scaffolds through a co-axial air-brushing system [41]. Oliveira et al. applied
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a blend of PEO and PLA to produce fibres with the core of amorphous PLA and the shell of semicrystalline PEO [59]. Cellulose solution and polyethylene oxide (PEO) solution were used as the core and shell liquids, respectively, to create core–shell structures submicron-scale amorphous cellulose fibres. Cellulose fibres with diameters in the range of 160 nm and 960 nm were subsequently produced after removing the PEO shell [60]. Another attracting purpose for core-shell blowing is the resulting barrier characteristics given by the shell material. Such a structure permits controlled release and self-healing applications. Rhodamine B was integrated in a core-shell of soy protein/nylon resulting in a longer release time of the dye compared to the monolithic fibres [29].
Figure 4. Schematic of the coaxial solution blowing apparatus [Courtesy: Park SC et al. RSC Advances. 2018; 8(57):32470-32480. https://doi.org/10.1039/C8RA05485A, © The Royal Society of Chemistry 2018, ref. 61]
MICRO SOLUTION BLOW SPINNING (ΜSBS) The gas dynamic virtual nozzle (GDVN) principle is used by micro solution blow spinning (μSBS) to produce micron-sized fibres in a continuous and stable process from a polymer solution. Hofmann et al. described microfluidic chip featured nozzle that is comprised of two inlet ports. One was attached to pressurized air, while the other was connected to a syringe pump carrying a polymer solution. Unlike solvent blow spinning with a concentric nozzle, the inner nozzle, which provides the polymer solution, does not protrude from the compressed air outlet. In a micro-fluid system, the polymer solution from orthogonal directions is centred on a steady flow of pressurized air, such that a fine liquid jet is generated [57,62]. The combined forces of tangential shear and extensional stress, viscous stress, and surface tension here contribute to acceleration and the collision of liquid without the wall interaction. This merging fluid meniscus results in a cylindrical microjet with the diameter down to a few micrometres and below [63]. Microfluidic solution blow spinning allows for effective jet diameter control. Hofmann et al. mentioned that the fibre spinning was carried out at atmospheric conditions with the temperature at 23 °C and the relative humidity in the range of 45-55%. In principle, this efficient use of the microfluidic nozzle system for continuous fibre processing could be applied to bio-based nanofibrils, which have recently shown to be a promising material for fibre spinning technology [57,63].
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ADVANTAGEOUS FEATURES OF SBS SYSTEM Due to miniaturization and future applications in various fields, such as electronics and medicine, the market for nanostructured materials can grow exponentially. Fast output rates are therefore necessary in order to make nanomaterials commercially available [64]. SBS is considered to be maturing among the new technologies used for the development of nanofibres, primarily because of its capacity to generate the most nanofibres in the shortest possible time [30]. Special characteristics of SBS include a way of investigating the effectiveness of nonwoven fibrous materials in new applications. SBS uses processes similar to those used in industrial production systems, which facilitate its potential application to large-scale manufacturing like the electrospinning system [35,65]. For instance, gas is used to cool or vaporize solvent from fibres after extrusion through a spinneret in a melt spinning or dry spinning system, respectively. SBS uses pressurized gas to extrude the polymer solution and to induce solvent evaporation, which results in a simplified operation, consisting of a single step, for producing polymer fibres [35]. It has been researched in relation to the production of functional polymer nanofibre coatings, nonwoven textiles, and stretchable electronics because of its flexibility and ability to convey conformal fibres directly. These investigations have shown that SBS is capable of producing high-precision, effective, and durable fibrous materials [35]. It should be mentioned that the fibre mats obtained by the process of solution blowing also have three-dimensional curly and loose fibrous morphologies, which are helpful in the application of catalysis [58]. Feng Liang et al. reported on the fabrication of a three-dimensional micro-nanofibre structure with the minimum fibre diameter of 200 nm in the structure and the maximum porosity of 89.9% [33]. Solution blow spinning (SBS) has emerged as an alternative technique that can overcome the limitations of electrospinning during the production of submicron/nano sized fibres. The value of SBS is that it can be applied to both electrically conducting and insulating systems and does not need the application of an electric field and conductive collectors to initiate the fibre processing. SBS has less process requirements and variables compared to the electrospinning system during the fibre fabrication. SBS also has the ability, on planar and nonplanar substrates, to deposit conformal fibres [35]. Large scale fabrication is possible in SBS as it is in electrospinning [65]. Although melt blowing is the key commercial technique for nonwovens in the production of polymer microfibres, this process is only applicable for thermoplastic polymers and not suited for other polymers (e.g., polytetrafluoroethane) which have extremely high viscosities because of their high crystallinity and high melting points. This technique is not also suitable for biopolymers as they tend to denaturalize at high temperature [66]. In addition, fibres of the same size as the electrospun fibres cannot be generated by the melt blowing technique [67]. In contrast, SBS can effectively prevent thermal degradation of the polymer as it requires normal temperature and