ZnO nano reactor on textiles and polymers: ex situ and in situ synthesis, application, and characterization.

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ZnO Nano Reactor on Textiles and Polymers: Ex-Situ and In-Situ Synthesis, Application and Characterization Majid Montazer, and Morteza Maali Amiri J. Phys. Chem. B, Just Accepted Manuscript • Publication Date (Web): 22 Nov 2013 Downloaded from http://pubs.acs.org on December 4, 2013

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The Journal of Physical Chemistry

ZnO Nano Reactor on Textiles and Polymers: Ex-Situ and In-Situ Synthesis, Application and Characterization Majid Montazer*, Morteza Maali Amiri Textile Department, Center of Excellence in Textile, Amirkabir University of Technology, Hafez Avenue, Tehran, Iran

*Corresponding to: Dr. Majid Montazer Associate Professor, Textile Department, Center of Excellence in Textile, Amirkabir University of Technology, Hafez Avenue, Tehran, Iran Email: [email protected] Phone: +9821 64542657 Fax: +9821 66400245

1

ACS Paragon Plus Environment


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Abstract The zinc oxide consumption increases in today’s world. It is one of the most popular nanoparticles with photocatalytic activity under light illumination utilized in different industries, especially in textile and polymers. Lately, textiles and polymers with new features produced through utilization of ZnO nano particles to create photocatalytic characteristics, UV absorption, self-cleaning and antimicrobial properties. Various approaches have been introduced to synthesize and apply nanoparticles on the textile and polymer surfaces such as cotton, polyester, wool and others. This review presents diverse aspects of nano zinc oxide application in textile and polymer industry and approaches used for in situ and exsitu synthesis and application of nano zinc oxide on different textiles and polymers. This also brings a brief overview on the several researches accomplished in this area.

Keywords: Nano zinc oxide, Photocatalyst, Textile, Polymer, Ex-situ synthesis, In-situ synthesis.

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1. Introduction Nanotechnology can be applied in many areas.1-3 This has been started to apply on textiles by Nano-Tex.4 Afterwards, other textile corporations commenced to invest in the nanotechnology development.4 Application of the nanoparticles on textiles has been the aim of various studies, to produce fabrics with diverse practical performance.5 For instance, nano silver, nano ZnO and nano TiO2 have been utilized

to

impart

antibacterial,6,7

UV-blocking/antibacterial8,9

and

self-

cleaning/UV-blocking/antimicrobial properties respectively.10-13 Nanoparticles can supply high durability against washing process, as possessing great surface area and elevated surface energy which guarantee more attraction for fabrics.14 In order to enhance the fastness of nanoparticles against washing, a specific binder solution can be used.8,15 This affects other properties of fabric such as tensile and bursting strength, friction and air penetrability.

16

The air permeability of cotton fabric

treated with nano ZnO is more than bulk ZnO.16 Also nano coating of titania partly increased cotton bursting strength.11 Metal oxide nanoparticles such as ZnO and TiO2 are more desirable than nano Ag and other nano materials, as being cheaper, more stable while exposing to high temperature, without toxic effect having photocatalytic activities.15,17 ZnO and TiO2, as semiconductors, can be utilized in textile productions18 however the most important advantage of ZnO as compared to 3



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TiO2 is absorbing a greater part of UV spectrum.19 Zinc oxide nanoparticles have been used in diverse applications such as solar cells,20 luminescence,21,22 gas sensors,23,24 disinfection of both drinking and waste water, 25 UV-blocking, surface acoustic wave filters and photo detectors31 due to its anti-bacterial, photocatalytic, electrical, electronic, optical, and dermatological characteristics.27-35 ZnO has also been used in textile industry for different purposes such as UV-absorbing and antibacterial effects on cotton,36,37 UV-protection on wool,16 self-cleaning characteristics on cellulosic fibers,38 hydrophobic on cotton fabrics,39 antistatic on polyester fabric40 and stain-releasing from textiles.1 Further, the use of nano ZnO in polymer nanocomposites for different application in diverse industries has increased due to dielectric constant, thermal stabilizing effect and specific mechanical properties.41-47 Polymer nanocomposites are used more than polymers with micro fillers due to enhanced resistance to degradation and higher thermal stabilization .43,48,49 These discoveries are related to our lives, and granted new characteristics to garments to make the quality better, altering the path of conventional industrial finishing. Textile industry has introduced new products to customers, using the new characteristics of semiconductors. Many researches have been worked on the topic of zinc oxide. This review brings different aspect of nano zinc oxide application in the textile and polymer industries 4


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in addition to a clear description of novel imparted characteristics to textiles and polymers such as UV-blocking, self-cleaning and wettability between other novel textile and polymer features. Indeed, in this paper properties of nano ZnO are deeply discussed and the affecting factors are also mentioned, to show the future trend to reach the final textile and polymer products with the best possible properties. To the best our knowledge this is the first review paper on application of nano ZnO in textile and polymer industry, which aims to bring the most useful properties of nano ZnO in terms of textile and polymer industry. This review also presents the numerous methods for applying nano ZnO on the textiles and their advantages and compare them to each other.

2. The photocatalytic mechanism of nano ZnO and the influencing factors Photocatalysts are widely used for destroying organic contaminants.50 TiO2, as one of the most active photocatalysts, has been widely examined.51 However zinc oxide has also been greatly utilized as a photocatalyst, due to its high activity, environmentally friendly and low cost characteristics.52-58 Moreover, TiO2 can be replaced with ZnO for degradation of organic materials59-61 because of its low cost and higher photocatalytic activity62 and close band gap energy (3.3 eV)63 to TiO2(3.2 eV).64 ZnO is a member of the metal oxides group having photo-oxidizing 5



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and photocatalytic potential against biological and chemical species. This employs a multifunctional nanoplatform to bombard harmful cells through generating reactive oxygen species (ROS)65 as the most important part of photocatalytic characteristics of metal oxides.66,67 ZnO photocatalytic activity result from donor states produced by the great number of defect locations such as oxygen vacancies and interstitial atom of zinc and the states of acceptor which caused with zinc vacancies and interstitial atoms of oxygen. During UV illumination, incident ray with energy equal or higher than energy of ZnO band gap cause the interfacial transfer of electron between the oxygen vacancies and interstitial atom of zinc leading to generation of the electrons of conduction band and holes of valence band.68-71 Holes are able to react with water sticking to ZnO surface to form

.

hydroxyl radicals (OH ), simultaneously oxygen, on the ZnO surface is reduced to superoxide by generated electrons which leads to generation of hydroxyl radicals

.

(OH ). The mechanism of reactions is summarized in reactions 1-7: 72

-

ZnO + hν → ZnO (e +h+)

(1) .

ZnO (h+) + H2O → ZnO + OH + H+

(2)

. -

ZnO(e-) + O2 → ZnO + O 2

(3)

. -

O 2 + H+ → .HO2

(4) 6


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HO2- + H+ → H2O2

(5)

.

2 HO2 → O2 +H2O2

(6) .

ZnO (e-) + H2O2 → ZnO + OH + OH-

(7)

.

