Smart Options for Functional Finishing of Linen-containing Fabrics

Smart Options for FunctionalFinishing of Linen-containing Fabrics

N. A. IBRAHIM,* B. M. EID, M. M. HASHEM AND R. REFAI

Textile Research Division, National Research Center, Cairo, Egypt

M. EL-HOSSAMY

Textile Dyeing Technology DivisionFaculty of Applied Arts, Cairo, Egypt

ABSTRACT: This study examined an innovative approach to functional finishesof linen-containing fabrics. Modification of surface properties along with creationon new interactive site onto the fabrics surfaces, i.e., –COOH or –NH2 groups,using oxygen-or nitrogen plasma followed by subsequent treatments with selectedionic dyes, certain metal salts, nano-scale metal or metal oxides, quaternaryammonium salt or nominated antibiotics were carried out to obtain linen-basedtextiles with upgrade UV-protection and/or antibacterial functions. The resultsdetailed in this paper demonstrate that: (i) post-basic dyeing of oxygen plasma-treated substrates with C.I. Basic Red 24 brings about a significant improvement inthe UV-protection and antibacterial activity against the G þve (Staphylococcusaureus) and G –ve (Escherichia coli) bacteria, (ii) post-reactive dyeing of nitrogenplasma-treated substrates with C.I. Reactive violet 5, results in a remarkableimprovement in both UV-blocking and antibacterial properties. (iii) the extentof improvement in the above-mentioned properties of the obtained dyeingsis determined by the type of substrate, kind and concentration of the ionic dye,(iv) loading of the metal ions onto the preactivated fabric surfaces upgradedtheir UV-protection valued as well as their antibacterial efficiency, and the extentof enhancement is governed by the kind and concentration of metal saltas well as type of bacteria, (v) loading of nano-scale Ag, TiO2, or ZrO onto theplasma-treated substrates brings about a remarkable improvement in theirfunctional properties, (vi) loading of the used antibiotics or choline chloride ontothe plasma-treated substrates gives rise to better antibacterial ability, (vii) both theUV-protection ability and the antibacterial activity of selected samples wereretained even after 10 laundering cycles, and (viii) the options described here for

*Author to whom correspondence should be addressed.E-mail: [email protected]; [email protected]

JOURNAL OF INDUSTRIAL TEXTILES, Vol. 39, No. 3—January 2010 233

1528-0837/10/03 0233–33 $10.00/0 DOI: 10.1177/1528083709103144� SAGE Publications 2010

Los Angeles, London, New Delhi and Singapore

attaining linen-containing fabrics with high functional properties are effective, simpleand applicable.

KEY WORDS: linen-containing fabrics, plasma pre-treatment, functional finishes,UV protection, antibacterial, subsequent treatments.

INTRODUCTION

RAW FLAX FIBER is mainly composed of cellulose, lignin with matrixpolysaccharides such as pectic substances and hemicelluloses in

addition to small amounts of fats, waxes, inorganic salts, nitrogenoussubstances and coloring matters [1]. Recent R&D activities have beenfocused on modifying or replacing the traditional harsh chemical processesused for removing hydrophobic impurities from and enhancing thewettability of linen-containing fabrics for subsequent wet finishing process,with energy efficient and environmentally benign alternatives such as,enzymatic treatments, application of ultrasonic energy, as well as plasma-treatment [2].On the other hand, current and new trends in the development of chemical

finishing of textiles, taking in consideration technical, commercial andecological issues, have been focused on: easier applications, using lesschemicals, water and energy cost reduction, better ecology, novel finishes,wellness finishes, medical finishes, bio-finishes, self-cleaning finishes, etc forattaining high performance textile products with high value added, morecompetitive edge along with less undesirable side effects [3–10].This study is directed towards pre-activation of linen-containing fabrics

using O2 or N2 plasma followed by subsequent treatment with ionic dyes,metal salts, nano metal or metal oxides, quaternary ammonium salt orantibiotics to enhance their functional properties, i.e., UV-protection and/orantibacterial properties.

EXPERIMENTAL

Materials

The specifications of linen-containing fabrics used throughout this workare shown in Table 1.Titanium isopropoxide, zirconium oxide nanoparticles, copper acetate,

choline chloride were supplied by Aldrich. Zirconium oxy chlorideoctahydrate and silver nitrate were supplied by Merck. C.I. Basic Red 24

234 N. A. IBRAHIM ET AL.

and C.I Reactive Violet 5 were kindly supplied by DyStar. Doxymycin andCiprofloxacin antibiotics were purchased from Nile Company for pharma-ceutical and chemical industries, Cairo, Egypt, in pure grade and used assupplied.