compressed air [65]. Melt blowing produces microfibres, whereas SBS are able to produce nanofibres as well as microfibres [67]. However, SBS technically generates fibres of the same size as the electrospun fibres with improved consumer scale potential [14]. In comparison to electrospinning, the SBS system has lower parameters and process requirements [35]. SBS has a high performance, simple function, fast planning time and high use value compared to the e-spinning technology. Furthermore, since no high-voltage electric field is needed in the spinning chamber, this device provides safe operation [37]. The thermo-degradation problems of polymers are eliminated as the solution blowing procedure applies compressed air at room temperature [66]. The higher velocity and characteristic forces of SBS are likely to support the chain orientation, contributing to the greater crystallinity of fibres compared to electrospinning [68]. One of the advantages of SBS is high spinning efficiency. According to Gao et al., the efficiency of solution blow spinning is 5-8 times higher than
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that of the single conventional electrospinning device. The SBS system produces fibres in the same size range as fibres produced by electrospinning, therefore, it has greater potential for being commercially scaled-up [14]. The electrical conductivity of the polymer solution has little impact on the fibre diameter in SBS and, subsequently, little reason to use extremely poisonous fluorinated solvents [35]. The diameter of the yttrium barium copper oxide (YBCO) superconducting fibres, for example, averaged 258 nm, 562 nm, and 984 nm, respectively, were produced with solution injection speeds of 60 μL/min, 80 μL/min and 100 μL/min [64]. In the case of an electrospinning technique, an injection rate of 1–6 μL/min is usually reported, whereas the injection rate for SBS lies in the range of 10–140 μL/min [69]. Besides, there is no need for a sophisticated support for a higher degree of protection, resulting in less system requirement [65]. In addition, the simple devices needed for SBS will allow researchers to explore new applications for nanofibrous and micro fibrous materials [35]. Santos et al. reported that the aqueous solutions of PVA were used to produce micro and nanofibres successfully through SBS [70]. Blending biopolymers is a mentionable advantage of solution blow spinning [67]. For instance, Liu et al. fabricated chitosan/PVA blended hydrogel nanofibre mats (HNMs) by SBS process [71]. It is very important to note that the processing of biopolymer fibres is not as easy and not as scalable as conventional polymers or thermoplastic polymers since biopolymers can be denaturalized at higher temperatures. Non-thermal methods are also the only feasible routes to produce biopolymer fibres. Researchers also use a polymer carrier to face the difficulties such as the globular shape, the absence of necessary viscoelasticity and low solubility in common solvents during biopolymer processing in electrospinning. However, it is notable that electrospinning can be problematic, and the charge distribution becomes difficult due to the regular polyelectrolytic nature. Solution blowing is a plausible solution in such a situation since the aerodynamic drag of the coaxial heavy air flow is the only driving force. This gives an excellent opportunity for the final composite to be maneuvered, especially with biopolymer blends [26]. SBS provides safe working conditions during the spinning operation [37]. Santos et al. also reported that the SBS method is suitable for producing alumina nanofibres at a low cost with reproducibility [72]. Besides, the airbrushing SBS can “paint” nanofibres on any target, while ES needs an electrically conductive target [13]. It is also worth mentioning that the airbrushing SBS has benefits over basic SBS in terms of cost and availability. The airbrushing SBS starts at $25, while solution blow spinning requires $260 for the nozzle and $690 for the syringe pump [48]. According to Areka, a single nozzle SBS system needs 300 l/min of compressed air and 1.5 kWh (approx.) of power, while electrospinning requires 200-500 Wh of power. It is also said that by using a central compressor instead of a portable one, the required level of power for the SBS system will be reduced to 0.1 kWh [37]. The energy efficiency of the compressor plays a significant role for power consumption of the SBS system since the cost of compressed air is significant. However, as the productivity of SBS is 30 times higher than that of electrospinning, the energy consumption rate per unit of production of the SBS system will be lower compared to that of electrospinning.
APPLICATIONS OF SBS SUBMICRON/ NANOFIBRE SBS-spun submicron/nanofibres have been applied widely due to their high surface area, crystalline structures, superior kinetic characteristic, and their practicability for a ready-to-scale-up system. Many fields have been already investigated regarding SBS-spun submicron/nanofibres, such as biomaterials, tissue engineering, textiles for environment, energy harvesting textiles and composites. Biomedical fields include tissue engineering, controlled release, antimicrobial films, and food packaging where SBS-spun nanofibres have been used successfully [29]. PLA nanofibre scaffolds fabricated by means of SBS provide favourable
