1. Eco-friendly Development in Textile Finishing
Nanotechnology for
Eco-friendly Development in
Textile Finishing
Punnama Siriphannon,
Yuwanda Iamphaojeen and Pratyaporn Tepmatee
1Department of Chemistry, Faculty of Science
2Functional Nanostructured Materials Laboratory, College of KMITL Nanotechnology
King Mongkut’s Institute of Technology Ladkrabang, Bangkok, Thailand

2. Textile Industry
In 2012, Thailand had a trade surplus of Textiles and Clothing trade, with exports accounted for 3.4% of GDP.

3. Pollution from Textile Industry
Textile manufacturing process
 high consumption of resources
- fuel, chemicals, water
 low process efficiency
generates a significant amount of waste
Environmental issues in textile industry
Wastewater
Air pollution
Energy consumption
Solid and liquid waste
Hazardous material management

4. Eco-Friendly Textile Industry
Pollution-free eco-friendly textiles have become the dominant market in the 21st century, the main products.
Profitability and Environmental
Protection
Integration of Productivity
and Environmental Management
Sustainability and
Quality of Life

5. Nanotechnology for Eco-Friendly Textile Industry
Fabrication and Immobilization of
Nanoparticles on Cotton Fabrics
by Eco-Friendly Process
Nanoporous Adsorbents
for Dye Containing
Wastewater Treatment

6. + Cotton Properties Nano ZnO Properties
Fabrication and Immobilization of ZnO Nanoparticles on Cotton Fabrics by Eco-Friendly Process
Motivation & Objective 1
Cotton Properties
 Soft touch
 Easy to maintenance
 High water absorbency
Nano ZnO Properties
 Antibacteria
 UV Protection
 Self-cleaning +
Nano ZnO coated cotton
In the first work, we focused on an improvement of cotton fabric, which is popular natural fiber due to its soft touch, easy to maintenance and high water absorbency, producing comfort and breathable properties of cotton. However, because the high water absorption of cotton causes this fiber more susceptible to microbial attack. To overcome these drawbacks, ZnO nanocrystals were selected to modify the surface of cotton fabric in order to improve the antibacterial, UV protection and self cleaning properties, leading to the first benefit of value adding by creating new properties and improving quality of cotton using nanotechnology.
Add value to cotton fabrics by creating new properties and improving quality using nanotechnology

7. Poor adhesion of inorganic nanoparticles
Fabrication and Immobilization of ZnO Nanoparticles on Cotton Fabrics by Eco-Friendly Process
Motivation & Objective 2
Poor adhesion of inorganic nanoparticles
 Performance drop after prolonged usage
Develop an effective and cost-saving technique for immoblization of nano ZnO on cotton fabrics

8. Polyelectrolyte assisted immobilization Anionic polyelectrolyte
Fabrication and Immobilization of ZnO Nanoparticles on Cotton Fabrics by Eco-Friendly Process
Purposed system
Polyelectrolyte assisted immobilization
Hydrothermal growth
of nano ZnO on cotton
non-toxic chemical
low chemical concentration
low treatment temperature
low energy consumption
minimize waste
Polymers whose repeating units bear an electrolyte group will dissociate in aqueous solutions, making the polymers charged.
Anionic polyelectrolyte
Poly 4-styrene
sulfonic acid
(PSS)
GREEN CHEMISTRY

9. Preparation of cationized cotton fabrics
3-chloro-2-hydroxypropyl-
trimethylammonium chloride
epoxypropyltrimethyl-ammonium chloride
Cellulose
Cationized cellulose

10. Layer-by-Layer treatment of cationized cotton
Immobilization of nano-ZnO on cotton fabrics
Layer-by-Layer treatment of cationized cotton
Hydrothermal treatment
NH4OH 0.1 M
PSS/Zn2+
cotton
Nano-ZnO
immobilized cotton
90 ºC 24 hr.
cotton
PSS 0.1 M
DI water
ZnNO36H2O
0.1 M
5 min
LbL
2,4,6 cycles