Other chemicals such as Hostapal� CV-ET (nonionic wetting agent basedon alkaryl polyglycol ether) was kindly supplied by Clariant. Absolute ethylalcohol, acetic acid, sulfric acid, calcium acetate, zinc acetate, sodiumcarbonate, and sodium sulfate were of commercial grade.

Plasma Device

The system used to study the atmospheric pressure dielectric barrierdischarge APDBD consisted of two stainless steel plates, each 4 � 15 cm.The lower plate was covered by a dielectric plate of 1mm thickness. Thesample was placed between the two electrodes and separated from the upperelectrode with a Teflon spacer of 2mm thickness. The system was placed in arectangular Pyrex glass enclosure into which the working gas was introducedto pass through the gap between the electrodes. The exhaust gas wascarried via plastic tubing to the fuming cupboard. The electrodes wereconnected to the power supply. The plasma was created by using AC sourcepower supply with frequency 20000Hz, 50 watts and an output of5 kV/20mA, The plasma reactor system used is schematically shown inFigure 1.

Methods

Plasma Pre-treatment

Bleached linen and linen-containing fabrics samples were placed betweenthe two electrodes of the APDBD reactor. The flow rate of the working gas(oxygen, nitrogen or air) was kept constant at 3 L/minute. The samples wereexposed to the plasma for 30 seconds.

Table 1. Specification of the experimental fabrics.

Type ofsubstrate Weave

Mixingratio YI WI

Wettability(seconds)

Wt/Area(g/m2)

Thickness(mm)

Linen I Plain 100% linen 15.97 18.73 4 207 0.77Linen II Plain 100% linen 20.7 11.45 4 344 1.05Linen/(C/PET)

Plain 50% linen–warp/50%cotton/polyester

(50/50)weft

13.09 32.22 3 250 0.65

Smart Options for Functional Finishing of Linen-containing Fabrics 235

Post Treatment With Metal Salts

Oxygen APDBD-treated fabric samples were treated twice with anaqueous solution of metal salts: copper acetate, calcium acetate, zinc acetateand zirconium oxy chloride (0.005, 0.01mole/L) along with non-ionicwetting agent (2 g/L) to wet pick up of 80% and dried at 80�C for 10minutes. The treated samples were then thoroughly washed to remove excessand unattached metal salts.

Post Treatment with Zirconium Oxide, Titanium Dioxide orSliver Nanoparticles

APDBD-treated fabric samples and untreated samples were dipped intitanium dioxide nanoparticles [11], silver nanoparticles [12] or zirconiumoxide nano-particles and soaked for 10 minutes and then padded to wet pickup of 80%. The samples were then dried at 80�C for 10 minutes, then curedat 150�C for 3 minutes. After curing the samples were thoroughly washed toremove excess and unattached nano-particles.

Post Treatment With Choline Chloride

Oxygen APDBD-treated fabric samples were treated twice withan aqueous solution containing choline chloride (2 g/L) along withnon-ionic wetting agent (2 g/L) at pH 9 to wet pick up of 80% and

Power supply

Exhaust

Dielectric plate

Spaces

Metal electrode

Metal electrode

Sample

Teflon holder

Gas

FIGURE 1. A schematic diagram of the dielectric barrier discharge plasma system.


dried at 120�C for 10 minutes. The treated samples were then thoroughlywashed.

OHN+

Cl−H3C

H3C

CH3Structure of choline chloride

Post Treatment with Antibiotics [13]

Oxygen APDBD-treated fabric and untreated plasma samples were post-treated with Doxymycin antibiotic at concentration of 1% and 2% (owf)using a liquor to fabric ratio 20 : 1 at pH 9 and 65�C for 3 hours.

Nitrogen APDBD treated fabric and untreated plasma samples were post-treated with Ciprofloxacin at concentration of 1% and 2% (owf) using aliquor to fabric ratio 20 : 1 at pH 3 and 65�C for 1 hour.

