Nano TiO2 as a New Tool for Mothproofing of Wool: Protection of Wool

Article pubs.acs.org/IECR

Nano TiO2 as a New Tool for Mothproofing of Wool: Protection of Wool against Anthrenus verbasci Ali Nazari,*,† Majid Montazer,*,‡ and Mehdi Dehghani-Zahedani§ †

Art & Architectural Department and §Plant Protection Department, Yazd Branch, Islamic Azad University, Yazd, Iran ‡ Textile Engineering Department, Centre of Excellence in Textile, Amirkabir University of Technology, Hafez Avenue, Tehran, Iran ABSTRACT: Wool protection against moths is an important concept in wool finishing that can obtained through application of various chemicals with different mechanisms of actions. In this paper, a novel mothproofing method is introduced through treatment of wool fabric with nano titanium dioxide (NTO) and citric acid (CA). Citric acid (CA) helps to enhance the washing durability, antifelting, and antibacterial properties of the NTO treated wool. Mothproofing was assessed through the study of damages on the wool surface by the larvae of the carpet beetle, Anthrenus verbasci, feeding on protein fibers. The damage intensity of wool fabric and TiO2 nanoparticles on the fabric surface were confirmed with scanning electron microscopy images and energy-dispersive spectrometry. X-ray diffraction (XRD) of NTO treated fabrics indicated the crystal structure of NTO on the wool surface. Overall, the wool fabrics treated with CA and NTO indicated the highest protection against moths compared with raw and bleached wool fabrics.

1. INTRODUCTION Wool is extensively used as a high quality textile material due to its softness, warmth, lightness, and hydrophilic properties. There has been remarkable interest in inventing novel ideas for wool.1−3 Most people are aware of the considerable damage from wool fabric moths, but varied carpet beetles cause extensive damage without their control. The p-dichlorobenzene (PDB) and naphthalene crystals that are commercially available as mothproofers are toxic and can be absorbed into the body through inhaled vapors, especially over a long period of time.4 The major pest species, the carpet beetle, Anthrenus verbasci, mainly exists in birds’ nests.5 Damage is created by the larval stage, which develops over 1−2 years depending upon environmental conditions.6 The larvae are far more difficult to kill as they often remain hidden within food sources; however, the adults could be controlled by residual insecticides.7,8 Much of the effort on the application of insecticides against A. verbasci has focused on the proofing of fabric to restrain damage. Permethrin is one of the insecticides known to be effective in reducing damage from carpet beetles and cloth moths.9−11 This has been widely adopted as an insect proofing for wool fabrics. However, it was not effective in controlling the wandering of Anthrenus larvae.12 Nakajima (1999) extensively investigated the feeding damages to wool fabrics dyed with natural dyes in the presence of mordants, by larvae of Tinea translucens and Tineola bisselliella, and concluded that the dyed sample with plant dyestuff from bayberry, Myrica rubra, demonstrated the highest antifeeding effect among the examined wool samples.13 Application of nanoparticles to textiles has been vastly investigated to produce finished fabrics with high efficiencies and new characteristics. Nano silver creates antimicrobial properties, and ZnO nanoparticles have been used for providing UV-blocking and antibacterial effects.14−17 Nano TiO2 with high photoactivity, thermal and chemical stability, © 2012 American Chemical Society

low cost, and nontoxicity has been used in recent applications.18−20 For instance, it has been used in different industries such as water and air purification and photodegradation of dyes.21−24 The wool fibers with a porous nature provide a desirable warmth25 able to provide considerable properties such as UV protection and self-cleaning26,27 when treated with TiO2 nanoparticles. Polycarboxylic acids (PCA) were utilized accompanied by nano TiO2 in order to develop remarkable properties on wool such as stability, antifelting, and antibacterial properties.28 Oxidized wool is more prominently able to absorb nanoparticles and more efficiently through the introduction of more carboxyl and hydroxyl groups to the fiber29−34 as demonstrated quantitatively by Montazer and coworkers.35,36 In this study nano TiO2 particles were utilized as an antifeeding compound on wool fabric. In addition, citric acid (CA) as a friendly cross-linking agent accompanied nano TiO2 to stabilize the nanoparticles on the fabric surface. The wool fabrics were treated with nano TiO2 and CA through the exhaustion method. Each treated wool fabric was placed in the proximity of 10 varied carpet beetles, A. verbasci, for a period of 6 months. The extent of damage on wool fabrics was evaluated through the images obtained by scanning electron microscopy (SEM).

