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Transcript of Viability of Dyeing of Natural and Synthetic Fibers with Nanopigments in Supercritical CO 2 Bàrbara...
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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
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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
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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
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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
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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
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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
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Schematic representation of clay sheet, dye molecule (methylene blue) and blue Nanopigment.
Capa de arcilla
Azul de metileno
Capa de arcilla
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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
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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
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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
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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
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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,..]
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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
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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
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Planta FSC500
EQUIPMENTS: AINIA PILOT PLANT
Planta PFS20
Planta SFF-58_60
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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
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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
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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
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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…
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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
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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