OH + Organic molecules → Decomposed products

Hydroxyl radicals have a potential of demolishing diverse compounds such as bacteria and organic molecules.73 The efficiency of the photo-generated electron hole pairs is dependant on incident photons intensity. 74 TiO2 and ZnO can be used as a photocatalyst under UV illumination for decomposition of organic pollutants.75-79 However ZnO with great number of active sites exhibits higher photocatalytic activity in comparison to TiO2 under visible light illumination.80 Since visible light has 45% of total energy in the solar radiation and UV light has less than 10%81 thus it is desirable for ZnO to absorb not only UV but also visible light. In order to achieve this, ZnO band gap should be narrowed, by doping with transition metal ions

82,83

such as Pt and Ag.84-86 The other problem for decreasing

photocatalytic efficiency which can be solved is rapid recombination of photoinduced, electron hole pairs.87 Therefore modification of semiconductor for enhancing photocatalytic activity has become the most important subject.88,89 Up to now, many methods have been employed to modify nano ZnO. For example, coupling two semiconductors such as ZnO/TiO2, ZnO/SnO2 and ZnO/Fe2O3,90-94 or 7



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doping with transition metal ions such as Fe, Ag95-97 and Co70 are some of the important ones. The combination of semiconductors and transition metals has been demonstrated to improve the photocatalytic activity and charge transfer.98,99 The proposed photocatalytic mechanism of Ag/ZnO is shown in reactions 8-12 :100,101 -

ZnO + hν → e 1+h+ -

(8) -

Ag → Ag+ + e 2(ore 1) -

(9)

. -

-

e 2(ore 1) + O2→ O 2

(10)

-

Ag+ + e 1→ Ag

(11)

.

h++ OH-→ OH (5)

(12)

ZnO produces electron hole pairs, Ag with sinking the electrons improve the electron hole separation. O2 as an electronic acceptor, trap photoelectrons generating superoxide radical anion, and photo-induced holes are able to be trapped with OH- producing hydroxyl radicals. Therefore with separation of electron hole pairs, the lifetime increases enhancing photocatalytic activity.102 Also the suggested mechanism for enhancing the efficiency of photocatalytic activity of ZnO/TiO2 is the photo-induced electrons from the excited ZnO conduction band into TiO2. In the same way, the photo-induced hole is transferred to the ZnO 8


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valence band from the TiO2 valence band. Thus the possible recombination of electron hole pairs decreases, their lifetime increases, prone to enhance photocatalytic reaction efficiency.103-105 The photocatalytic mechanism of ZnO, ZnO doped with Ag and ZnO coupled with TiO2 has been shown in Fig.1.

Fig.1. Photocatalytic mechanism of ZnO, ZnO doped with Ag and ZnO coupled with TiO2

The other factors influencing photocatalytic efficiency are surface oxygen vacancies and defects which have a direct relation with particle size.106,107,108 This means smaller particle size (higher specific surface area) result in the more surface oxygen vacancy and higher photocatalytic activity.106,107,108 Defects and surface oxygen vacancies are capable of trapping photo-induced electrons during photocatalytic reaction resulting in effective interaction between the adsorbed O2 and trapped electrons preventing electron hole pairs recombination.106 These defects can be intentionally produced in ZnO structure with higher annealing temperature which also leads to the formation of smaller particles.72,109 Therefore 9



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their mechanism is similar to the transition metal ions, because defects, surface oxygen vacancies and transition metal ions, improve photocatalytic efficiency of ZnO through trapping photo-induced electrons. ZnO has so far been generated with diverse morphologies through different synthesis approaches. The nanocrystal catalytic performance is dependant either on the composition or the morphologies that influence the atomic coordination and arrangements.110 Morphology of the ZnO can directly affect the photocatalytic performance of nanoparticle.110 ZnO can be found in numerous shape, including flower-like, rod-like, hourglass-like, spherical and others, with different photocatalytic activity.110 Precursor, solvent type and thermodynamic factors such as temperature and pressure result in different ZnO morphology.110 The difference in photocatalytic activity of various shapes arises from differences in polar planes, surface areas and oxygen vacancies.110 ZnO hollow sphere with high surface area possesses high photocatalytic activity.110 The flower-like ZnO with macrostructure has a higher photocatalytic activity than nanoparticles, nanorods and nanosheets due to the netlike arrangement of nanosheets in the 3D flower-like ZnO. This inhibits aggregation and maintains a huge active surface area.112 ZnO nanoflower has a higher photocatalytic activity than nanorods owing to the larger oxygen vacancy on the surface of ZnO nanoflower.113 The polar planes of ZnO are of the great importance, favoring the formation of more oxygen vacancies.110 The detailed

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effect of polar planes on the photocatalytic performance of ZnO is as follows. The proportion of diverse crystal facets present on the particles’ surface is the reason for difference in photocatalytic performance between particles with different morphology.114 The surface of rod-shaped ZnO is mostly composed of nonpolar faces along the rod axis, while the most of surfaces present on a hexagonal plate are polar (001) Zn face and the (00ī) O face.114 Exposure of more proportion of polar faces results in the higher photocatalytic activity. The great activity of the (001) Zn face can be ascribed to the (001) face of ZnO, the face with the highest -

energy among the whole faces.114 The OH can be absorbed onto this face due to its .

positive charge, leading to higher production rate of OH radicals.114 There is a direct relation between the surface oxygen vacancy content and the proportion of polar faces exposed.114 Also to improve photocatalytic activity of ZnO non-metal ions has been used as a doping agent such as N and C, which has the same effect as metal ions.115 The photocatalytic mechanism of carbon-coupling ZnO (C/ZnO) and the reason for enhancing photocatalytic activity of ZnO is discussed in more details. 116 Carbon tiny particles attach on the nano ZnO surface; upon irradiation of UV or visible light, the photo-generated electrons from ZnO are transmitted to the carbon particles, and trapped in them, leading to separation of the electron hole pairs, 11



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preventing from recombination and enhancing the photocatalytic activity of nano ZnO.116 Also utilizing ZnO or TiO2 nanocomposites and carbon including carbon nanotubes (CNTs) and activated carbon, or nanocomposites of semiconductor and reduced graphene (GR), which is another allotrope of carbon has been usual.117-122 Semiconductor-GR

and

semiconductor-CNTs

have

the

same

effect

on

enhancement of the photocatalytic activity of semiconductors,117,118 even though GR has unique structure and electronic characteristics.117 These effects can be narrowing the band gap of the semiconductor, increasing adsorptivity of the contaminants, enhancing light absorption range and intensity and simple charge transportation and separation.117-119 Indeed, there is a synergistic effect between semiconductors and GR or CNTs, which is achievable in the specific composition ratio in the nanocomposite.117,119,120 The other method to increase the synergistic effect is to cover the 2D GR sheet with semiconductor ingredients completely, to maximize the electron conductivity of GR, due to adequate interfacial contact between semiconductors and GR.118,120 In case of ZnO, the other way to reach the adequate interfacial contact is to use smaller particles of nano ZnO in the composite of ZnO-GR.120 As a consequent, photo-generated charge carriers are more efficiently separated, leading to enhanced photocatalytic activity.118,120 ZnO have also been combined with graphene, which not only enhance the photocatalytic activity but also improve the anti-photocorrosion properties of the