2-. MATERIALS AND METHODS 2.1. Materials. CA, sodium hydroxide, sodium hypophosphite (SHP), and hydrogen peroxide (37%) were supplied by Merck Chemical Co., Germany. Nonionic detergent (Rucogen DEN) composed of fatty alcohol ethoxylate was obtained from Received: Revised: Accepted: Published: 1365

August 15, 2012 November 30, 2012 December 31, 2012 December 31, 2012 dx.doi.org/10.1021/ie302187c | Ind. Eng. Chem. Res. 2013, 52, 1365−1371

Industrial & Engineering Chemistry Research

Article

2.2. Instrumentation. The contents of the finishing baths were prepared by using an ultrasonic bath (200 V, 50 W, 40 kHz). Scanning electron microscopic (SEM) observations on treated fabrics were carried out using an LEO 440i electron microscope (United Kingdom). An X-ray diffractometer type 3003 PTS, SEIFERT, Germany (λ = 1.540 60 Å, at 40 kV and 30 mA), with Cu Kα irradiation was used to identify the crystalline phase and also crystal size, using the Scherrer equation.37 2.3. Scouring and Bleaching Treatment. The wool fabric samples were prepared in 15 × 5 cm2 swatches. Scouring of wool fabrics was performed using 1% nonionic detergent (based on weight of fabric, OWF) at 60 °C for 60 min with a liquor to goods ratio of 30:1. Bleaching was performed using 3.5% hydrogen peroxide and 0.2% sodium hydroxide (OWF) at 50 °C for 50 min with a liquor to goods ratio of 8:1.

Table 1. Fabric Preparation run

wool

NTO (%)

SHP (g/L)

CA (g/L)

1 2 3 4 5

raw bleached treated treated treated

0.0 0.0 0.0 0.5 1.0

0.0 0.0 36.0 0.0 36.0

0.0 0.0 60.0 0.0 60.0

Rudolf Chemie Co. (Tehran, Iran). Nano titanium dioxide was employed as the photocatalyst with average particle size of 21 nm and 80% anatase and 20% rutile crystalline structure from Evonik Co., Duisburg, Germany. The raw twill weave 100% wool fabric was used with a weight of 230 g/m2 from Iran Merinous Co.

Figure 1. Raw and different treated fabrics in the proximity of A. verbasci in the period of 6 months after the beginning of the feeding test. 1366

dx.doi.org/10.1021/ie302187c | Ind. Eng. Chem. Res. 2013, 52, 1365−1371


Article

Scheme 1. Feeding Process of Larvae of A. verbasci on (a) Control Sample and (b) Sample Treated with CA and NTO

Figure 2. Images of (a) the larvae in the proximity of raw wool and (b) adult of A. verbasci in the proximity of treated wool with NTO and CA after the beginning of the feeding test.

detergent (Rucogen DEN), and finally dried at ambient conditions. 2.5. Insects. The extent of wool damage by the insect larvae through feeding differed depending on the growth stage and size of the larvae and the food availability. The larvae were feeding before the test.38,39 The following experiments were carried out on an insect attack with high reproducibility and universality of the results. A. verbasci larvae found in a cotton bag were collected and reared at 22−24 °C under 22−26% relative humidity (RH). Dried and powdered silkworm pupa was used as the rearing food for the successive generations of insects due to earlier reports on good growth of larvae with low mortality.40,41 Third to fifth instar young larvae (body length 4.0−5.0 mm and width 1.0−1.5 mm) were selected and used in the feeding tests.

2.4. CA and Nano Titanium Dioxide (NTO) Treatment. The aqueous solution was prepared by CA and SHP (60% CA) and required distilled water in an ultrasonic bath for 10 min (Table 1) at 70 °C. The raw and bleached wool fabrics were impregnated by freshly prepared aqueous solutions at 80 °C for 50 min. The CA treated fabrics were dried at 100 °C and cured at 150 °C for 90 s. NTO particles were then applied on different wool samples in various concentrations (Table 1). The impregnated bath was prepared by nano titanium dioxide powder in an ultrasonic bath that was sonicated for 45 min at 50 °C to disperse the nanoparticles. The CA treated fabrics were impregnated into the prepared NTO colloid solution at 80 °C and treated for 50 min. The treated fabrics were dried at 100 °C for 45 min and then washed at 70 °C for 30 min using a solution containing 2 g/L Na2CO3 and 1 g/L nonionic 1367



Article

Figure 3. SEM images of wool samples: (a) raw, (b) bleached, (c) treated with 60.0 g/L CA and 36.0 g/L SHP, (d) treated with 0.5% NTO, and (e) treated with 1.0% NTO, 60.0 g/L CA, and 36.0 g/L SHP (5000×).