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physical and chemical properties for being applied in tissue engineering [73]. Bhullar et al. mentioned that the airbrushed Nylon-6/AgCl composite nanofibres may be used as a potential candidate for fabricating antibacterial scaffolding system suitable for tissue engineering fields [46]. The production of biometrics scaffold for tissue regeneration mimicking the geometry of the native extracellular matrix (ECM) of tissues has been reported by many researchers [48,74]. SBS system also permits for portable device and conformal fibre deposition on any substrate [35]. For example, Gao et al. developed portable SBS device to guide fibre deposition and completed liver haemostasis in a minimally invasive surgical environment [38]. The core-shell PLA/PEG nanofibres incorporated with amphotericin B (AmpB) were synthesized through SBS for a controlled release and a successful encapsulation, as well as antifungal and antileishmanial activity. According to Gonçalves et al., the approach should be regarded as a therapeutic alternative for the treatment of fungal diseases and leishmaniasis in the production of drug delivery systems [75]. SBS core−shell fibres with epoxy precursors or other self-healing monomers loaded into the core provided self-healing properties and improved fatigue strength [76,77]. SBS nanofibres have gained an increased attention in wound healing. Several researchers already investigated the performances of SBS nanofibre dressings for wound healing purposes [78]. It can reduce the pain associated with wound healing and dressing change. Medical applications are distinctively fitted for direct fibre deposition in targets and would be able to take advantage of the properties of SBS that make it especially biocompatible: low toxicity, high porosity, and compatibility with biodegradable materials [35]. For instance, Liu et al. fabricated chitosan/PVA blended hydrogel nanofibre mats (HNMs) by the SBS process and recommended CS/PVA hydrogel nanofibre mats as a perfect moist dressing [71]. Stafford et al. conducted a research to create a conductive smart wound dressing for diabetic foot ulcers through solution blow spinning system [79]. SBS spun nanofibre offer significant opportunities to solve the environmental problem. It is a promising system to address the pollutions related to oil [80]. For example, Zhang et al. produced the polystyrene (PS) fibrous sponge and polyvinylidene fluoride (PVDF)/polystyrene (PS) composite package with the ultrahigh oil adsorption capacity through the SBS system. According to Zhang et al., it is viable for a large-scale industrial production of oil sorbents and oil spill clean-up for the protection of the environment [81]. The SBS-spun nanofibrous polystyrene membranes (NPS) could separate oil from water surface in a matter of seconds [82]. A composite membrane of SBS poly (methyl methacrylate) nanofibres wrapped with reduced graphene oxide (PMMA-rGO) was fabricated to adsorb the typical dye called methylene blue (MB) [83]. Membranes for the removal of methylene blue (MB) dyes from water were successfully developed by other researchers as well [84]. Tan et al. developed composite multi-layered filter mask from nanofibre materials (i.e., cellulose diacetate (CDA), poly (acrylonitrile) (PAN), and poly- (vinylidene fluoride) (PVDF)) produced by solution blow spinning. They reported better filter performances compared to the commercial surgical masks [85]. 500 mm wide PAN nanofibre membranes were realized by SBS that allows preparation of multi-level filter materials [86]. Zhuang et al. found that the mean pore size of the SBS mat is larger than that of the electrospun mat and smaller than that of the melt-blown fabric, making them a potential candidate for filtration [87]. Heat-resistant air filters based on polyimide were fabricated by this spinning system [88]. Micronutrient delivery systems comprised of Zn-loaded poly (butylene adipate-co-terephthalate) (PBAT) nanofibres were fabricated by SBS and results demonstrated that the SBS-spun nanofibres slowly released Zn to the soil in a controlled fashion [89]. SBS has developed a new type of modified Nafion membrane with sulfonated poly (ether ketone) (SPEEK) nanofibres for being utilized as a proton exchange membrane fuel cells [90]. Furthermore, PVDF nanofibre membranes (NFMs) produced by SBS were successfully used as self-powered nanogenerators [27]. Dong et al. developed β-phase-preferential SBS fabrics for wearable TENGs and a textile interactive interface application [91]. Moreover, CaFe2O4 nanofibres were successfully synthesized 190 www.textile-leather.com
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via solution blow spinning (SBS) for photocatalytic applications [92]. Production of ceramic nanofibres such as TiO2 nanofibres was performed through the SBS system followed by calcination [15]. Polystyrene nanofibrous (PSNF) mats containing the bromothymol blue (BTB) indicator for sensing the pH of wine was made by this spinning principle [93]. Conductive nonwoven fabric has successfully been developed and applied in smart textronics to detect various biosignals [94]. Huang et al. built highly flexible, 2D and 3D conductive electrodes using silver nanofibres (AgNFs) made by a modified blow spinning method [95]. SBS spun fibres sprayed as continuous mats on the surface or woven into textiles can be used in displays, thermochromic temperature sensors, chemical sensors or biological sensors. They allow for a huge potential in wearable textiles [96]. The fabrication of cellulose-based nanofibres remains a global challenge, particularly in terms of using alternative cellulosic materials. However, cellulose-based nanofibre membrane can be successfully fabricated through the assistance of an easy-to-spin polymer precursor (e.g., PAN) by using solution blow spinning (SBS) [97]. Zein fibres were successfully produced through (SBS) by using acetic acid as the solvent [98]. Food-grade gelatine nanofibres from pork skin gelatines (PGs) and fish skin gelatine are prepared by the SBS system [99]. Renewable polymers [100], such as starch, chitosan, cellulose [98], alginate, fibrinogen, fibrin, gelatine, and collagen need to be explored more and more because of their excellent performances in cell adhesion, proliferation [101], migration, differentiation, and characteristics analogous to those of ECM. However, many research works are supposed to be conducted to materialize fully the possibilities of the SBS spinning system for application in different fields.