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nano ZnO.119,120 Carbon materials are well electron acceptors and ZnO is a well electron donor. Therefore, the synergistic effect will reduce the recombination of photo-induced electron hole pairs, leading to enhanced photocatalytic activity.119,120 Although ZnO has a higher photocatalytic activity than TiO2, it suffers from a photo-corrosion drawback, during light irradiation, in the aqueous media, which diminishes its photocatalytic activity and stability,120,123 which also depend on the pH value of the solution.120,123 The detailed ZnO photo-corrosion process when serves as decomposing dyes in the aqueous environment, are shown in reactions 13-19:

.

h+ / OH + dye

colorless product

ZnO + 2h+ + nH2O

(13)

Zn(OH)n(2-n)+ +0.5H2O + nH+

Where n is dependant upon the solution pH.120,

123

(14)

The photo-decomposition of

ZnO is comprised of two gradual steps, where two holes are captured on the surface, followed with the quick creation of a molecule of oxygen and Zn2+ rapid expulsion from the surface,120,123 -

-

O2 surface + h+ -

(15)

O surface -

O surface + 3O2 +3h+

2(O___O2-)

(16)

13



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O___O2- +2h+ 2Zn2+

O2

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(17)

2Zn2+ (aq)

(18)

The whole reaction can be shown as reaction 19. ZnO + 2h+

Zn2+ + 0.5O2

(19)

According to reactions 13 and 19, the photocatalytic reaction and photo-induced dissolution are two contest processes. For bare nano ZnO most of the photogenerated h+, during exposing to the UV irradiation, will take part in the photocorrosion reaction (reaction 19). Coating of ZnO surface with carbon layer, owing to the powerful adsorption of dye molecules, some h+ is consumed for the photooxidation of dye (reaction 13) which competes with the photo-corrosion process, and notably prevents the photo-induced dissolution.123 Nano-sized ZnO particles suffers from photo-corrosion, changes their morphology produces the web-like structure during photocatalysis process.123 Coating with carbon layer inhibits the surface reaction between ZnO particles prevents the formation of the web-like structure.123 Several approaches including, embedding ZnO into the membranes of perfluorinated ionomer, organic coating, hybridization by graphite-like carbon such as fullerenes (C60) and monolayer polyaniline, and fabrication of surface complex, have so far been employed for prevention of ZnO nanoparticles photo14


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corrosion.120,123 Moreover the effective interfacial hybridization between GR sheets and nano ZnO prevents the photo-corrosion of nano ZnO. Such prevention has also been verified in other ZnO-carbon composites.119,120 However it is worth mentioning that in textile industry ZnO nanoparticles are mostly used for decomposing dyes or other natural impurity on the fabric surface, which is almost dry with a low moist content. In case of spreading dye drops, dirt or small fatty stain from food on the fabric surface, exposure of fabric to the sun or UV lights generates electron hole pairs which reacts with oxygen, in the air, and water, in the moisture, and produces reactive species decomposing the impurities on the fabric surface.38 Therefor, in the textile field, the photo-corrosion of nano ZnO is a matter of importance in the high relative humidity and in this case, the proposed methods can be useful. It should be noted that GR does not always act as an electron reservoir to trap the photo-generated electrons during the photocatalytic reactions.121 In case of ZnS-GR, under visible light irradiation, GR is photo-excited and injects electrons into the conduction band of ZnS by which oxygen is activated, and generating super oxide radicals.121 Combining ZnS with GR narrows the band gap of ZnS however this is not enough to activate ZnS under visible light irradiation and the primary active species is electrons photogenerated from GR.121 In the case of UV light irradiation, the photocatalytic mechanism of ZnS-GR will be similar to TiO2- or ZnO-GR.121 Also the utilization of core-shell nanocomposite 15



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in the photocatalysts has recently investigated.124 They are fabricated in the form of metal core semiconductor shell, which have the unique advantages as heterogeneous

photocatalysts.124

Encapsuling

metal

nanoparticles

in

the

semiconductor’s shell avoids corrosion and dissolution in time of practical applications and able to enhance its stability against aggregation. Metal core can be used as a reservoir for trapping photo-generated electrons and prolong the lifetime of the charge carriers and enhancing the photocatalytic performance. Core shell nanostructure develops 3D contact between metal and semiconductor facilitates the process of charge transfer. Providing a homogeneous media for prolonged reaction is the final advantage of core shell nanoarchitecture.124

3. Application of nano ZnO on textiles and polymers Stability of nanoparticles is one of their effective aspects in application on the suggested surface.64 A few substrates such as silica, glass, polymers, activated carbon and textiles have been utilized to examine the substrate effect on the nanoparticles stability.125-128 The main object is to improve the nanoparticles stability on the diverse materials surface, with no negative impact on the nanoparticles’ intrinsic characteristics.1129-1132 Various methods have been generally proposed to stabilize the nanoparticles on the textile and polymer surfaces.64 Fibers supply the best substrate where a huge surface area is available

16


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for a determined fabric weight or volume. The corporation between textile industry and nanotechnology utilizes this characteristic of huge interfacial area and with supramolecular or macromolecular groups in the neighborhood of a fiber severe alteration in energies is experienced, when altering to a dry state from a wet state.5 The most approaches used for application of nano ZnO on the fabric surface belongs to cotton and polyester/cotton fabrics, however wool fabrics were not used much. Application of nano ZnO on textiles can be classified into one-step process (in situ method) and two-step process (ex situ method). Two-step process is first discussed as being used more than one-step process. Various approaches including homogeneous precipitation,16 wet chemical8,15,18,133 and hydrothermal methods134 used for preparing ZnO treated cotton fabrics. Becheri et al fabricated nano ZnO through a homogeneous phase reaction and then applied on the cotton fabric. Zinc chloride and sodium hydroxide in water and 1, 2-ethandiol was used to synthesize nano ZnO. The fabric was then immersed into the ZnO dispersion. Synthesis of nano ZnO in 1, 2-ethandiol leads to the formation of smaller particles than in pure water.16 Wang and colleagues devised a depleted temperature growth method for growing ZnO nanorod onto the cotton fabrics.134 Yadav and co-workers synthesized nano ZnO with a mean size of 40 nm through wet chemical approach and applied onto the cotton fabrics using acrylic binder. Zinc nitrate and sodium hydroxide was used to synthesize nano ZnO, and then cotton fabric was immersed