2.6. Bioassay. 2.6.1. Feeding Tests. The treated fabric was cut into 5 × 5 cm2 pieces (the weight of each fabric was about 0.5 g) and placed in a plastic breeding plate (20 cm × 3 cm) in order to determine the efficacy of materials. Ten A. verbasci larvae were selected in each treatment, and five replicates of plastic breeding plates of each treated fabric were prepared. Larvae were placed in the plastic breeding plates at laboratory conditions. All rearings was conducted at 25 ± 2 °C, 22−26% RH, and a photoperiod of 16:8 (light:dark) h for a period of 6 months. Raw and bleached wool fabrics were used as the control. The wool damage by an insect was determined through weighing the residual fabric measured by a balance (BP310S, Sartorius AG). Small detached fibers from fabric samples produced by insect feeding were included in the insect-fed fraction, as the shape of the fiber had been changed and was difficult to weigh. Figure 1 shows the condition of raw and treated wool fabrics in the proximity of 10 varied carpet beetles, A. verbasci, for the period of 6 months after the feeding test began.

2.6.2. Feeding Preference Test. Eleven pieces of treated fabric with different conditions were placed in a plastic breeding plate along with 10 A. verbasci larvae. Three replicate plates were incubated at 22−24 °C and 22−26% RH; 85% of larvae adjacent to the control sample had transformed to pupae. 2.7. Morphological Characterization. A scanning electron microscope (SEM) (KYKY-EM 3200) was used to determine the morphologies of raw, bleached, and nano TiO2 treated wool fabrics. The crystalline phase and crystal size of the nano TiO2 treated wool surface were studied using an X-ray diffractometer (XRD Bruker) with Cu Kα light.

3. RESULTS AND DISCUSSION 3.1. Protective Properties of Wool. The feeding process of the larvae of A. verbasci on untreated wool fabric and wool fabric treated with NTO and CA is illustrated in Scheme 1. The larvae of A. verbasci were not nurtured by the wool treated with NTO and CA, which led to their becoming thinner and their death after 6 months (Figure 2a), while the larvae in 1368



Article

Figure 4. XRD patterns of different samples: (a) pure NTO powders, (b) raw wool fabric, (c) treated fabric with 0.50% NTO (run 4), and (d) treated fabric with 1.0% NTO and 60 g/L CA (run 5).

the proximity of the untreated wool had a complete feeding from the fabric (Figure 2b), which confirmed the suitability of proteins as a nutrient for A. verbasci. 3.2. Scale Analysis. In the fed cases, the larval length and width are 5.0 mm and 3.0 mm, respectively, but in the unfed cases, they are 4.0−5.0 mm and 1.0−1.5 mm respectively. Thus, the ratio of the width to length of the larvae increased in the fed case condition (the criterion of the width relative to length could be considered in the scale).42−44 3.3. Scanning Electron Microscopy (SEM). The scanning electron microscopy (SEM) images of the treated and untreated fabrics are presented in Figure 3. The superficial damages generated on the raw and bleached fabrics are indicated in Figure 3a,b. The highest feeding of larvae occurred in the raw and bleached wool fabrics and led to remarkable damages on the wool fibers. The larvae available in the proximity of these samples were fat with some transformation to adult beetles during the 6 months. This proves the suitability of the keratin protein of wool as a nutrient for the larvae of A. verbasci. Figure 3e indicates no changes on the fiber surfaces, confirming the unsuitability of the treated wool with NTO and CA as a feeding material for larvae that led to the death of some larvae. Therefore, wool treatment with CA and NTO was proposed as a novel idea to obtain superior protection against moths. Hence, the serious problem of the wool vulnerability with larvae of A. verbasci can be solved through treatment with NTO/CA. Further, the antibacterial

