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Viability of Dyeing of Natural and Viability of Dyeing of Natural and Synthetic FibersSynthetic Fibers with Nanopigments in with Nanopigments in
Supercritical COSupercritical CO22
Bàrbara Micó, Verónica Marchante,Francisco Martínez-Verdú, Eduardo Gilabert
Ciencia y Tecnología del ColorSeminario 2009
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
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
ADVANTAGESNo waste water
(problem in textile industry)
No require additivesNo final dryingRecycling
Solvent Colorants
Environmental friendly
DYEING IN SUPERCRITICAL CARBON DIOXIDE
DRAWBACKS Investment Solve colorantsTime of process
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
Scheme of nanopigments’ synthesis at laboratory Nanoclay
Sieving
H2O deionized
Dispersion
Sta
ge
1
+
Colorant solution
Ionic Exchange
Washing and Filtering
Drying
Sta
ge
2
APLICATIONS:- Coloration of Plastics- Printing Inks- Functional materials
Schematic representation of clay sheet, dye molecule (methylene blue) and blue Nanopigment.
Capa de arcilla
Azul de metileno
Capa de arcilla
OBJECTIVES: PROJECT AITEX-AINIA-UA1.
ST
AT
E O
F T
HE
AR
T
2. SELECTION/MATERIAL DEVELOPMENT
3. DISSOLUTION OF MATERIALS IN SC CO2
4. POLYMER IMPREGNATION IN
SC-CO2
6. REENGINIEERING
5. CHARACTERIZETREATED MATERIAL
WITH SC-CO2
7. VIABILITY / ECONOMIC
8. R
ES
UL
TS
AN
D D
OF
US
ION
2.1. POLIMERS 2.2. COLORANTS 2.3.AGENTS ANTIBACTERIAL
Colorants that can be solved in scCO2
Textile dyes classification:DirectsReactiveAcids/BasicsSulphurVatMordantDispersePigments
STATE OF THE ART
NOT DISSOLVED IN SC- CO2
DISSOLVED IN SC-CO2
Azoic [ N N ]The most important disperse dyesCheaper and easy manufacture From non polar fibers
DISPERSE DYESCOLORANT SELECTION
Anthraquinone It’s more soluble [1]
More expensive
MORE SOLUBILITY
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
N N
N ClR
Colorante
+ Fibra-OH N N
NR
Colorante
O Fibra
Fibre
Colorant
Fibre
Colorant
Vinylsulphone : Improve fixations [3]
Are suitable for dyeing textiles containing polyester, nylon, silk or wool.
Fixations between 70 – 90%
REACTIVE DYESCOLORANT SELECTION
Solubility : [4]
-Decrease: OH, NH2,COOR’-Increase: HX NO2
[X=F,Cl,Br,..]
Dyeing stepsTransport of dye to the fibres: SOLUBILITY
Works: different cosolventsAcetonitrileMethanolWaterAcetone
Reaction of the dye with the textile: AFFINITYDIFFUSSION of dye into the fibres: D coefficient.
PROCESS VARIABLES
IMPROVE THE RESULTS
REACTIVE GROUPS
PARTICLE SIZE
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
Planta FSC500
EQUIPMENTS: AINIA PILOT PLANT
Planta PFS20
Planta SFF-58_60
PET the most studied Changes in the structure of polymers:
Plastics: >TgSize stability
Natural fibres [5]
Pre-treatments: Hydrophobic and nonpolar Polyurethane DMDHEU Solvents: Alcohol and water
FIBRES
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
SOLUTIONS / FUTURE PERSPECTIVES Pre-treated fibres:
PET: with UV, N,N-dimethylacrylamideCO: 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
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…
REFERENCESREFERENCES
[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
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.
AcknowledgementsAcknowledgements