17



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into the ZnO solution.15 Mao and colleagues’ synthesized nano ZnO by hydrothermal method and applied on the cotton fabrics. The SiO2 coated fabric was immersed into the solution of zinc nitrate and hexamethylenetetramine and then temperature was risen to 80˚C to fabricate nano ZnO.134 ZnCl2/NaOH, Zn(CH3COO)2/NaOH or Zn(NO3)2/NaOH as precursors, water, water/alcohol as media and soluble starch as a stabilizer are used.5,15,26,136,137 Nano ZnO can be applied on the fabric surface through soaking into 2-propanol dispersion or solution of nano ZnO4,5,15,37,38 and fixed with the use of acrylic binder, heating at 130˚C and curing at 160˚C.15, 40 Wool, polyester and polyester/cotton fabrics have been treated with similar finishing process as cotton fabrics.4,5,15,136 Baruah et al synthesized nano nanowire ZnO on nonwoven polyethylene fiber with hydrothermal method .138 The substrate treated with solution of dodecane thiol in ethanol was seeded by dipping into a nano ZnO concentrated colloidal solution in isopropanol for 15 min three times. The substrate was then heated at 150˚C for 15 min. The wires growth was carried out in a sealed bath containing a solution of hexamethylenetetramine and zinc nitrate at 90˚C.138 The other method used for application of nano ZnO on the cotton fabric surface is known as layer-by-layer assembly.139 The multilayer decomposition was rarely employed in textile fibers.140,141 For deposition of nano ZnO multilayer on cotton fabric, cationic cotton fabric was prepared with cationization process142 created positive charge on the

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cotton surface. Then the positively charged cotton was soaked into the following recipe alternately: anionic ZnO solution (ZnO solution at pH=11), deionized water, cationic ZnO solution (ZnO solution at pH=3) and deionized water until 10 and 16 ZnO layers were deposited. Cotton fabrics were finally dried at 60˚C and cured at 130˚C for 3 min.139 The other novel method is electrospinning which applied zinc oxide nanoparticles on the polypropylene nonwoven fabrics143 in which electrospun ZnO nanocomposite fibers from DMF deposited on to a substrate of polypropylene nonwoven to generate a layered fabric. Kim and co-workers applied nano ZnO on nylon 6 fiber using electrospinning method.144 They blended ZnO nanoparticles with solution of nylon 6 to attain fine distribution of ZnO nanoparticles on/into the fibers.144 Teli et al prepared a polyester nonacomposite (PET) containing ZnO nanoparticles.145 The chips of PET were blended with nano ZnO master batch prepared with compounding nano ZnO and linear low density polyethylene and then melt spun.145 These methods consist of two steps: synthesis of nano ZnO and bonding the as-obtained nano ZnO to the surface of fabric. Furtherer for enhancing the durability against washing, nano ZnO was applied with immersing the fabric into the binder solution.8, 15 However, the mentioned methods are complex and take long time.36 There are a few methods which are called in situ or one-step method that nanoparticles are synthesized in the presence of fabric such as in situ synthesis of ZnO on cotton fibers utilizing microwave by Li et al.36

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As-fabricated precipitate ZnO was placed into flask, ammonia was added drop wise and after producing clear solution while stirring with magnetic stirrer, cotton were immersed into the flask and placed into the ultrasonic oscillator. The cotton were extracted from solution and placed into the microwave oven.36 Also ZnOassembled

on

cotton

with

dropping

zinc

nitrate

solution

to

the

hexamethylenetetramine solution under vigorous stirring and immersing cotton into the growth solution and increasing temperature to 90˚C.137 Nano ZnO has assembled into the lumen of fibers.137 Zhang et al used the in situ synthesis method for producing nano ZnO/PET hybrid nano fibers through electrospinning.146 They dissolved zinc acetate and PET separately in trifluoro acetic acid/dichloromethane at room temperature. Zinc acetate solution was then added into the PET solution drop wise, and electro spun.146 The ZnO precursor/PET hybrid nano fibers were soaked in ethanol-ammonia mixture to obtain nano ZnO/PET hybrid nano fiber.146 The latest in situ synthesis method belongs to Montazer et al. 147 They synthesized nano ZnO within the wool fabric in the presence of Zn(CH3COO)2 and NaOH/NH3 as precursors and water or water/ethanol as media.147 In their approach wool fabric was immersed into a solution of zinc acetate under constant stirring utilizing magnetic stirrer. Ammonia was then added to obtain pH above 9 and NaOH was added into the solution rather than ammonia at 90˚C, to keep the pH above 9,for 1

20


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h. 147 The SEM images of wool fabrics treated with nano ZnO and untreated fabric are shown in Fig.2.

Fig.2. SEM images of a: untreated wool fabric and b, c, d: wool fabrics treated with nano ZnO

The EDX patterns of the samples treated with nano ZnO in ethanol/water mixture and water media are shown in Fig.3 (a: ethanol/water, b: water).

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Fig.3. EDX patterns of wool samples treated with nano ZnO in a: ethanol/water, b: water media

EDX patterns showed C, S and some O from wool64 also the Zn percentage on wool in ethanol/water media is more than water media demonstrated the higher absorption of nano ZnO by wool fabric in water/ethanol which is in agreement with the prior works.148 They also reported smaller particles synthesized in water/ethanol medium than in water.147 The application methods of nano ZnO on textiles and polymers are affecting the properties of the substrates. The mechanical or UV-absorption properties are the only examined properties of the fabric. Yadav et al applied nano ZnO on cotton fabric using acrylic binder (ex-situ synthesis method) and reported lower the tensile strength for the treated fabrics. Becheri et al also applied nano ZnO on cotton and wool fabrics with the different application methods using nano ZnO dispersion and soaking the fabrics into the dispersion (ex-situ synthesis method). They observed 7% increase in the tensile strength of the wool fabric as compared 22


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to the untreated fabric. However Montazer et al observed 13% increase in the tensile strength of the wool fabric using in-situ synthesis method.15,16,147 The reason for these phenomenon are given in the section 8. Moreover, through in-situ synthesis method, the nanoparticles are able to enter the fabric structure resulting in the higher washing durability.36,102,147 Li et al applied nano ZnO on cotton fabric and reported excellent UV shielding property of the fabric with reasonable washing durability.36 These properties besides lower complexity and shorter application time highlights the more benefits of the in-situ synthesis method in comparison to the ex-situ one. Fig.4 illustrates the methods used for application of nano ZnO on textiles and polymers.

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Fig.4. Different methods employed for application of nano ZnO on textiles and polymers

4. Self-cleaning properties on various substrates using nano ZnO Creating the self-cleaning properties on different substrates is one of the most admiring nanotechnology applications.149 This technology is able to be used in different substrates such as glass, building substances, paper, polymers, and textile industry.149 Hydrophilic and hydrophobic surface are two types of self-cleaning

24


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surface exist which can eliminate the contamination and soil from the substrate on the basis of diverse mechanism.149 A hydrophobic surface prohibits the contamination and soil absorption, always keeping the surface clean which was inspired with lotus effect. On the other hand, water droplets on the hydrophilic surface are distributed and the contaminations are eliminated with a water stream.150 The cohesive force between a liquid droplets located on the surface and a substrate play more important roles than the interior cohering ones inside the liquid; as a result, the droplet will be spread.149-151 On the other hand, the surface is hydrophobic, if these types of common effects between the droplet and the surface are lower than inside the liquid; consequently, droplets are keeping their own specific shape. Droplets of water on these types of surfaces have a large contact angle.149-151 Diminishing the surface energy of the suggested substrate is the important key to generate a hydrophobic surface.151 There are two kinds of stainremoving surfaces in nanotechnology.4 First is rough surface, which can be waterproof and soils cannot remain on their surface and removed with simple rinsing.4 The second one possesses a surface granted with photo catalysts such as ZnO and TiO2. Their mechanism is turning oxygen in the water or air into the active oxygen causing the organic substances to be destroyed generating the sterilizing impact.4 These two groups can be combined with each other, in which the rain water takes away the destroyed organic dirt and cleans the surface swiftly with no left