and antifelting properties of the treated wool fabric with CA and NTO have been proved by Montazer et al.28 The death of larvae in the proximity of the wool treated with CA and NTO could be attributed to the conversion of the wool to an antifeeding material as it has not been fed on by the larvae after 6 months, which led to their death. The other possibility of the larval death can be related to the utilization of NTO as a nutritional material in such a manner that the nano TiO2 particles cause the hampering of their life. In any case, there has not been reported any reliable information in this area. Also, less superficial damage on wool fabrics indicated in Figure 3c,d showed the complementary effect of NTO in addition to CA on the wool. The CA as a polycarboxylic acid is not only capable of creating cross-linking between molecular chains of protein structure but also can stabilize nanoparticles on the surface of wool fabric.45,46 3.4. X-ray Diffraction (XRD). The XRD patterns of pure NTO, raw wool (run 1), fabric treated NTO (run 4), and fabric treated with NTO and CA (run 5) are presented in Figure 4. The crystal phase of nano TiO2 on wool fabric was studied using the XRD technique. The XRD pattern in Figure 4a shows the intense peak for anatase structure compared to rutile. Particle sizes of different structures were compared based on the full width at half-maximum (fwhm) of the peaks. The XRD pattern of the treated fabrics with NTO is shown in Figure 4c,d. The anatase peak appeared at 2θ = 27.42 in Figure 4c and at 2θ = 24.32 in Figure 4d, and their crystal size was obtained by 1369



Article

(14) Becheri, A.; Dürr, M.; Lo Nostro, P.; Baglioni, P. Synthesis and characterization of zinc oxide nanoparticles: application to textiles as UV-absorbers. J. Nanopart. Res. 2008, 10, 679−689. (15) Sivakumar, P. M.; Balaji, S.; Prabhawathi, V.; Neelakandan, R.; Manoharan, P. T.; Doble, M. Effective antibacterial adhesive coating on cotton fabric using ZnO nanorods and chalcone. Carbohydr. Polym. 2010, 79 (3), 717−723. (16) Dastjerdi, R.; Montazer, M.; Shahsavan, S. A new method to stabilize nanoparticles on textile surfaces. Colloids Surf., A 2009, 345, 202−210. (17) Dastjerdi, R.; Montazer, M.; Shahsavan, S. A novel technique for producing durable multifunctional textiles using nanocomposite coating. Colloids Surf., B 2010, 81, 32−41. (18) Yang, H.; Zhu, S.; Pan, N. Studying the mechanisms of titanium dioxide as ultraviolet blocking additive for films and fabrics by an improved scheme. J. Appl. Polym. Sci. 2004, 92, 3201−3210. (19) King, D. G.; Pierlot, A. P. Absorption of nanoparticles by wool. Color. Technol. 