11. Immobilization of nano-ZnO on cotton fabrics
PSS
Zn OH- Zn(OH)2
Zn(OH)2 ZnO + H2O
NH4OH
Hydrothermal 90 C

12. Morphology of cotton fabrics (SEM)
PSS/Zn2+ coated cotton
Zn60m-cot
Nano ZnO Cotton
LbL 2 cycles
Zn60m-cot-G
Nano ZnO Cotton
LbL 4 cycles
Nano ZnO Cotton
LbL 6 cycles

13. XPS spectrum of Nano ZnO immobilized cotton
O(–2) in ZnO
531.7 eV
and eV
O–H in
Zn(OH)2

14. Number of PSS/Zn2+ layer
Zn content (AAS)
& UV protection properties
Samples
Number of PSS/Zn2+ layer
Zn content
(ppm/g)
UPF
UV protection
category*
Neat cotton
n/a 21
GOOD
ZnO-cot-2s 2
57.3  4.6 27
VERY GOOD
ZnO-cot-4s 4
222.5  19.2 30
ZnO-cot-6s 6
727.4  29.5 35
* UV protection category was classified according to AS/NZS 4399: 1996

15. UV-protection property
AATCC
Ultraviolet Protection Factor (UPF)
E = relative erythemal spectral effectiveness
S = solar spectral irradiance (Wm−2 nm−1)
T = spectral transmission of the specimen
obtained from UV spectrophotometric
experiments
 = wavelength interval for measurements(nm)
 = wavelength(nm)
Wavelength 280 – 400 nm

16. UV protection category Effective transmission (%)
UPF classification system AS/NZ 4399
UPF Range
UV protection category
Effective transmission (%)
GOOD
6.7 to 4.2
VERY GOOD
4.1 to 2.6
40 – 50 , 50+
EXCELLENT
2.5

17. Antimicrobial activity ASTM E2149-01
Soaked fabric sample in 50 ml E. Coli
1.5 – 3.0 x 106 cfu/ml
Incubated with shaking for 24 h
E.coli after soaking was plated in nutrient agar then incubated at 37 °C for 24 h and surviving cells were counted
A = surviving colonies in neat cotton (CFU/ml)
B = surviving colonies in nano-ZnO immobilized cotton (CFU/ml)

18. Zn content & Antimicrobial activity
Sample
Zn content
(ppm/g)
Antimicrobial activity
Surviving cells
(CFU/ml)
% Reduction
Neat cotton
n/a
2.93  106 -
ZnO-cot-2s
57.3  4.6
1.41  106
51.9
ZnO-cot-4s
222.5  19.2
0.72  106
75.4
ZnO-cot-6s
727.4  29.5
0.49  106
83.3

19. Conclusion Self-assembled Nano-ZnO immobilized
Hydrothermal
Self-assembled Nano-ZnO immobilized
PSS/Zn2+ nanolayer cotton fabric
Basic solution
The purposed method is simple and eco-friendly using low amount of non-toxic chemicals and low energy consumption, resulting in the reduction of residual chemicals and investment cost.
The nano-ZnO could effectively enhance the UV protection and antimicrobial activity of the treated cotton fabrics, improving quality and value.

20. Nanoporous Adsorbents for Dye Containing Wastewater Treatment
Motivation & Objective
Dyes are regularly stable and withstand to degrade with time, sunlight and biological and chemical treatments.
Dyes in wastewater can severely affect the aquatic life due to the reduction of light penetration and their toxicity.
The turbidity and color create an unsightly appearance. O2

21. Dye Removal Method Montmorillonite
Amongst the numerous techniques of dye removal, adsorption is the procedure of choice and gives the best results as it can be used to remove different types of coloring materials.
Adsorption is physico-chemical method for dye removal.
Inexpensive alternative adsorbents have been developed from natural materials.
Montmorillonite
A layered structure can act as host material with high sorption properties.