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marks.152 Kathirvelu et al synthesized nano ZnO by homogeneous phase reaction and then applied on the cotton fabric to obtain the stain-eliminating function.4 The untreated sample stain profiles were compared with treated with nano ZnO and found a little effect.4 A long time required to remove stains from the substrate due to the inefficient utilizing energy by ZnO from sunlight. It functions as a catalyst for eliminating dirt molecules by supplying electrons which ionize oxygen molecules in the surrounding air. The electrons are released from ZnO through photoelectric impact.4 ZnO is able to utilize only a small part of solar energy to eliminate stains because of its high band gap energy. Electron excitation to the band of conduction is only the initiation of cleaning stage. These electrons should make reaction with atoms of oxygen and makes reaction with dirt. All these reactions are restricted to the quantity of electrons released from the ZnO. Therefore for a large staining, lots of energy is required. Sunlight is the best light source for activation of the stain-eliminating process, especially for hikers or military individuals remaining in sun for long time.4 Kathirvelu et al found that there is an influential increase in stain-removing property of the nano ZnO treated fabrics.4 They also demonstrated that self-cleaning property of cotton and cotton/polyester fabrics treated with nano ZnO synthesized through homogeneous phase reaction improve with application of the smaller particle of ZnO.

136

Moafi

and co-workers also synthesize nano ZnO with wet chemical route and applied

26


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onto the cotton fiber and assessed the self-cleaning properties of ZnO with decomposing methylene blue in solution under UV illumination.38 They concluded that ZnO modified fibers could decompose dye due to its photocatalytic activity which cause to generate reactive oxidative species such as hydroxyl radicals under UV illumination which can oxidize organic materials.32 The other excellent selfcleaning effect can be achieved by lotus effect, which has been attracted much attention, in the recent decades.153-156 Cotton has prominent characteristics such as comfort and soft handle with too many hydroxyl groups on its surface absorbs abundant amount of water. Therefore finishes are needed to make the cotton fabric water-proof and easy-cleaning textile.39 To make cotton fabric super-hydrophobic numerous

approaches

polytetrafluoroethylene

have films,

been

employed

such

plasma

treating,

deposited

as

deposited fluorocarbon

nanoparticulate film, silica nanoparticles’ layer, treating with gold and then modifying by n-dodecanethiol and in situ growth of silica microparticles.157-159 Diverse ZnO nanostructures, generating different roughness, are apt to create super-hydrophobic surface.39 Wu and co-workers prepared ZnO microstructure in Zn+2 solution at low temperature followed with modifying the as-generated harsh surface with monolayers of organic self-assembled (SAMs) to reach the hydrophobic surface. However this was not suitable for cotton fabric, because micro ZnO would not be achieved on bare fibers of cotton due to mismatching of

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the crystalline structure of cotton fiber and ZnO.160 Xu et al synthesized nano ZnO through hydrothermal method and with pad-dry-cure approach on the cotton fabric surface

and

then

immersed

into

the

solution

of

zinc

nitrate

and

hexamethylenetetramine for growing ZnO nanorod on the fabric surface at 90˚C for 3 h. The as-obtained fabric was then immersed into the DTMS (ndodecyltrimethoxysilane) ethanol solution at room temperature for 24 h. DTMS was hydrolyzed and Si-OCH2CH3 groups in DTMS were changed to Si-OH and reacted with ZnO on the fabric surface which achieved a hydrophobic and selfcleaning surface for cotton fabric.39 Fig.5 shows the brief mechanism of this work.

Fig.5. Mechanism of creating super-hydrophobic surface by Xu et al39

5. UV protection properties of nano ZnO UV radiation is a portion of sunlight reaches the earth with some deficient impact on some fabric properties.152 UV radiation wavelength is shorter than visible light however; the energy of each photon is more in UV region. UV rays with high energy create many problems for human such as eye difficulties, skin cancer, sunburn, erythema and cataracts.152,161-163 To reduce the health risks resulted from 28


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exposure to UV radiation, the World Health Organization, recommend utilizing dense clothes with high protection factor.164 However most clothes used in summer time and sport do not assure an effective UV-protection. UV-protection with fabrics are dependent on fiber type, thickness, color, presence of UV-absorber and other finishing processes, wearing and laundering conditions.164-166 Thus, producing clothes with UV-protection property is necessary to protect people from UV radiation. There are two approaches to improve UV-shielding property of fabrics, coating of the surface and putting UV-shielding fillers into fabrics. The second approach is more traditional, because able to grant textiles higher UVshielding property, more durability and less impact on textile appearance.167 The UV-shielding agents are subdivided into two types of inorganic and organic UV absorber.168-170 Inorganic UV absorbers are utilized more abundantly due to their non-toxicity and thermal stability in comparison to organic ones. ZnO is one of the most popular inorganic UV absorber with high UV-shielding performance in the range of 240-380 nm regarded as a perfect UV absorber.171,172 Cotton is abundantly utilized as a material of clothing on account of its outstanding characteristics including softness, warmness, comfort and others.173 However UV radiation can readily transmit through the cotton fabric.137 Lately, many researches have been tried to produce cotton fabric with better UV protection function using ZnO nanoparticles.15,127,134,174-178 Yadav et al applied nano ZnO on cotton fabric using

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acrylic binder to impart UV-blocking property to the fabric.15 They used both nano and bulk ZnO on the fabric surface and showed higher UV light absorption by nano ZnO due to their high surface area and uniform distribution on the fabric surface.15 Vigneshwaran and co-workers treated cotton fabric with ZnO-soluble starch nano-composite to improve UV-shielding characteristic.26 Wang et al grew nano ZnO on cotton fabric to achieve UV-blocking property.133 Becheri et al applied ZnO nanoparticles through fabrication of a homogeneous phase reaction on cotton fabric for UV-blocking property.16 They also applied ZnO nanoparticles through mentioned method, on wool fabric for UV-blocking property.16 They reported significantly lower

the standard values needed for excellent UV-

shielding. They also advise other methods for enhancing this property such as more compact fabric, using polyester and utilizing a diverse procedure to cure the fabric treated with dispersion of ZnO.16 Moreover Becheri et al and Kathirvelu et al concluded that synthesis of nano ZnO in 1, 2-ethandiol media leads to formation of smaller particles with higher absorption of UV radiation.16,5 Sricharussin et al synthesized various ZnO shape including multi-petals, rod and spherical, through wet chemical method and applied on the cotton fabric surface.26 They indicated that spherical and multi-petals shaped ZnO coated fabrics have an excellent UVblocking property and rod shape has a lower UV-blocking property.26 They related these results to the lower nano ZnO content on the fabric as those coated with rod