2009, 125, 111−116. (20) Martel, B.; Weltrowski, M.; Ruffin, D.; Morcellet, M. Polycarboxylic acids as crosslinking agents for grafting cyclodextrins on to cotton and wool fabrics: Study of the process parameters. J. Appl. Polym. Sci. 2002, 83, 1449−1456. (21) Kühn, K. P.; Chaberny, I. F.; Massholder, K.; Stickler, M.; Benz, V. W.; Sonntag, H.; Erdinger, L. Disinfection of surfaces by photocatalytic oxidation with titanium dioxide and UVA light. Chemosphere 2003, 53, 71−77. (22) Yao, K. S.; Wang, D. Y.; Ho, W. Y.; Yan, J. J.; Tzeng, K. C. Photocatalytic bactericidal effect of TiO2 thin film on plant pathogens. Surf. Coat. Technol. 2007, 201, 6886−6888. (23) Valentine Rupa, A.; Manikandan, D.; Divakar, D.; Sivakumar, T. Effect of deposition of Ag on TiO2 nanoparticles on the photodegradation of reactive yellow-17. J. Hazard. Mater. 2007, 147, 906− 913. (24) Rincon, A. G.; Pulgarin, C. Photocatalytical inactivation of E. coli: effect of (continuous-intermittent) light intensity and of (suspended-fixed) TiO2 concentration. Appl. Catal., B 2003, 44, 263−284. (25) Davidson, R. S. The photodegradation of some naturally occurring polymers. J. Photochem. Photobiol., B: Biol. 1996, 33, 3−25. (26) Tung, W. S.; Daoud, W. A. Photocatalytic self-cleaning keratins: A feasibility study. Appl. Catal., B: Environ. 2009, 5, 50−56. (27) Montazer, M.; Pakdel, E. Functionality of nano titanium dioxide on textiles with future aspects: Focus on wool. J. Photochem. Photobiol. C 2011, 12, 293−303. (28) Montazer, M.; Pakdel, E.; Behzadnia, A. Novel feature of nanotitanium dioxide on textiles: antifelting and antibacterial wool. J. Appl. Polym. Sci. 2011, 121, 3407−3413. (29) Qi, K.; Daoud, W. A.; Xin, J. H.; Mak, C. L.; Tang, W.; Cheung, W. P. Self-cleaning cotton. J. Mater. Chem. 2006, 16, 4567−4574. (30) Daoud, W. A.; Leung, S. K.; Tung, W. S.; Xin, J. H.; Cheuk, K.; Qi, K. Self-cleaning keratins. Chem. Mater. 2008, 20, 1242−1244. (31) Montazer, M.; Pakdel, E. Self-cleaning and color reduction in wool fabric by nano titanium dioxide. J. Text. Inst. 2011, 102, 343− 352. (32) Nazari, A.; Montazer, M.; Rashidi, A.; Yazdanshenas, M.; Moghadam, M. B. Optimization of cotton crosslinking with polycarboxylic acids and nano TiO2 using central composite design. J. Appl. Polym. Sci. 2010, 117, 2740−2748. (33) Nazari, A.; Montazer, M.; Rashidi, A.; Yazdanshenas, M.; AnaryAbbasinejad, M. Nano TiO2 photo-catalyst and sodium hypophosphite for cross-linking cotton with poly carboxylic acids under UV and high temperature. Appl. Catal., A 2009, 371, 10−16. (34) Dastjerdi, R.; Montazer, M. A review on the application of inorganic nano-structured materials in the modification of textiles: focus on anti-microbial properties. Colloids Surf., B 2010, 79, 5−18. (35) Montazer, M.; Pakdel, E.; Moghadam, M. B. Nano titanium dioxide on wool keratin as UV absorber stabilized by butane tetra carboxylic acid (BTCA): a statistical prospect. Fibers Polym. 2010, 11, 967−975.