22. Chitosan Intercalated Montmorillonite (Chi-MMT)
Monolayer of chitosan in MMT
Adsorbent
Chitosan Intercalated Montmorillonite (Chi-MMT)
Bilayers of chitosan in MMT
Chi-MMT adsorbent showed higher adsorption capacity for cationic dye than anionic dye.
Problem : Releasing of acetate couterions during adsorption
Cannot regeneration by simple method
Thermal stability
Monvisade, P., and Siriphannon, P., Chitosan Intercalated Montmorillonite: Preparation, Characterization and Basic Dye Adsorption. Appl.Clay.Sci.; 2009; 42(3-4):

23. Aluminium-pillared Montmorillonite (Al-MMT)
Adsorbent
Aluminium-pillared Montmorillonite (Al-MMT)
The intercalation of polynuclear hydroxy metal cations and metal cluster cations such as aluminium polyoxocation in montmorillonite affords pillared clay structure.
(Al13O4(OH)24(H2O)12)7+
Al13-Keggin
Advantages:- relatively large pore size
high specific surface area
good thermal stability

24. Preparation of Al-MMT Modified MMT Drying 105oC AlOH-MMT
2 ml/min
Sonication
Aging RT 24 hr.
Filter and Wash with
distilled water
Drying 105oC
AlOH-MMT
Al13-polyoxocation
solution
2.5 g Na+- MMT
in 100 ml water
XRD, XRF, FTIR,
TGA, BET
Calcining
500oC 4hr.
Al-MMT

25. Chemical composition (mass%)
Sample
Chemical composition (mass%)
Al/Si
Molar ratio
Al2O3
SiO2
Na2O
Other
Na+-MMT
11.99
73.44
2.31
12.26
0.19
AlOH-MMT
20.65
71.92
0.58
6.85
0.33
Al-MMT
20.48
71.71
0.54
7.27
0.34

26. XRD patterns 2q = 5.00o  d001 17.7 Å 2q = 4.80o  d001 18.6 Å

27. Gas adsorption analysis
Specific surface area Na+-MMT m2/g Al-MMT m2/g
3.8 nm nm

28. Aluminium-pillared Montmorillonite (Al-MMT)
House of card

29. Adsorbates
Basic dye
Acid dye
Basic blue 66 (BB66)
Acid red 91 (AR91)

30. Dye adsorption Centrifugation 1 g adsorbent + 100 ml dye solution
3500 rpm
10 min
1 g adsorbent +
100 ml dye solution
Shaking 30, 60, 120 min
UV-Visible
spectrophotometer
BB66 l 615 nm
AR91 l 519 nm
Standard curve
Concentration
Absorbance

31. Adsorption capacity
Initial concentration 500 mg/l

32. Dye adsorption of Na+-MMT
Cation exchange between Na+ and dye cations
Surface adsorption
Dye _
Na+
Na+ _

33. Dye adsorption of Al-MMT
The broaden pore structure with multiple pore sizes of Al-MMT facilitating the penetration of macromolecular dyes.
The increases of surface area and hydroxyl content promoting the electrostatic interaction between Al-MMT adsorbent and dye molecules.
Dye

34. Percentage of dye removal
Adsorbent
AR91
BB66
Dye
Removal
(%)
Adsorption capacity (mg/g)
Na+-MMT 15
7.7 29
14.7
Al-MMT 72
36.2 93
46.6
Adsorption time 60 min

35. Conclusion
The aluminium pillared montmorillonite adsorbents were successfully prepared by high power ultrasonic assisted synthesis and in situ intercalating the aluminium polyhydroxy cations into the interlayer spacing of MMT.
Existence of aluminium pillared structure could enlarge the pore diameter and increase the specific surface area of Al-MMT, facilitating the penetration of macromolecular dyes and also electrostatically interacting with the applied dyes.

36. Acknowledgements Thai government's budget for fiscal year 2011-2012
The National Nanotechnology Center (NANOTEC), Thailand

37. Thank you for your attention