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Viability of Dyeing of Natural and Synthetic Fibers with Nanopigments in Supercritical CO 2

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. ÍNDEX. Introduction Supercritical CO 2 Dyeing in supercritical CO 2

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Viability of Dyeing of Natural and Synthetic Fibers with Nanopigments in Supercritical CO 2

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  1. Viability of Dyeing of Natural and Synthetic Fiberswith Nanopigments in Supercritical CO2 Bàrbara Micó, Verónica Marchante, Francisco Martínez-Verdú, Eduardo Gilabert Ciencia y Tecnología del Color Seminario 2009

  2. ÍNDEX • Introduction • Supercritical CO2 • Dyeing in supercritical CO2 • 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 CO2: 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. DYEING IN SUPERCRITICAL CARBON DIOXIDE • ADVANTAGES • No waste water (problem in textile industry) • No require additives • No final drying • Recycling • Solvent • Colorants • Environmental friendly • 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. Nanoclay Stage 1 H2Odeionized Sieving Dispersion + Colorant solution Stage 2 Ionic Exchange Washing and Filtering Drying Scheme of nanopigments’ synthesis at laboratory APLICATIONS: - Coloration of Plastics - Printing Inks - Functional materials

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

  8. 2 . SELECTION / MATERIAL DEVELOPMENT 2.3. ANTIBACTERIAL 2 . 1 . POLIMERS 2 . 2 . COLORANTS AGENTS 3 . DISSOLUTION OF MATERIALS IN SC CO2 RESULTS AND DOFUSION 1.STATE OF THE ART 4 . POLYMER IMPREGNATION IN SC-CO2 CHARACTERIZE TREATED MATERIAL WITH SC-CO2 5 . . 8 6 . REENGINIEERING 7 . VIABILITY / ECONOMIC OBJECTIVES: PROJECT AITEX-AINIA-UA

  9. STATE OF THE ART NOT DISSOLVED IN SC- CO2 DISSOLVED IN SC-CO2 • Colorants that can be solved in scCO2 • Textile dyes classification: • Directs • Reactive • Acids/Basics • Sulphur • Vat • Mordant • Disperse • Pigments

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

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

  12. COLORANT SELECTION • REACTIVE DYES • Solubility : [4] • Decrease: OH, NH2,COOR’ • Increase: HX NO2 • [X=F,Cl,Br,..] Vinylsulphone : Improve fixations [3] Are suitable for dyeing textiles containing polyester, nylon, silk or wool. Fixations between 70 – 90%

  13. IMPROVE THE RESULTS REACTIVE GROUPS PARTICLE SIZE PROCESS VARIABLES • 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.

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

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

  16. FIBRES • 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

  17. CHALLENGES • We only can use non polar colorants in scCO2: • 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, O2, 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

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