using eq 1, 35.11and 37.81 nm, respectively. The main peaks of anatase phase are seen in both treated wool fabrics. The peak intensity of the cross-linked wool was higher than the un-crosslinked one and presented more anatase phase on the crosslinked fabric. crystal size (Å) =

K ·λ ·180 fwhm·π ·cos θ

(1)

This study examines a new approach for superior protective finishing on wool against A. verbasci using nano TiO 2 accompanied by CA as a cross-linking agent that helps increase the stability of nano TiO2 on the fabric. Irretrievable damages occurred on raw and bleached wool fabrics compared with wool fabrics treated with nano TiO2 and CA. Overall, the successful idea was proposed based on the utilization of nano TiO2 for the creation of protective finishing on wool against A. verbasci.

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected] (A.N.); [email protected] (M.M.). Tel.: +989132742611 (A.N.); +982164542657 (M.M.). Notes

The authors declare no competing financial interest.

■

REFERENCES

(1) Xu, W.; Ke, G.; Wu, J.; Wang, X. Modification of wool fiber using steam explosion. Eur. Polym. J. 2006, 42, 2168−2173. (2) Mahbubul Hassan, M.; Falcon Davies-McConchie, J. Removal of arsenic and heavy metals from potable water by bauxsol immobilized onto wool fibers. Ind. Eng. Chem. Res. 2012, 51 (28), 9634−9641. (3) Sun, S. S.; Tang, R. C. Adsorption and UV protection properties of the extract from honeysuckle onto wool. Ind. Eng. Chem. Res. 2011, 50 (8), 4217−4224. (4) Cardamone, J. M. Biodeterioration of wool by microorganisms and insects. Bioactive Fibers and Polymers; ACS Symposium Series 792; Edwards, J. V., Vigo, T. L., Eds.; American Chemical Society: Washington, DC, 2001; Chapter 16, pp 263−298. (5) Woodroffe, G. E.; Southgate, B. J. Birds nests as a source of domestic pests. Proc. Zool. Soc. London 1951, 121, 55−62. (6) Blake, G. M. Diapause and the regulation of development in Anthrenus verbasci (L.) (Col., Dermestidae). Bull. Entomol. Res. 1958, 49, 151−155. (7) Shepard, H. H. The status of agricultural chemicals. Trends in pesticidal chemicals. J. Agric. Food Chem. 1953, 1 (12), 756−770. (8) Tyler, P. S.; Binns, T. J. The toxicity of seven organophorphorous insecticides and lindane to eighteen species of stored-product beetles. J. Stored Prod. Res. 1977, 13, 329−343. (9) Thomas, A.; Harland, D. P.; Clerens, S.; Deb-Choudhury, S.; Vernon, J. A.; Krsinic, G. L.; Walls, R. J.; Cornellison, C. D.; Plowman, J. E.; Dyer, J. M. Interspecies comparison of morphology, ultrastructure, and proteome of mammalian keratin fibers of similar diameter. J. Agric. Food Chem. 2012, 60, 2434−2446. (10) Friedman, M.; Ash, J. F.; Bry, R. E.; Simonaitis, R. A. Mothproofing wool and wool blends with permethrin. J. Agric. Food Chem. 1979, 27, 331−336. (11) Bry, R. E.; Simonaitis, R. E. Long term protection of woollen fabric with permethrin. Soap, Cosmet., Chem. Spec. 1989, 65 (4), 66− 70. (12) Hillyer, L.; Blyth, V. Carpet beetles: A pilot study in detection and control. Conservator 1992, 16, 65−77. (13) Nakajima, T. Managements of Rats and Pests in Environmental Sanitation; Shibazaki, I., et al., Eds.; Fuji Techno System, Ltd.: Tokyo, Japan, 1999; pp 521−549 (in Japanese). 1370



Article

(36) Montazer, M.; Pakdel, E. Reducing photoyellowing of wool using nano TiO2. Photochem. Photobiol. 2010, 86, 255−260. (37) Wang, H.; Wu, Y.; Xu, B. Q. Preparation and characterization of nanosized anatase TiO2 cuboids for photocatalysis. Appl. Catal., B 2005, 59 (3−4), 139−146. (38) Kuwana, Z.; Nakamura, S.; Sugiyama, H. Change with larval growth of the feeding amount on wool fabrics of Attagenus piceus and Anthrenus verbasci larvae. Sanshi Kenkyu [Acta Sericol.] 1960, 33, 57− 63 [in Japanese with English summary]. (39) Nakamoto, N. Damage to silk by textile insect pests. Sen’i Seihin Shohi Kagaku [J. Jpn. Res. Assoc. Text. End-Uses] 1997, 38 (8), 416− 423 [in Japanese]. (40) Kato, H. Feeding of Anthrenus verbasci on wool fabric dyed with insect pigment. Nihon Silk Gakkaishi [J. Silk Sci. Technol. Jpn.] 2000, 9, 23−27 [in Japanese]. (41) Nakamoto, N.; Nakamura, S. Amount of feeding on cocoons attacked by Attagenus piceus (OLIVIER). Seishi Kinu Kenkyu Happyo Shuroku [Contain. Res. Filature Silk] 1979, 29, 1−9 [in Japanese]. (42) Daly, H. V. Insect morphometrics. Annu. Rev. Entomol. 1985, 30, 415−438. (43) Klingenberg, C. P.; Zimmermann, M. Dyar’s rule and multivariate allometric growth in nine species of waterstriders (Heteroptera: Gerridae). J. Zool. 1992, 227, 453−464. (44) Coxa, P. D.; Pinniger, D. B. Biology, behaviour and environmentally sustainable control of Tineola bisselliella (Hummel) (Lepidoptera: Tineidae). J. Stored Prod. Res. 2007, 43, 2−32. (45) Montazer, M.; Seifollahzadeh, S. Enhanced self-cleaning, antibacterial and UV protection properties of nano TiO2 treated textile through enzymatic pretreatment. Photochem. Photobiol. 2011, 87, 877−883. (46) Montazer, M.; Pakdel, E.; Moghadam, M. B. The role of nano colloid of TiO2 and butane tetra carboxylic acid on the alkali solubility and hydrophilicity of proteinous fibers. Colloids Surf., A 2011, 375, 1− 11.

1371


Nano TiO2 as a New Tool for Mothproofing of Wool: Protection of Wool

Recommend Documents