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shaped with sharp pointed resulting in lower deposition on the cotton fabric surface.26 Mao et al also showed that cotton fabric coated with needle-shaped ZnO has a higher UV-blocking property.134 The coated cotton fabric with nano ZnO treated in boiling water to complete transformation of Zn(OH)2 into ZnO, also leading to dissolving and re-nucleating ZnO crystallites in the water and formation of ZnO nano rod with needle shape and higher UV-shielding performance.134 Li et al prepared a novel ZnO/cotton composite with excellent UV-blocking property for cotton fibers.137 They also fabricated ZnO on cotton fabric with use of microwave produced excellent UV-blocking and durability properties.36 Polyester among other fibers absorbs UV radiation under 300 nm. Nano ZnO can be applied with polymerization process of polyester to improve skin protection.178 However large specific surface area and high surface energy of nano ZnO leads to their agglomeration subsequently, making a homogeneous dispersion in polymer is difficult.178 He et al prepared PET-ZnO nanocomposites with ZnO coupled with silane leading to a better dispersion and higher UV-protection.178 Abdelhady used chitosan-ZnO complex and precipitation approach to apply chitosan/ZnO nanoparticles on cotton fabric to impart UV-blocking property and to enhance UVblocking.179

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6. Wettability of nano ZnO Wettability is a prominent characteristic regulated with two factors, geometrical structure and chemical composition of surface.180 Super-hydrophilic surface with water contact angle about 0° and super-hydrophobic surface, by water contact angle greater than 150° have been widely examined because of their significance for various applications in different industrial areas.181-1183 Feng et al observed a reversible change from super-hydrophobic to super-hydrophilic film of ZnO nanorod under UV illumination.184 Since then, nano metal oxides mainly TiO2 and ZnO, were examined in terms of induced wettability under UV illumination.185,186 During UV illumination electron hole pairs will be generated on the surface of ZnO, holes are able to make reaction with lattice oxygen to produce surface oxygen vacancies. Further, water and oxygen compete to occupy the vacancies. The defect sites are kinetically more approving for adsorption of hydroxyl than oxygen. Consequently the hydrophilicity is improved. However, the hydroxylated surface energetically unstable after the adsorption on the surface. On the other hand, the adsorption of oxygen is thermodynamically approving, and oxygen can produce stronger bond with defect sites in comparison to hydroxyl group.187 Thus, oxygen atoms can gradually occupy the site of the hydroxyl groups and eject them in dark. Therefore, the surface comes back to its earlier stage, and the wettability reverse from superhydrophilic to super-hydrophobic.187 Complete return from induced hydrophilic 32


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surface to its primary hydrophobic surface needs several days remaining in dark. However, heating process at 200°C makes this recovery faster.188,189 The wettability alteration mechanism of ZnO and TiO2 surfaces has been proposed to be similar.189 Montazer et al applied nano ZnO on wool fabric,147 to evaluate its wettability after daylight illumination for seven days in summertime in Tehran, Iran. They claimed that nano ZnO is able to decompose microbial and other organic cells,65 on account of photocatalytic activity under UV irradiation,65 therefore it possess a potential of decomposing hydrophobic compounds available on the wool fabric surface such as wax which is containing fatty acids, lipids, esters, alcohols, ethers and cholesterols.190 They reported that during daylight illumination, ZnO nano particles are generating some reactive oxygen species (ROS)191 decomposing organic compounds, alcohols and acids lading to more hydrophilic wool fabric surface. They also proposed other mechanism for producing hydrophilic wool surface. Structure of wool divided into three parts, including medulla, cortex and cuticle.192 Cuticle consists of three parts of epicuticle, endocuticle and exocuticle.192,193 Epicuticle and exocuticle make the wool fabric with a hydrophobic surface. Therefore, wool surface morphology is the most important factor affects its physiochemical properties.194-196 Water droplet cannot retain its spherical shape on the hydrophilic substrate.197 Presence of ZnO on the wool fabric surface possessing photocatalytic activity under light

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illumination generates hydrophilic surface, in which electrons and holes play a prominent role through making reduction and oxidation reactions. The proposed mechanism is illustrated in Fig.6 demonstrated that electrons participate in the reduction reaction in which Zn2+ is transformed to Zn1+, producing the oxygen -

anions (O2 ), afterwards the holes alter superoxide anions to oxygen molecules through oxidation reactions.

Fig.6. Mechanism of producing hydrophilic wool fabric through irradiation of nano ZnO

The generated oxygen molecules leave their place and remaining oxygen vacancies which may be occupied by water molecules while producing OH groups, make the better fabric hydrophilic characteristics.147 The density of hydroxyl groups has an excellent impact on the hydrophilic properties through generating 34


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more hydrogen bonds with water molecules.198 After exposure to the light, the water contact angles can be decreased and water can be spread faster on the surface of fabric.199 The substrate with higher photocatalytic activity produces more hydroxyl radicals. This leads to creation of more photo induced holes and more hydroxyl groups taken up from water and subsequently generation of more hydroxyl groups.200 This also creates a higher absorption rate of water and a smaller contact angle of water.199 Montazer et al showed excellent hydrophilic properties on the fabrics containing nano ZnO synthesized in water/ethanol media with time of water absorption and water contact angle of zero.147 This was related to the smaller nano particles fabricated on the fabric surface by using water/ethanol media.147 There is a relation between particle size (surface to volume ratio), surface oxygen vacancies and photocatalytic activity, thus the smaller particle size (higher specific surface area) results in the more surface oxygen vacancy and higher photocatalytic activity106,107 and more hydrophilic surface.

7. Antimicrobial properties of nano ZnO Textile products are excellent media for the reproduction and growth of bacteria and microorganisms. The chemical structure of natural fibers supplies nutrition for bacteria and microorganisms resulting in higher growth. This develops lots of difficulties such as strength loss, undesirable odor, staining and consumer health problem. It is necessary to grant antimicrobial property to the textile products in 35



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order to protect the consumer health.201 Many people in today world concentrated their attention on protecting themselves from dangerous pathogens.201 It is important for finishing processes in textile industry to protect the consumer against bacteria and as a result, the clothes against fibers degradation.15 Numerous antibacterial agents have been utilized in textile applications.201 Antimicrobial properties are mostly performed on the basis of AATCC 100-1999 method against S. aureus and E. coli as pathogenic Gram-positive and Gram-negative bacteria, respectively.64 Ag nanoparticles span a broad range of pathogenic bacteria and microorganisms through reacting with cell wall in microorganisms, preventing metabolism, resulting in their destruction.202,203 Cotton, wool and silk fabrics have been treated with Ag to produce antimicrobial effect.204,205 The utilization of nano silver in textile applications has its specific limitations, such as particles with size of smaller than 50 nm are able to have an injurious effect on human body and the surrounding.206 Inorganic substances such as metal oxides have drawn great attention during the last decade because of their stability in difficult conditions.207 These metal oxides, such as ZnO, TiO2, CaO and MgO are also unharmed to animals and especially human.208 The utilization of ZnO has been regarded as a practical solution to cease contagious ailments because of its antimicrobial characteristics.201 It has been demonstrated that, ZnO prevents wide spectrum of bacteria from growing and reproduction.209 The proposed mechanism of ZnO

