1. Viability of Dyeing of Natural and Synthetic Fibers with Nanopigments in Supercritical CO 2 Bàrbara Micó, Verónica Marchante, Francisco Martínez-Verdú, Eduardo Gilabert Ciencia y Tecnología del Color Seminario 2009

2. ÍNDEX Introduction  Supercritical CO 2  Dyeing in supercritical CO 2  Nanopigments and nanoclays Objectives State of the art  Colorant selection  Fibres  Process variables Challenges Solutions / Future perspectives Advantages of using Nanopigments References / Acknowledgements

3. INTRODUCTION Supercritical CO 2 : Solvent Properties  Low cost  Non-Toxic  Density: liquid  Viscosity: Gas  Recycling up to 90%  Inert  Non-explosive  Low critical point Pressure: 73.858 ± 0.005 bar Temperature: 31.05 ± 0.05 ºC

4. ADVANTAGES  No waste water (problem in textile industry)  No require additives  No final drying  Recycling Solvent Colorants  Environmental friendly DYEING IN SUPERCRITICAL CARBON DIOXIDE DRAWBACKS  Investment  Solve colorants  Time of process

5. NANOPIGMETS NANONATERIALS: since 90’s  Hybrid materials consisting of organic dyes and layered silicate nanoparticles  Nanoclay: particle size < 20nm  Ionic-exchange reaction: Colorant + Nanoclay (H + )  Nanoclays: Smectite group Montmollonite: laminar Sepiolite: acicular

6. Scheme of nanopigments’ synthesis at laboratory Nanoclay Sieving H 2 O deionized Dispersion Stage 1 + Colorant solution Ionic Exchange Washing and Filtering Drying Stage 2 APLICATIONS: - Coloration of Plastics - Printing Inks - Functional materials

7. Schematic representation of clay sheet, dye molecule (methylene blue) and blue Nanopigment.

8. OBJECTIVES: PROJECT AITEX-AINIA-UA 1.STATE OF THE ART 2.SELECTION/MATERIAL DEVELOPMENT 3.DISSOLUTION OF MATERIALS IN SC CO 2 4.POLYMER IMPREGNATION IN SC-CO 2 6.REENGINIEERING 5. CHARACTERIZE TREATED MATERIAL WITH SC-CO 2 7.VIABILITY / ECONOMIC 8. RESULTS AND DOFUSION 2.1.POLIMERS2.2.COLORANTS 2.3. AGENTS ANTIBACTERIAL

9. Colorants that can be solved in scCO 2 Textile dyes classification:  Directs  Reactive  Acids/Basics  Sulphur  Vat  Mordant  Disperse  Pigments STATE OF THE ART NOT DISSOLVED IN SC- CO 2 DISSOLVED IN SC-CO 2

10. Azoic [ N N ]  The most important disperse dyes  Cheaper and easy manufacture  From non polar fibers DISPERSE DYES COLORANT SELECTION Anthraquinone  It’s more soluble [1]  More expensive MORE SOLUBILITY

11. REACTIVE DISPERSE DYES [2] (mono-di-)chlorotriazine  Dyeing of natural fibers  Protein or synthetic fibers COLORANT: SELECTION (mono-di-)-fluorotriazine  Dyeing cotton  Using different co-solvents  Methanol improves the solubility REACTIVE GROUPS CHANGE THE COLORANT’S SOLUBILITY Fibre Colorant Fibre Colorant

12. Vinylsulphone : Improve fixations [3] Are suitable for dyeing textiles containing polyester, nylon, silk or wool. Fixations between 70 – 90% REACTIVE DYES COLORANT SELECTION Solubility : [4] -Decrease: OH, NH 2,COOR’ -Increase: HX NO 2 [X=F,Cl,Br,..]

13. Dyeing steps  Transport of dye to the fibres: SOLUBILITY Works: different cosolvents  Acetonitrile  Methanol  Water  Acetone  Reaction of the dye with the textile: AFFINITY  DIFFUSSION of dye into the fibres: D coefficient. PROCESS VARIABLES IMPROVE THE RESULTS REACTIVE GROUPS PARTICLE SIZE

14. EQUIPMENTS Gas cylinder Carbon dioxide pump Pump head cooler Cosolvent reservoir Cosolvent pump Stop valves Pressure gauge Back pressure regulator Dyeing vessel Stirrer Heating jacket Dyeing beam

15. Planta FSC500 EQUIPMENTS: AINIA PILOT PLANT Planta PFS20 Planta SFF-58_60

16. PET the most studied Changes in the structure of polymers:  Plastics: >Tg  Size stability Natural fibres [5]  Pre-treatments: Hydrophobic and nonpolar Polyurethane DMDHEU Solvents: Alcohol and water FIBRES

17. CHALLENGES We only can use non polar colorants in scCO 2 : These kind of colorant haven’t affinity of natural fibres. There are a lot of variables in the process: Solubility can change with:  Colorants (Reactive group, Particle size…)  Pressure  Temperature  Substrates: Natural or synthetic fibers The time of process is too long: 4h

18. SOLUTIONS / FUTURE PERSPECTIVES Pre-treated fibres:  PET: with UV, N,N-dimethylacrylamide  CO: DMDHEU, PUR, acetone… Changes in structure of colorants  [6] Novel reactive disperse dyes has been synthesized. Control the solubility and dye process.  Equations to predict the solubility. NANOPIGMENTS

19. ADVANTAGES OF NANOPIGMENTS Nanopigments are a viable and environmental- friendly alternative to traditional pigments because of their easy synthesis and conventional processing. Increase the color gamut: We can use a lot of conventional organic dyes. Increase the resistance of colors: UV, O 2, Temperature Improve substrate properties: stability, strength, permeability…

20. REFERENCES [1] S. N. Joung et all. “Solubility of Disperse Anthraquinone and Azo Dyes in Supercritical Carbon Dioxide at 313.15 to 393.15 K and from 10 to 25 MPa” J. Chem. Eng. 43, 9-12. 1998 [2] M.V. Fernandez et all “A significant approach to dye cotton in supercritical carbon dioxide with fluorotriazine reactive dyes” J. of Supercritical Fluids 40 477–484. 2007 [3] M. van der Kraan et all. “Dyeing of natural and synthetic textiles in supercritical carbon dioxide with disperse reactive dyes” J. of Supercritical Fluids 40 470–476. 2007 [4] Gerardo A. Montero et all. “Supercritical Fluid Technology in Textile Processing: An Overview” Ind. Eng. Chem. Res., 39, 4806-4812. 2000 [5] P. L. Beltrame, et all.“Dyeing of Cotton in Supercritical Carbon Dioxide”. Dyes and Pigments, 39, 335-340. 1998 [6] Andreas Schmidt, Elke Bach and Eckhard Schollmeyer. “Supercritical fluid dyeing of cotton modified with 2,4,6-trichloro-1,3,5-triazine”. Color. Technol., 119. 2003

21. This work is supported by Ministry of Science and Innovation (MICINN) with the project “Aplicación de la tecnología de fluidos supercríticos en la impregnación de sustratos poliméricos” ref.: CIT- 20000-2009-2. Acknowledgements