LIMITATIONS AND CHALLENGES OF SBS SBS nanofibre nonwovens have some drawbacks, such as larger fibre diameter and more beaded fibres [102]. The reproducibility and alignment of nanofibres remain as one of the challenges of SBS [66]. Fibre morphology is weak for the solution blow spinning method, whereas the electrospinning process provides the optimized morphology of the resulting nanofibrous material in terms of porosity and fibre orientation [28]. However, a number of improvements to the SBS system are being made to address the shortcomings of this spinning system. For instance, Zheng et al. have devised a new cylindrical-electrode-assisted blowing solution (CSBS) technique to produce high-grade, ultra-fine nanofibres by combining air stretching and electrostatic forces. PEO nanofibre mats were successfully produced by using CSBS with satisfactory quality. The standard deviation in the diameter of the CSBS fibres decreased by 21% and the average fibre diameter decreased by 6.17% compared to the traditional SBS. In other words, the CSBS fibres had a greater uniformity and a higher fineness [70,102]. Moreover, the microfluidic spinning system is also considered as a modification of the solution blow spinning system. Well-aligned BaTiO3 membrane was obtained by modifying a fibre collection device for the SBS system [103]. Cryogenic solution blow spinning is another type of modification developed for producing 3D macroporous scaffold [104]. An aqueous solution blow spinning (ASBS) method is designed for the fabrication of seawater‐stable polyamidoxime/alginate nanofibres on a large scale in order to extract uranium from seawater [105]. However, there are still huge scopes of work needed in order to enable the incorporation of different types of modifications in the basic SBS setup for producing better quality nanofibrous mats along with the optimization of process parameters. Obtaining consistent fineness as similar as the fineness of the electrospun nanofibres and maintaining a smaller number of fibre beads should be recognized as significant challenges for the solution blow spinning system. Creation of a full range of SBS equipment to adapt to the commercial-scale production is still in its research stage. Owing to the short development period, SBS stays in the laboratory experimental stage [65]. However,
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it is one of the most industrially viable spinning systems for mass production of submicron/nanofibres without the need for major changes in business practices. Already, Kolbasov investigated the industrial approach of a multi-orifice SBS to generate soy protein-PEO nanofibrous nonwovens [106]. SBS has still a long way to go, particularly in the context of basic theory and material application research, which requires a considerable amount of planning. The mass processing of fibres may lead to a significant amount of solvent evaporation, increasing production costs and polluting the environment. Therefore, these issues need to be considered as challenges for the SBS system. SBS technology will advance with further product innovation [65]. The portable SBS technology also should be used in the field of rapid wound dressings, with a wide range of applications. It is desired that more sophisticated structures made from SBS nanofibre assemblies (e.g., nanofibre yarns from different polymers) be produced for novel applications. SBS-spun nano yarn may allow for obtaining complicated fibrous structures for diverse applications, including apparels. Additionally, research studies should focus on ameliorating the properties of the products made of the SBS-spun nanofibres as well as functionalizing the fabricated materials. Flame retardancy, thermal and electrical conductivity, magnetic properties, anisotropic properties, and improved mechanical stability can all be studied by using the SBSspun nanofibres. For example, recently Liu et al. incorporated a natural preservative (cinnamaldehyde) into fish skin gelatine (FSG) nanofibres fabricated by SBS, resulting in the increased level of antimicrobial activity. Tandon et al. integrated hydroxyapatite particles during the fabrication of stimuli responsive piezoelectric PVDF SBS-spun fibrous membranes in order to increase the bioactivity of tissue engineering scaffolds [107 -108]. Airbrushed Nylon-6/AgCl composite nanofibres have been fabricated in order to increase the antibacterial functionality that could be used for tissue engineering and regenerative medicine [46]. Dias et al. expected from their research that the Nickel nano particles incorporating the SBS-spun PVDF fibres can be utilized in magnetic sensors, flexible magnets, spintronic instruments, and the removal of impurities from oil, water, and blood [109]. In addition, further studies may be carried out to investigate the effects of hybrid nanofibre mats which may be produced by incorporating different polymers and tailoring the structure for specific and mass applications. It is also expected to look for the options for a greener solvent for solution blow spinning process. For instance, Parize et al. applied dimethyl carbonate (DMC) as a greener solvent for the PLA fibre production through SBS [34]. SBS will be crucial to the scientific community in the future as a means of finding new types of polymers and solvents that are not suitable for electrospinning, as well as a tool for producing translatable fibrous materials quickly [35]. Polymer/layered silicate (PLS) nano composites may be a possible research area for solution blow spinning. The conjugated nanofibre such as Janus fibre also needs to be explored through solution blow spinning system. However, it is required to study the structure-property relationship, theoretical modelling, and commercialization of the process. The prime issue of solution blow spinning still waiting to be resolved is commercialization. In a nutshell, solution blow spinning system presents a huge research opportunity for researchers interested in it.
CONCLUSION Solution blowing is a revolutionary method for spinning submicron/nanofibres from polymer solutions by using high-speed gas flow as a fibre-forming driving force at higher output rates, from different polymers and in an economical manner. This technique has been developed in order to overcome the constraints of traditional electrospinning and melt blowing techniques. Various types of improvements have already been made to this spinning system (e.g., CSB, CSBS, μSBS etc.). Airbrushing is commonly used as a promising tool in the production of nanofibre polymers based on the same technique as SBS. However, SBS is expected to
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grow significantly due to many advantages of nanofibres and their use in a wide range of industrial fields, including the atmosphere, electricity, electronics, biotechnology, pharmaceutics, and so on. More specifically, the SBS system is gaining its popularity in bio-medical applications due to its capability to produce nanofibrous mats without electricity. In the literature, nanofibres made by SBS are being reported on at a growing pace. Still, there are lot of areas in which the researchers can study the spinning process and SBSspun nanofibres. Although some significant issues in this spinning system must be addressed, continued research activities will undoubtedly allow advancements in the SBS technology in the near future, allowing solution blow spinning (SBS) processes and products to reach commercialization. Author Contributions All authors have contributed to the final mauscript. All authors provided critical feedback and helped to shape the final manuscript. Conceptualization – Khan MKR conceived and planned the study; methodology – Hassan MN developed the framework; Figures- Hassan MN collected the figures; writing-original draft preparation – Khan MKR wrote the manuscript; writing-review and editing – Khan MKR. All authors have read and agreed to the published version of the manuscript. Funding This research received no external funding. Conflicts of Interest The authors declare no conflict of interest.