36


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antibacterial activity is on the basis of releasing reactive oxygen species (ROS)210,211 which destroy the bacteria membrane.209 The anti-bactericidal characteristics of nano ZnO are due to the electrostatic interaction of nano ZnO with the microbial cell surface and elevated coalition of nano ZnO leads to the increased cell damage.65 The antibacterial activity of ZnO increase with decreasing the particle size. 209,210 Nanoparticles with smaller size enter the microbial cell wall by means of ion channels or carrier proteins and adhere to diverse organelles, then obstruct the metabolic processes through producing reactive oxygen species.209 Other mechanism suggests the antibacterial effect of nano ZnO due to chemical interaction between membrane proteins and hydrogen peroxide as one of the nano ZnO photoactive products. The generated H2O2 enters the cell membrane of bacteria and destroys them.212 Sricharussin et al found that antimicrobial activity of nano ZnO is almost independent of its shape and crystalline structure, and dependent upon concentration and surface area of nano ZnO.26 Kathirvelu and colleagues applied ZnO nanoparticles fabricated through a homogeneous phase reaction on cotton and cotton/polyester fabrics to study the antimicrobial activity of nano ZnO against S. aureus.136 They observed that nano ZnO synthesized in 1, 2ethandiol media have a smaller particle size and more antibacterial activity than those of in water media.121 Rajendran et al synthesized and applied nano and bulk ZnO on cotton fabric to assess antibacterial effect of nano ZnO against E. coli and

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S. aureus.213 They concluded that nano ZnO has a higher antimicrobial activity than bulk ZnO and also in both nano and bulk ZnO antibacterial activity was higher in case of S. aureus in comparison to E. coli. Further, the reduction percentage for nano ZnO was very higher than bulk ZnO, in both bacteria.213 It is worthwhile to mention that TiO2 is not able to destroy S. aureus as having thicker cell wall in comparison to E. coli, however ZnO can easily demolish both of them.26,64,213 Different methods including, fabrication of nano ZnO through homogenous phase reaction, wet chemical and melt-spinning have been employed to synthesize and apply ZnO nanoparticles on different substrates, including, cotton fabrics, polyester and polyurethane composites. Antibacterial activity of nano ZnO on was higher on all substrates against S. aureus than E. coli.145,212,214,215 This can be related to the more affinity of nano ZnO to S. aureus than E. coli.

8. Other effects of nano ZnO on textile and polymer properties Becheri et al reported higher tensile strength with application of nano ZnO on cotton and wool fabrics due to the possible more stiffness on treated fabrics.

16

Nanoparticles with small size enter to the polymer chains leading to generation some bonds with them. Indeed, nanoparticles are acting similar to a cross-linking agents inside the polymer structure resulting in the stiffness of the fabrics.216 The

38


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increase in tensile strength of wool fabric treated with nano ZnO is due to the shrinkage of wool fabric in aqueous medium especially in alkali media, which diminish its stability and deteriorate the wool structure.16 Yadav et al, found that applying nano ZnO on cotton fabric using acrylic binder, has decreased the tensile strength of the fabric in warp direction and the tensile strength has not changed much in the weft direction.15 They stated that the tensile strength of cotton fabric has generally reduced after chemical finishes. The air permeability of cotton fabric treated with nano ZnO is more than that of untreated fabric and in case of bulk ZnO permeability has decreased as compared to untreated fabric. They suggested the uniformity and narrow distribution of nano ZnO on fabric surface as influencing factors.15 The difference between tensile strength results reported by Yadav et al and Becheri et al is due to the difference in application of nano ZnO onto the fabrics. Becheri et al applied nano ZnO onto the fabrics by soaking the fabrics into the nano ZnO dispersion, which allows the nanoparticles to enter the fabric structure and make bonds with some groups on the fabric.216 However Yadav et al used acrylic binder, which does not allow the nanoparticles to enter the fabric structure, and prevent the nanoparticles from acting in a similar manner as cross-linking agent. Teli et al reported lower tensile strength on the polyester fiber applied with nano ZnO through melt spinning.145 They observed that more nano ZnO content in the nanocomposite led to the more reduction in the tensile strength.

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This is related to the reduction of macromolecules arrangement of PET along the axis of the fiber.145 Lam et al applied ZnO/nano ZnO as catalysts in combination with fire retardant treatment, on cotton fabric pretreated with plasma.217 They described that ZnO/nano ZnO have a significant impact on flame retardant performance of fabrics. The reason for decreasing rate of flame spread can be related to catalytic impact on dehydration and cross-linking reactions. Both plasma as pretreatment and ZnO/nano ZnO as catalysts improved the cross-linking procedure of the flame retardant, an organic phosphorus compound (Pyrovatex CP New), with cotton fabric.217 Zhang and Yang synthesized nano ZnO through homogeneous phase reaction and applied onto the cotton and polyester fabrics to evaluate their antistatic performance in terms of decrease in charge density.40 They reported significantly decrease in charge density of treated fabrics. Moreover antistatic impact of nano ZnO on polyester fabric was better than that of cotton fabric.40 Kim and co-workers, applied nano ZnO through electro spinning on nylon 6 and found better electrical conductivity on ZnO included nylon 6 composite.144 They also reported that increasing nano ZnO content above 10% decrease the conductivity of nanocomposie owing to the agglomeration of nanoparticles.129 Further, the thermal stability of the nanocomposite is lower than the pure nylon 6 due to lowering of intermolecular hydrogen bonds on account of the presence of

40


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nano ZnO.144 The suitable nnao ZnO intermixing with solution of nylon 6 breaks the intermolecular hydrogen bonds between nylon 6 molecules. In animal fibers there are two types of pigments including pheomelanin and eumelanin which cause the fibers to appear colored.218 These pigments must be decomposed to bleach the wool fabric. Oxidation mechanism of eumelanin by reactive oxygen species produced during light illumination is shown in Scheme 1.

Scheme 1, Mechanism of eumelanin oxidation by reactive oxygen species -

The ring structure in the eumelan is opened upon OOH nucleophilic attack, resulting in eumelanin destruction.219 Montazer et al exposed the treated wool

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fabrics with nano ZnO to daylight and reported yellowness index after daylight illumination for seven days in summer time in Tehran, Iran.147 They also stated that treated wool fabric prevented from yellowing16 and even produced whiter surface.147 They showed that fabrics containing nano ZnO synthesized in the water/ethanol have whiter surface in comparison to distilled water as the smaller particles fabricated in water/ethanol media.147 There is an inherent relation between particle size, surface oxygen vacancies and photocatalytic activity, thus the smaller particle size results in the more surface oxygen vacancy and higher photocatalytic activity.106,107 Therefore surface with higher photocatalytic activity is able to decompose more natural pigments leading to lower yellowness index.147 They also indicated significantly higher tensile strength for the nano ZnO treated wool fabric. To verify this conclusion they examined alkali solubility of samples which was in good agreement with data obtained from tensile strength.147 This means wool fabrics with higher tensile strength have lower alkali solubility.147 They claimed that nano ZnO might act similar to a cross-linking agent on wool chemical structure.147 Harifi and Montazer stated that nanoparticles due to their small size can easily enter the chains of polymer and act similar to the cross-linking agent through making bonds within polymeric chains.216 Montazer et al related this to the possible effect of nanoparticles147 which is shown in Scheme 2, regarding the fact

42


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that ZnO has a positive charge and wool has a negative charge in alkali media used for nano ZnO application on the fabric.221,212

Scheme 2, Nano cross-linking of wool protein chains with nano ZnO

They also stated that the effect of ethanol can be related to the more absorption of nano ZnO by wool in this condition,148 which lead to more bonds created between 43



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peptide chains and nanoparticles and wool fabric with higher tensile strength.147 Fig. 7 demonstrating the influence of particle size on the ZnO properties discussed in this paper.