Chemical structure of doxymycin

H3C OH

OH

CONH2HO HOO O

N(CH3)2

F

O O

OH

N

HN

N

Chemical structure of ciprofloxacin

Post-dyeing of Linen Fabric Samples

A portion of nitrogen and oxygen plasma-treated fabric samples weredyed using certain reactive and basic dyes respectively, according to theconventional exhaustion method. Reactive dyeing bath solution containing0.5%, 1%, or 2% dye (owf). 40 g/L sodium sulfate and 15 g/L sodium


carbonate was used. The dyeing process was performed at 70�C for 45minutes using a material to liquor ratio 1 : 30. After dyeing, the dyed sampleswere thoroughly washed, in presence of 2 g/L non-ionic detergent, at 90�Cfor 10 minutes, rinsed with cold water and finally air dried.

C.I Reactive violet 5

NaO3SOCH2CH2SO2

OO

Cu HNCOCH3

SO3NaNN

NaO3S

Basic dyeing bath solution containing 0.5%, 1%, or 2% dye (owf), 40 g/Lsodium sulfate and acetic acid for adjusting the pH at 4.5. The dyeing processwas performed at 100�C for 60 minutes using material to liquor ratio 1 : 30.The dyed fabric samples were washed, soaped rinsed and then air dried.

C.I. basic red 24

CN

O2NC2H5

CH2CH2N(CH3)3

CH3SO4

+

−

N N N

–

Tests

Surface Morphology

A scanning electron microscope (SEM) examination was carried out forAPDBD plasma-treated and untreated, control, linen fabric samples bymounting the samples on stub with double stick adhesive tape and coatedwith gold in a S150A sputler coater unit (Edwards, UK). The gold filmthickness was 150 A. The samples were then viewed in a JEAOL JXA-840Aelectron probe microanalyzer.

Dye Bath Exhaustion

The extent of dye exhaustion was measured by sampling the dyebath solution before and after the dyeing process. The absorbance ofthe dye solution was measured using an Ultraviolet-Visible (UV-Vis)


spectrophotometer (Shimatzu� UV-1200), at the absorption wavelength ofeach dye. The percentage of dye exhaustion (%E) was calculated using thefollowing equation:

%E ¼ðA0 �AtÞ

A0� 100

where A0 is the absorbance of dye solution at zero minute, and At is theabsorbance of dye solution at t minute.

Color Strength

Dyeability of treated and untreated fabric samples was determined bymeasuring K/S values (K: absorption coefficient, S: scattering coefficient) atwave length of maximum absorbance for the used dyes, with Colour-Eye�

3100 Spectrophotometer supplied by SDL Inter. England [14].

Nitrogen Content

Nitrogen content of treated and untreated linen fabric samples wasdetermined using micro-Kehjeldal method [15].

Carboxyl Content Determination

The carboxyl content of treated and untreated linen fabric samples wasdetermined according to reported method [16].

Metal Content

The metal content of the untreated and treated fabric samples expressedas mmole/mg fabric samples, was quantitatively determined by using FlameAtomic Absorption Spectrophotometer, GBC-Avanta Australia, as follow:0.5 g from dried fabric samples was dissolved in 10mL of 72% sulfuric acidat 3�C followed by taking 0.5mL of this solution and diluting up to 25mLusing buffer solution (0.06M Na2HPO4þ 0.02M NaOH) before analysis.

UV Protection Factor UPF

UPF values were calculated according to the Australian/New ZealandStandard (AS/NZS 4399-1996). According to the Australian classificationscheme, fabrics can be rated as providing good protection, very goodprotection and excellent protection if their UPF values range from 15 to 24,25 to 39 and above 40 respectively [17].


Antimicrobial Activity

Antibacterial activity against Gram-positive bacteria (Staphylococcusaureus) and Gram-negative bacteria (Escherichia coli) was tested:

. Quantitatively according to AATCC Test method 100-1999, and thereduction percent in bacteria (RPC) count was calculated.

. Agar diffusion test according to AATCC Test Method 147-1988.

RESULTS AND DISCUSSION

In order to impart functional properties on linen-based textiles,pretreatment with O2 or N2 plasma, for surface modification along withintroducing –COOH or NH2 groups to the fiber surface, followed bysubsequent treatments with proper dyestuffs, metal salts or certain metal ormetal oxides in nano form or proper antibiotics were studied. Resultsobtained along with their appropriate discussion follow.