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[57] Hofmann E, Krüger K, Haynl C, Scheibel T, Trebbin M, Förster S. Microfluidic nozzle device for ultrafine fiber solution blow spinning with precise diameter control. Lab on a Chip. 2018; 18(15):2225– 2234. https://doi.org/10.1039/C8LC00304A [58] Li L, Kang W, Li F, Li Z, Shi J, Zhao Y, Cheng B. Coaxial solution blowing of modified hollow polyacrylonitrile (PAN) nanofiber Fe complex (Fe-AO-CSB-HPAN) as a heterogeneous Fenton photocatalyst for organic dye degradation. RSC Advances. 2015; 5(84):68439–68445. https://doi.org/10.1039/C5RA09953F [59] Oliveira JE, Moraes EA, Marconcini JM, Mattoso LH, Glenn GM, Medeiros ES. Properties of poly(lactic acid) and poly(ethylene oxide) solvent polymer mixtures and nanofibers made by solution blow spinning. Journal of Applied Polymer Science. 2013; 129:3672-3681. https://doi.org/10.1002/ app.39061 [60] Zhuang X, Yang X, Shi L, Cheng B, Guan K, Kang W. Solution blowing of submicron-scale cellulose fibers. Carbohydrate Polymers. 2012; 90(2):982-987. https://doi.org/10.1016/j.carbpol.2012.06.031 [61] Park SC, Kim MJ, Choi K, Kim J, Choi S. Influence of shell compositions of solution blown PVP/PCL core–shell fibers on drug release and cell growth. RSC Advances. 2018; 8(57):32470-32480. https:// doi.org/10.1039/C8RA05485A [62] Hofmann E, Dulle M, Liao X, Greiner A, Förster S. Controlling polymer microfiber structure by micro solution blow spinning. Macromolecular Chemistry and Physics. 2020; 221:1900453. https://doi. org/10.1002/macp.201900453 [63] Vakili M, Vasireddi R, Gwozdz PV, Monteiro DC, Heymann M, Blick RH et al. Microfluidic polyimide gas dynamic virtual nozzles for serial crystallography. Review of Scientific Instruments. 2020; 91(8):085108. https://doi.org/10.1063/5.0012806 [64] Rotta M, Motta M, Pessoa AL, Carvalho CL, Ortiz WA, Zadorosny R. Solution blow spinning control of morphology and production rate of complex superconducting YBa2Cu3O7−x nanowires. Journal of Materials Science: Materials in Electronics. 2019; 30(9):9045–9050. https://doi.org/10.1007/s10854019-01236-w [65] Gao Y, Zhang J, Su Y, Wang H, Wang XX, Huang LP et al. Recent progress and challenges in solution blow spinning. Materials Horizons. 2021; 8(2):426-446 https://doi.org/10.1039/D0MH01096K [66] Zhang L, Kopperstad P, West M, Hedin N, Fong H. Generation of polymer ultrafine fibers through solution (air‐) blowing. Journal of Applied Polymer Science. 2009; 114(6): 3479-3486. https://doi. org/10.1002/app.30938 [67] Kakoria A, Ray SS. A review on biopolymer-based fibers via electrospinning and solution blowing and their applications. Fibers. 2018; 6(3):45. https://doi.org/10.3390/fib6030045 [68] Souza MA, Sakamoto KY, Mattoso LH. Release of the diclofenac sodium by nanofibers of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) obtained from electrospinning and solution blow spinning. Journal of Nanomaterials. 2014; 56:1-8. https://doi.org/10.1155/2014/129035 [69] Cena CR, Silva MJ, Malmonge LF, Malmonge JA. Poly (vinyl pyrrolidone) sub-microfibers produced by solution blow spinning. Journal of Polymer Research. 2018; 25(11):238. https://doi.org/10.1007/ s10965-018-1633-0 [70] Santos, AM, Medeiros EL, Blaker JJ, Medeiros ES. Aqueous solution blow spinning of poly(vinyl alcohol) micro- and nanofibers. Materials Letters. 2016; 176:122–126. https://doi.org/10.1016/j. matlet.2016.04.101 [71] Liu R, Xu X, Zhuang X, Cheng B. Solution blowing of chitosan/PVA hydrogel nanofiber mats. Carbohydrate Polymers. 2014; 101:1116-1121. https://doi.org/10.1016/j.carbpol.2013.10.056
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[72] Mota MF, Santos AM, Farias RM, Neves GA, Menezes RR. Synthesis and characterization of alumina fibers using solution blow spinning. Cerâmica. 2019; 65(374):190-193. https://doi.org/10.1590/036669132019653742618 [73] Granados-Hernández MV, Serrano-Bello J, Montesinos JJ, Alvarez-Gayosso C, Medina-Velázquez LA, Alvarez-Fregoso O et al. In vitro and in vivo biological characterization of poly (lactic acid) fiber scaffolds synthesized by air jet spinning. Journal of Biomedical Materials Research Part B: Applied Biomaterials. 2018; 106(6):2435–2446. https://doi.org/10.1002/jbm.b.34053 [74] Suarez-Franco JL, Vázquez-Vázquez FC, Pozos-Guillen A, Montesinos JJ, Alvarez-Fregoso O, AlvarezPerez MA. Influence of diameter of fiber membrane scaffolds on the biocompatibility of hPDL mesenchymal stromal cells. Dental Materials Journal. 2018; 37(3):465–473. https://doi.org/10.4012/ dmj.2016-329 [75] Gonçalves IM, Rocha ÍM, Pires EG, Muniz IA, Maciel PP, Lima JM et al. Effectiveness of core-shell nanofibers incorporating amphotericin B by solution blow spinning against leishmania and candida species. Frontiers in Bioengineering and Biotechnology. 2020; 8:571821. https://doi.org/10.3389/fbioe.2020.571821 [76] Lee MW, Yoon SS, Yarin AL. Solution-blown core-Shell self-healing nano- and microfibers. ACS Applied Materials & Interfaces. 