Viability of Dyeing of Natural and Viability of Dyeing of Natural and

Synthetic FibersSynthetic Fibers with with NanopigmentsNanopigments in 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

� 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

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.

CH3C

H3

N

CH3

CH3

S

N

CH3

CH3

N

S

N CH3

N

CH

3

CH3

N

S

N CH3

N

CH3

CH3

N

N

C H3

CH3

CH

3C

H3 N

N

S

CH3

CH3 N

S

N

CH3

N

CH3

N

CH3

CH3

N

S

N

CH3

CH 3

N

CH3

C H3

N

S

N

CH3

CH

3

N

CH3

CH3

N

S

N

CH3

CH3

N

CH

CH

N

S

N

CH3

CH3

CH3

CH

3

CH 3

N

S

N

CH3

CH3

N

CH3

CH3

N

S

N

CH3

CH3

N

N

CH3

CH3

N

CH3

CH3

N

S

N

CH

3

CH3

OBJECTIVES: PROJECT AITEX-AINIA-UA1

.STA

TE

OF

TH

E A

RT

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.

RE

SU

LT

S A

ND

DO

FU

SIO

N

2 .1. POLIMERS 2.2. COLORANTS 2.3.

AGENTS

ANTIBACTERIAL

� Colorants that can be solved in scCO2

� Textile dyes classification:

�Directs

�Reactive

�Acids/Basics

�Sulphur

�Vat

�Mordant

�Disperse

�Pigments

STATE OF THE ART

NOT DISSOLVED

IN SC- CO2

DISSOLVED IN

SC-CO2

� 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

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 DYES

COLORANT SELECTION

Solubility : [4]

-Decrease: OH, NH2,COOR’

-Increase: HX NO2

[X=F,Cl,Br,..]

� 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

RESULTSREACTIVE

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: >Tg

�Size 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 sizeQ)

� 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-dimethylacrylamide

�CO: DMDHEU, PUR, acetoneQ

� 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,

permeabilityQ

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