Preparation of Titanium Dioxide Sol and Its Application on Tussah Silk

Fixation with Vegetable Dye

LU Yanhuaa, SONG Mingshub and LIN Jiec

Department of Light Chemical Engineering, Eastern Liaoning University, 325 Wenhua Road, Dandong, Liaoning, 118000, China

aemail: yanhualu@aliyun.com,

bemail: songmingshu@163.com,

cemail:linjieln@163.com

Keywords: titanium dioxide sol, dye fixation, vegetable dye, tussah silk dyeing

Abstract. In this paper, nano-sol of titanium dioxide was prepared by sol-gel method using

tetrabutyl-titanate as a precursor. The Particle Size Analyzer test results showed that the average

diameter of the particles was less than 10 nm, and most particle size ranged from 6nm to 16nm. The

prepared mechanism was discussed and then applied to fixation of vegetable turmeric dyed tussah

silk. The fixation results indicated that the rubber fastness and washing fastness increased remarkably

and the K/S values changed a little.

Introduction

Vegetable dyes are friendly to the environment in comparison with synthetic dyes and can exhibit

better biodegradability and generally have a higher compatibility with the environment[1]. In recently

years, a revival interest in the application of vegetable dyes in textile dyeing process has been growing.

This is a result of the stringent environmental standards imposed by many countries in response to the

toxic and allergic reactions associated with synthetic dyes [2]. However, the unsatisfying fastness

properties of the vegetable dyes limited their wide application on textile dyeing fields. Therefore, in

order to reuse the vegetable dyes in modern times, researchers must be understood as an indicator for

a distinct need for study to overcome these fastness problems[3]. In the application of the synthesized

dyes, different techniques of mordanting and post-treatment were used to improve color fastness

properties [4,5]. For natural dyes, the plant tannic acid fixatant was applied to natural dyeing cotton

fabric, and the main fixation mechanism is the crosslinking film forming in the cotton fiber[6].

Nano-sol has the advantage of modified easily by physics and chemical methods. Use of different

nano-sol can provide many excellent properties for textile. The prepared nano-sol can form a

transparent oxide thin film. According to this mechanism, the nano-sol can be used to fix synthesized

dyes in textile fiber and increase the dyeing fastness for textiles[7,8]. For natural dyes fixation, there is

few reports. In this work, the nano-sol of titanium dioxide prepared mechanism was investigated and

the particle size was characterizated. Then the effect of nano-sol of titanium dioxide on fixation on

vegetable turmeric dyed tussah silk was discussed.

Experimental

Materials. Tussah silk fabric ( Type 5023), vegetable turmeric （ Commercial available

Chinese herbal medicine ） ; tetrabutyl-titanate, glacial acetic acid, absolute ethyl alcohol and

hydrochloric acid are all chemical pure reagents.

Extraction of vegetable turmeric dye. In this experiment, the direct method in water was used to

extract turmeric vegetable dye. 40 g beforehand crushed Chinese herbal medicine turmericmiddling

was first to added 500 mLdipped in deionized water，then heated to 80°C for 60min，then volumed

to 1000 mL called original extract solution [9].

Dyeing process of vegetable turmeric dyestuff on tussah silk fabric. The direct dyeing process

was used to dye tussah with turmeric according to the previous reference[10]. The amount of turmeric

original extract solution was 30% at a dyeing ratio of 1:40，pH value was 4. The dyeing process

curve is as follows.

Advanced Materials Research Vols. 821-822 (2013) pp 618-621Online available since 2013/Sep/18 at www.scientific.net© (2013) Trans Tech Publications, Switzerlanddoi:10.4028/www.scientific.net/AMR.821-822.618

All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of TTP,www.ttp.net. (ID: 131.151.244.7, Missouri University of Science and Technology, Columbia, USA-16/08/14,21:11:45)

Fig. 1 Dyeing process of vegetable turmeric dyestuff on tussah silk fabric

The dyeing silk fabric was then treated with 2% detergent at a ratio of 1:40 at 60°C for 5 min.

Preparation and characterization of nano-sol of titanium dioxide. The titanium dioxide nano-Sol

was prepared according to the previous method. 100 mL tetrabutyl titanate and 10 mL glacial acetic

acid were added to 1000mL absolute ethyl alcohol while magnetic stirring to form solution A. 5mL

hydrochloric acid and 20 mL deionized water were added to another 20mL anhydrous alcohol while

magnetic stirring to form solution B. Then the solution B was added dropwise to the solution A while

vigorously stirring at room temperature for 60 minutes. The mixed solution was then adjusted to pH

3.0 with HCl. After mixing uniformly, the stable, transparent and flaxen titanium dioxide nano-Sol

was obtained.

3～5mL of the titanium dioxide nano-Sol was used to test the diameter and its distribution with

ZEN3500 Particle Size Analyzer ( Malven Co.England ) at 25°C.

Fixation process and characterization of tussah silk fabric. The fixation process of turmeric

dyeing tussah silk fabric was adopted padding method for two times at a pick - up rate of 100%, dried

at 105°C for 3min and then cured at 180°Cfor 2min[11].