2016; 8(7):4955-4962. https://doi.org/10.1021/acsami.5b12358 [77] Pelot D, Ray SS, Zhou Z, Rahman A, Wu XF, Yarin AL. Encapsulation of self-healing materials by coelectrospinning, emulsion electrospinning, solution blowing and intercalation. Journal of Materials Chemistry. 2012; 22(18):9138-9146. https://doi.org/10.1039/C2JM15696B [78] Bhullar SK, Buttar HS. Perspectives on nanofiber dressings for the localized delivery of botanical remedies in wound healing. AIMS Materials Science. 2017; 4(2):370-382. https://www.aimspress. com/article/10.3934/matersci.2017.2.370 [79] Stafford G. Nanocomposite conductive fibers via solution blow spinning for real-time wound sensing. South Carolina Junior Academy of Science. 2019; 132. [80] Zhang T, Tian H, Yin X, Li Z, Zhang X, Yang J et al. Solution blow spinning of polylactic acid to prepare fibrous oil adsorbents through morphology optimization with response surface methodology. Journal of Polymers and the Environment. 2020; 28:812–825. https://doi.org/10.1007/s10924-019-01617-6 [81] Zhang H, Wang R, Li P, Jia L, Wang F, Liu Y, Wang H, Yu L, Li B. One-step, large-scale blow spinning to fabricate ultralight, fibrous sorbents with ultrahigh oil adsorption capacity. ACS Applied Materials & Interfaces. 2021; 13(5):6631-6641. https://doi.org/10.1021/acsami.0c20447 [82] Zhang X, Lv J, Yin X, Li Z, Lin Q, Zhu L. Nanofibrous polystyrene membranes prepared through solution blow spinning with an airbrush and the facile application in oil recovery. Applied Physics A: Materials Science Processing. 2018; 124(5):362. https://doi.org/10.1007/s00339-018-1769-0 [83] Mercante LA, Facure MH, Locilento DA, Sanfelice RC, Migliorini FL, Mattoso LC et al. Solution blow spun PMMA nanofibers wrapped with reduced graphene oxide as efficient dye adsorbent. New Journal of Chemistry. 2017; 41(17):9087-9094. https://doi.org/10.1039/C7NJ01703K [84] Tan NP, Paclijan S, Franco SM, Abella R, Lague JC. Fresh and uncalcined solution blow spinning - spun PAN and PVDF nanofiber membranes for methylene blue dye removal in water. Journal of Membrane Science and Research. 2020. https://doi.org/10.22079/jmsr.2020.122267.1356 [85] Tan NP, Paclijan SS, Ali HH, Hallazgo CJ, Lopez CF, Ebora YC. Solution blow spinning (SBS) nanofibers for composite air filter masks. ACS Applied Nano Materials. 2019; 2(4):2475–2483. https://doi. org/10.1021/acsanm.9b00207
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[86] Song J, Liu Z, Li Z, Wu H. Continuous production and properties of multi-level nanofiber air filters by blow spinning. RSC Advances. 2020; 10: 19615-19620. https://doi.org/10.1039/D0RA01656J [87] Zhuang X, Jia K, Cheng B, Guan K, Kang W, Ren Y. Preparation of Polyacrylonitrile Nanofibers by Solution Blowing Process. Journal of engineered fibers and fabrics. 2013; 8(1):88-93. https://doi. org/10.1177/155892501300800111 [88] Li Z, Song J, Long Y, Jia C, Liu Z, Li L et al. Large-scale blow spinning of heat-resistant nanofibrous air filters. Nano Research. 2020; 13:861–867. https://doi.org/10.1007/s12274-020-2708-x [89] Natarelli CVL, Lopes CMS, Carneiro JS, Melo LCA, Oliveira JE, Medeiros ES. Zinc slow-release systems for maize using biodegradable PBAT nanofibers obtained by solution blow spinning. Journal of Materials Science. 2021; 56:4896–4908. https://doi.org/10.1007/s10853-020-05545-y [90] Wang H, Zhuang X, Li X, Wang W, Wang Y. Cheng B. Solution blown sulfonated poly(ether sulfone)/ poly(ether sulfone) nanofiber‐Nafion composite membranes for proton exchange membrane fuel cells. Journal of Applied Polymer Science. 2015; 132(38):42572. https://doi.org/10.1002/app.42572 [91] Ho DH, Han J, Huang J, Choi YY, Cheon S, Sun J et al. β-Phase-Preferential blow-spun fabrics for wearable triboelectric nanogenerators and textile interactive interface. Nano Energy. 2020; 77: 105262. https://doi.org/10.1016/j.nanoen.2020.105262 [92] Araujo RN, Nascimento EP, Sales HB, Silva MR, Neves GA, Menezes RR. CaFe2O4 ferrite nanofibers via solution blow spinning (SBS). Cerâmica. 2020; 66(380):467-473. https://doi.org/10.1590/036669132020663802932 [93] Miranda KWE, Natarelli CVL, Thomazi AC, Ferreira GMD, Frota MM, Bastos MDSR, et al. Halochromic polystyrene nanofibers obtained by solution blow spinning for wine pH sensing. Sensors (Basel). 2020; 20(2):417. https://doi.org/10.3390/s20020417 [94] Ho DH, Cheon S, Hong P, Park JH, Suk JW, Kim DH, Han JT, Cho JH. Multifunctional smart textronics with blow‐Spun nonwoven fabrics. Advanced Functional Materials. 2019; 29(24):1900025. https:// doi.org/10.1002/adfm.201900025 [95] Huang Y, Bai X, Zhou M, Liao S, Yu Z, Wang Y, Wu H. Large-scale spinning of silver nanofibers as flexible and reliable conductors. Nano letters. 2016; 16(9):5846-5851. https://doi.org/10.1021/acs. nanolett.6b02654 [96] West JL, Wang JR, Jákli A. Airbrushed liquid crystal/polymer fibers for responsive textiles. Advances in Science and Technology. 2016; 100:43–49. https://doi.org/10.4028/www.scientific.net/ast.100.43 [97] Dadol GC, Lim KJA, Cabatingan LK, Tan NPB. Solution blow spinning-polyacrylonitrile-assisted cellulose acetate nanofiber membrane. Nanotechnology. 