Fig.7, The influence of ZnO nanoparticle size on its properties

This is showing the importance of size control in the synthesis of nano ZnO. Table 1 shows some of the works has been carried out in the application of nano ZnO on textiles.

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Table 1. Different works performed on the application of nano ZnO on textiles Authors

Goods type

Method

Assessed features

Becheri et al

Cotton fabric

Ex situ: immersion of fabric into the ZnO dispersion

UV protection,

Wang et al

Cotton fabric

Ex situ: immersion of fabric into the ZnO suspension

tensile strength UV protection, antimicrobial properties

Ref. 16

133

UV protection, Cotton fabric

Ex situ: immersion of fabric into the ZnO solution

Mao et al

antimicrobial properties, tensile strength

15

Cotton fabric

Ex situ: immersion of fabric into the solution of zinc nitrate and hexamethylenetetramine

UV protection

134

Kim et al

Nylon 6 fiber

Ex situ: electro spinning

electrical properties

144

Teli et al

Polyester nonacomposite

Ex situ: melt spinning

antimicrobial properties, tensile strength

145

Ex situ: Soaking fabric into the nano ZnO dispersion

Self-cleaning

4

In situ: fabrication of ZnO on cotton fiber using microwave

UV protection with high washing durability

36

Yadav et al

Kathirvelu et al

Li et al

Cotton and cotton/polyester fabric Cotton fiber

Wettability, Montazer et al

Wool fabric

In situ: immersion of fabric into the ZnO precursors

45


bleaching effect, alkali solubility, tensile strength

147


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The authors of the present article attempted to offer a succinct perception of the nano substance application, especially nano zinc oxide particles on the fabric, fiber and polymer surface. The application of nanoparticles on the fabric and polymer surface is a novel way for researchers to appraise diverse new possible characteristics on the fabrics and polymers, succeeding in the recent challenging issues in the textile and polymer field. Utilizing the photocatalytic characteristics of nano zinc oxide, researchers have been able to impart novel characteristics in textile and polymer products. UV-blocking, self-cleaning and antibacterial properties, improving the physical difficulties of fabrics and polymers are a few prominent properties that researchers have focused on. They have used different fixation approaches to find the best of them. Clearly this type of research has not finished, and moreover examinations are necessary to reinforce the attained results, thinking over diverse facets of the novel products on man life.

9. Future outlook Although ZnO has more benefits as compared with TiO2, such as lower cost, higher photocatalytic activity 62, more effective antimicrobial properties,26,213 easier synthesis method and less sensitivity to the synthesis conditions,223 the use of nano TiO2 according to literatures is more than nano ZnO in textiles and polmers.224-227 TiO2 has been used as substitute for carrier in disperse dyeing of polyester, mothproofing of wool, cross-linking of cotton, color reduction in wool, photo46


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bleaching and photo-scouring of raw cotton fabric, diminishing the photoyellowing of wool, self-cleaning, UV-blocking and antimicrobial properties on different types of textiles and polymers.224-227 TiO2 should be composed of specific percentage of rutile, anatase and amorphous phase to have an appropriate photocatalytic activity.68,223 Antase due to its higher photocatalytic activity is more desirable than the other phase for photocatalysis.68,223 The transformation of amorphous phase to anatase commenced over 250˚C and close to 600˚C will be completed68,208 which is more than the most textiles and polymers stability making the in situ synthesis of nano TiO2 very difficult. Montazer et al applied nano ZnO on the wool fabric at 90˚C without fabric damage and enhanced the fabric properties.147 They stated that these improved properties are associated with the in situ synthesis of nano ZnO through synthesis of nano ZnO within the fabric structure.147 It has been demonstrated that nano ZnO can be a great alternative for nano TiO2.67 Therefore, through utilizing nano ZnO and its application on the textiles and polymers with in situ synthesis method, the textile and polymer products benefit from the desirable properties of metal oxides besides the other improved properties obtained on the products such as higher tensile strength, washing durability, UV-absorption and possibly higher photocatalytic activity leading to the higher self-cleaning, antimicrobial and wettability properties of the substrate. Textile and polymer products are made of carbon, nitrogen and other

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elements acting similar to the non-metal doping agents trapping the photo-induced electron, leading to enhanced photocatalytic activity of nano ZnO. This is not questionable; because application of nano ZnO on the textiles and polymers using the in-situ synthesis method will result in the well-grafted nano ZnO on the substrates,

36,102,147

which will possibly enhanced their properties synergistically.

Finally, it should be noted that the area of in-situ synthesis method requires more works to prove its own superiority over ex-situ synthesis method.

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665x516mm (96 x 96 DPI)


Comparison of in-situ and ex-situ catalytic pyrolysis in a micro-reactor system.

Eu-doped ZnO nanoparticles: Sonochemical synthesis, characterization, and sonocatalytic application.

Ex situ and in situ characterization of patterned photoreactive thin organic surface layers using friction force microscopy.

Investigation of in situ and ex situ catalytic pyrolysis of miscanthus × giganteus using a PyGC-MS microsystem and comparison with a bench-scale spouted-bed reactor.

Applications of chitosan powder with in situ synthesized nano ZnO particles as an antimicrobial agent.

ZnO nanocomposites.

Digestive efficiencies of ex situ and in situ West Indian manatees (Trichechus manatus latirostris).

Assembly of amorphous clusters under floating monolayers: a comparison of in situ and ex situ techniques.

In Situ and Ex Situ TEM Study of Lithiation Behaviours of Porous Silicon Nanostructures.

Preparation and characterization of in situ ionic cross-linked pectin films: unique biodegradable polymers.

Evaluation of uncertainties in in situ and ex situ gamma measurements on land areas with low contamination levels.

Ex-situ in-vivo liver surgery.

Synthesis, characterization and spectroscopic investigations of novel nano multi-metal oxide Co3O4·CeO2·ZnO.

The Red Queen and the seed bank: pathogen resistance of ex situ and in situ conserved barley.

Ultrasonic-assisted synthesis and structural characterization of two new nano-structured Hg(II) coordination polymers.

On the characterization of ultra-precise X-ray optical components: advances and challenges in ex situ metrology.

Hemostatic studies of ex situ hepatic surgery.

In situ sonochemical synthesis of ZnO particles embedded in a thermoplastic matrix for biomedical applications.

Maize Germplasm Conservation in Southern California's Urban Gardens: Introduced Diversity Beyond ex situ and in situ Management.

ZnO porous hybrids as anode materials for lithium ion batteries.

Development, characterization and application of in situ gel systems for intranasal delivery of tacrine.

Simultaneous in-situ synthesis and characterization of Co@Cu core-shell nanoparticle arrays.

Ex situ reimplantation technique, in central lung tumors.

Complementary DNA synthesis in situ: methods and applications.