Characterization of dyeing properties dyed tussah silk fabric before and after treatment.

Relative color strengths (K/S values) were measured by a spectrophotometer (Color-Eye 7000A

U.S.). The reflectance values at maximum absorption wavelength were converted into K/S values.

( )21

/2

RK S

R

−= (1)

Where R is light reflectance at the maximum wavelength, K/S is color shade depth on tussah silk

fabric sample surface. Washing fastness tests were performed according to AATCC61-2003（3A)

with SW-12A washing fastness tester (Wuxi Textile Instrument Factory, China). Rubbing fastness

tests were performed according to AATCC8-2004 with LFY- 304 rubbing fastness tester (Shandong

Textile Research Institute, China).

Results and Discussion

Nano-sol of titanium dioxide preparation mechanism. In this experiment, tetrabutyl-titanate was

used as a precursor to prepared nano-sol of titanium dioxide. The reason was that there exists the

reactive butoxy groups in tetrabutyl-titanate molecules, and these groups could react with hydroxyl or

Hydrogen of some materials. The mechanism of titanium dioxide nano-sol formation is shown from

the reaction scheme (1) to (6).

The three reactions was almost simultaneous with each other, in the hydrolysis action process, the

condition could be controlled to obtain expected nanomaterials. In this experiment, the

hydrolysis rate of tetrabutyl-titanate was exceedingly fast, and in order to control the hydrolysis rate,

glacial acetic acid was used as chelating agent to decreade the reactivity of tetrabutyl-titanate to

prepared titanium dioxide nano-sol rather than gel. The size distribution of nano-particles in the

aqueous dispersion system can be seen in Fig.2

Advanced Materials Research Vols. 821-822 619

Fig.2 Particles size distribution in itanium dioxide nano-sol

Fig.2 showed that the particles in titanium dioxide nano-sol were dispersed perfectly, and the

distribution of the nano-particles was relatively narrow. The size of most particles ranged from 6 nm

to 16 nm, and the average diameter of the particles was 9.73 nm, and the polydispersion coefficient

was 0.41. The prepared nano-sol was then used to fixation of turmeric dyed tussah silk fabric.

Dyeing and fixation of with turmeric dyed tussah silk fabric. According to the optimized process

condition, 6 tussah silk fabric samples were dyed with direct process in about 2.0 g was put into

dyeing solution at a ratio of 1:50, then washing and dried in a drying oven at 80°C. The fixation

process of turmeric dyeing tussah silk fabric was adopted padding method for two times at a pick - up

rate of 100%, dried at 105°C for 3min and then cured at 180°Cfor 2min. The concentration of titanium

dioxide nano-sol range from 0 to 0.1 mol/L. The results of rubbing fastness and washing fastness of

dyed silk fabric were shown in Table 1.

Table 1. Rubbing fastness and washing fastness of dyed tussah silk fabric

Titanium dioxide nano-sol

concentration（mol/L） 0 0.01 0.02 0.03 0.04 0.05 0.1

Rubbing

fastness

dry 3.0 3.5 3.5 4 4 4 4

wet 2.5 2.5 3.0 3.5 3.0 3.0 3.0

Washing

fastness

Staining Cotton 3 3.5 4 4.5 4.5 4.5 4

Silk 3.5 4 4 4.5 4.5 4.5 4

Fading 3 3 3.5 4 4.5 4.5 4.5

It can be seen from Table 1 that the dry and wet rubbing fastness increased with the increase of

titanium dioxide nano-sol concentration, however, the increased degree of dry rubbing fastness was

more than that of wet fastness. On the other hand, the fading fastness was up to maximum when the

titanium dioxide nano-sol concentration was greater than or equal to 0.03 mol/L. Therefore, the

suitable titanium dioxide nano-sol concentration was selected 0.03 mol/L.

620 Advances in Textile Engineering and Materials III

Effect of titanium dioxide nano-sol fixation of K/S values of turmeric dyed tussah silk fabric.

The effects of titanium dioxide nano-sol concentration on K/S values of the turmeric dyed tussah silk

fabric with was shown in Fig. 3.

4.54.64.74.84.955.15.20 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1

Titanium dioxide nano-sol concentration（mol/L）K

/S v

alu

e

Fig. 3 K/S values of turmeric dyed tussah silk fabric with titanium dioxide nano-sol fixation

The result of Fig. 3 indicated that K/S values decrease greatly when the titanium dioxide nano-sol

concentration was greater than 0.04 mol/L, so ij overall evaluation of the effect of titanium dioxide

nano-sol concentration on color fastness, the suitable concentration was selected 0.03 mol/L.

Conclusion

Nano-sol of titanium dioxide was prepared by sol-gel method using tetrabutyl-titanate as a precursor.

The average diameter of the particles was less than 10 nm, and the polydispersion coefficient was

0.41. When applied to fixation of vegetable turmeric dyed tussah silk, the rubber fastness and washing

fastness increased remarkably and the K/S values changed a little.

Acknowledgements

This work was financially supported by Natural Science Foundation of Liaoning Province

(No.201202081), and the Foundation of Key Discipline Project of Liaoning Province Universities

(No. 2012310).

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