2020; 31(34):345602. https://doi.org/10.1088/13616528/ab90b4 [98] Liu F, Avena-Bustillos RJ, Woods R, Chiou BS, Williams TG, Wood DF et al. Preparation of zein fibers using solution blow spinning method. Journal of Food Science. 2016; 81(12):N3015-N3025. https:// doi.org/10.1111/1750-3841.13537 [99] Liu F, Avena-Bustillos RJ, Bilbao-Sainz C, Woods R, Chiou BS, Wood D, Williams T et al. Solution blow spinning of food-grade gelatin nanofibers. Journal of Food Science. 2017; 82(6):1402-1411. https:// doi.org/10.1111/1750-3841.13710 [100] Zhao, Y, Qiu Y, Wang H, Chen Y, Jin S, Chen S. Preparation of nanofibers with renewable polymers and their application in wound dressing. International Journal of Polymer Science. 2016; 1-17. https://doi. org/10.1155/2016/4672839
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Instructions for Authors TEXT LEATH REV 4 (3) 2021 201-204.
INSTRUCTIONS FOR AUTHORS EDITING YOUR MANUSCRIPT Please use our template to edit your article before submitting for review. • Volume of a manuscript should not exceed 10.000 words, without Tables, Figures and Images. • Title of a manuscript should not exceed 15 words. • Full names and surnames of the authors, as well as full names of the author’s affiliation – university, institute, company, department, town and country should be clearly given. Corresponding author should be indicated, and their e-mail address provided. • Abstract of a manuscript should be no longer than 250 words. • Keywords should contain 3-7 items. • SI units should be used throughout. • Abbreviations should be used according to IUPAC and ISO standards and defined when first used. • Footnotes should be avoided. When their use is absolutely necessary, they should be numbered consecutively using Arabic numerals and appended at the end of the manuscript. • References should be cited using Arabic numbers in square brackets, according to the Vancouver referencing style. Please use our Quick Reference Guide (or look at the next page) • Figures and illustrations with a title and legend should be numbered consecutively (with Arabic numerals) and must be referred in the text. Images should be numbered as Figures. Additionally, Figures should be supplied as a separate file saved as jpg or tif at 300 dpi minimum. Type size in the description of axes should be proportional to the size of the Figure. • Tables with a title and optional legend should be numbered consecutively and must be referred in the text. • Acknowledgements may be included and should be placed after Conclusions and before References.
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Conference paper is the work presented at a professional conference organized on local, regional or state level. It will be published if it has not been published in full in Proceedings, as a report, a study etc. Professional paper deals with the issues in the profession. It gives professional instructions and suggestions for how to solve the issue (technique, technology, methodology). Professional review is a complete review of a professional issue (technique, technology, methodology) based on already published work indicating the best ways for solving the issue. The papers that are not categorized include: Presentation and communication from practical experience deals with solving the problem of particular laboratory, institution or industry and serve to inform interested parties of the solution applied. Position paper is an essay that presents an arguable opinion about an issue. Commentary is paper connected with actual news and condition in science and textile/clothing industry.
QUICK REFERENCE GUIDE Vancouver referencing style consists of: • citations to someone else’s work in the text, indicated by the use of a number, • a sequentially numbered reference list at the end of the document providing full details of the corresponding in-text reference. In-text citations • Insert an in-text citation: o when your work has been influenced by someone else’s work, for example: ▪ when you directly quote someone else’s work ▪ when you paraphrase someone else’s work • General rules of in-text citation: o A number is allocated to a source in the order in which it is cited in the text. If the source is referred to again, the same number is used o Use Arabic numerals in square brackets [1], [2], [3], … o Superscripts can also be used rather than brackets o Reference numbers should be inserted to the left or inside of colons and semi-colons o Reference numbers are placed outside or after full stops and commas Multiple works by the same author: Each individual work by the same author, even if it is published in the same year, has its own reference number. Citing secondary sources: A secondary source, or indirect citation, occurs when the ideas on one author are published in another author’s work, and you have not accessed or read the original piece of work. Cite the author of the work you have read and also include this source in your reference list.
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In-text citation examples The in-text citation is placed immediately after the text which refers to the source being cited: ...and are generally utilized as industrial textile composites.[1] Including page numbers with in-text citations: Page numbers are not usually included with the citation number. However should you wish to specify the page number of the source the page/s should be included in the following format: …and are generally utilized as industrial textile composites.[1 p23] Hearle [1 p16-18] has argued that... Citing more than one reference at a time: The preferred method is to list each reference number separated by a comma, or by a dash for a sequence of consecutive numbers. There should be no spaces between commas or dashes For example: [1,5,6-8] Reference List • References are listed in numerical order, and in the same order in which they are cited in text. The reference list appears at the end of the paper • Begin your reference list on a new page and title it References • The reference list should include all and only those references you have cited in the text • Use Arabic numerals [1], [2], [3], … • Full journal titles are prefered • Check the reference details against the actual source - you are indicating that you have read a source when you cite it Scholarly journal articles • Enter author’s surname followed by no more than 2 initials (full stop) • If more than 1 author: give all authors’ names and separate each by a comma and a space • For articles with 1 to 6 authors, list all authors. For articles with more than 6 authors, list the first 6 authors then add ‘et al.’ • Only the first word of the article title and words that normally begin with a capital letter are capitalized. • Use Full journal titles • Follow the date with a semi-colon; • Abbreviate months to their first 3 letters (no full stop) • Give the volume number (no space) followed by issue number in brackets • If the journal has continuous page numbering through its volumes, omit month/issue number. • Page numbers, eg: 123-129. Digital Object Identification (DOI) and URLs The digital object identifier (DOI) should be provided in the reference where it is available. Use the form as it appears in your source. Print journal article – Ferri L de, Lorenzi A, Carcano E, Draghi L. Silk fabrics modification by sol-gel method. Textile Research Journal. 2018 Jan;88(1):99-107. ▪ Author AA, Author BB, Author CC, Author DD. Title of article. Title of journal. Date of publication YYYY Mon DD;volume number(issue number):page numbers.
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Electronic journal article – Niculescu O, Deselnicu DC, Georgescu M, Nituica M. Finishing product for improving antifugal properties of leather. Leather and Footwear Journal [Internet]. 2017 [cited 2017 Apr 22];17(1):31-38. Available from: http://revistapielarieincaltaminte.ro/revistapielarieincaltaminteresurse/en/ fisiere/full/vol17 -nr1/article4_vol17_issue1.pdf ▪ Author AA, Author BB. Title of article. Title of Journal [Internet]. Date of publication YYYY MM [cited YYYY Mon DD];volume number(issue number):page numbers. Available from: URL Book – Hu J. Structure and mechanics of woven fabrics. Cambridge: Woodhead Publishing Ltd; 2004. 61 p. ▪ Author AA. Title of book. # edition [if not first]. Place of Publication: Publisher; Year of publication. Pagination. Edited book - Sun G, editor. Antimicrobial Textiles. Duxford: Woodhead Publishing is an imprint of Elsevier; 2016. 99 p. ▪ Editor AA, Editor BB, editors. Title of book. # edition[if not first]. Place of Publication: Publisher; Year. Pagination. Chapter in a book - Luximon A, editor. Handbook of Footwear Design and Manufacture. Cambridge: Woodhead Publishing Limited; 2013. Chapter 5, Foot problems and their implications for footwear design; p. [90-114]. ▪ Author AA, Author BB. Title of book. # edition. Place of Publication: Publisher; Year of publication. Chapter number, Chapter title; p. [page numbers of chapter]. Electronic book – Strasser J. Bangladesh’s Leather Industry: Local Production Networks in the Global Economy [Internet]. s.l.: Springer International Publishing; 2015 [cited 2017 Feb 07]. 96 p. Available from: https://link. springer.com/book/10.1007%2F978-3-319-22548-7 ▪ Author AA. Title of web page [Internet]. Place of Publication: Sponsor of Website/Publisher; Year published [cited YYYY Mon DD]. Number of pages. Available from: URL DOI: (if available) Conference paper – Ferreira NG, Nobrega LCO, Held MSB. The need of Fashion Accessories. In: Mijović B. editor. Innovative textile for high future demands. Proceedings 12th World Textile Conference AUTEX; 13-15 June 2012; Zadar, Croatia. Zagreb: Faculty of Textile Technology, University of Zagreb; 2012. p. 1253-1257. ▪ Author AA. Title of paper. In: Editor AA, editor. Title of book. Proceedings of the Title of the Conference; Date of conference; Place of Conference. Place of publication: Publisher’s name; Year of Publication. p. page numbers. Thesis/dissertation – Sujeevini J. Studies on the hydro-thermal and viscoelastic properties of leather [dissertation]. Leicester: University of Leicester; 2004. 144 p. ▪ Author AA. Title of thesis [dissertation]. Place of publication: Publisher; Year. Number of pages Electronic thesis/dissertation – Covington AD. Studies in leather science [dissertation on the internet]. Northampton: University of Northampton; 2010. [cited 2017 Jan 09]. Available from: http://ethos.bl.uk/ OrderDetails.do?uin=uk.bl.ethos.579666 ▪ Author AA. Title of thesis [dissertation on the Internet]. Place of publication: Publisher; Year. [cited YYYY abb. month DD]. Available from: URL This quick reference guide is based on Citing Medicine: The NLM Style Guide for Authors, Editors, and Publishers (2nd edition). Please consult this source directly for additional information or examples.
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