UV Protective Function

Ionic Dyes

For a given set of plasma-treatment and subsequent dyeing condition,Table 2 shows that: (i) the UV-blocking function is determined by the typeof substrate, Linen II (very good)> linen (not rateable) � linen/(C/PET)(not rateable) which reflects the differences among the used substrates inweight, thickness, compactness, cellulosic/noncellulosic materials content[4,5,18,19], along with the extent of surface modification by the used plasma,(ii) pre-treatment of the used substrates with N2 plasma followed by reactivedyeing with C.I. Reactive violet 5, results in an enhancement in K/S andUPF values of the obtained dyeings, regardless of the used substrate, (iii) thehigher the dye concentration the better are the K/S and UPF values, (iv) theextent of improvement in the aforementioned properties reflects the positiveimpacts of pretreatment using N2 plasma on [20–23]: changing of the fabricsurface area, removing both the surface fibers and remnant impurities, aswell as modifying chemically the fiber surface through introducing newactive sites, i.e., –NH2 groups thereby leading to the enhancement inwettability and accessibility of the modified structure to reactive dyeingalong with increasing the extent of dye interaction and fixation, expressed asK/S values, which should in turn, enhance the UV-absorption capacity andresult in a remarkable improvement in UV-Protection [6], expressed as UPF


Tab

le2

.E

ffe

ct

of

pla

sma

tre

atm

en

tan

dsu

bse

qu

en

td

yein

go

nth

eU

V-p

rote

ctio

np

rop

ert

ies

of

line

n-c

on

tain

ing

fab

ric

s.

N2

Pla

sma

tre

ate

dS

ub

stra

te

Dye

1

O2

Pla

sma

tre

ate

dsu

bst

rate

Dye

2

UP

FU

PF

Tre

atm

en

tE

xha

ust

ion

(%)

K/S

Va

lue

Pro

tect

ion

Ca

teg

ory

Exh

au

stio

n(%

)K

/SV

alu

eP

rote

ctio

nca

teg

ory

Un

treate

dLi

nen

I–

–12.6

4N

ot

rate

ab

leLi

nen

I–

–12.6

4N

ot

rate

ab

leLi

nen

II–

–28.2

2V

ery

go

od

Lin

en

II–

–28.2

2V

ery

go

od

Lin

en

/(C

/PE

T)

––

10.9

2N

ot

rate

ab

leLi

nen

/(C

/PE

T)

––

10.9

2N

ot

rate

ab

leO

nly

pla

sma

treatm

en

tL

ine

nI

(NC

0.2

0,

wet<

1se

con

ds)

––

15.9

5G

oo

dLi

nen

I(C

C12.7

,w

et<

1se

con

ds)

*

––

13.3

5N

ot

rate

ab

le

Lin

en

II(N

C0.2

8,

wet<

1se

con

ds)

––

32.0

0V

ery

go

od

Lin

en

II(C

C26.2

2,

wet<

1se

con

ds)

*

––

30.5

6V

ery

go

od

Lin

en

/(C

/PE

T)

(NC

0.1

8,

wet<

1se

con

ds)

––

13.9

6N

ot

rate

ab

leLi

nen

/(C

/PE

T)

(CC

20.4

,w

et<

1se

con

ds)

*

––

11.8

6N

ot

rate

ab

le

Pla

sma

treatm

en

tfo

llow

ed

by

dye

ing

at

con

c.(g

/l)o

f:

0.5

Lin

en

I60.3

21.5

325.4

6V

ery

go

od

Lin

en

I66.9

61.5

416.0

2G

oo

d

(Co

ntin

ued

)


Tab

le2

.C

on

tinu

ed

.

N2

Pla

sma

tre

ate

dS

ub

stra

te

Dye

1

O2

Pla

sma

tre

ate

dsu

bst

rate

Dye

2

UP

FU

PF

Tre

atm

en

tE

xha

ust

ion

(%)

K/S

Va

lue

Pro

tect

ion

Ca

teg

ory

Exh

au

stio

n(%

)K

/SV

alu

eP

rote

ctio

nca

teg

ory

Lin

en

II58.2

01.3

641.9

0E

xcelle

nt

Lin

en

II71.8

91.7

545.7

8E

xcelle

nt

Lin

en

/(C

/PE

T)

58.0

91.0

518.0

0G

oo

dLi

nen

/(C

/PE

T)

64.5

10.9

619.6

6G

oo

d1

Lin

en

I61.1

32.5

930.4

4V

ery

go

od

Lin

en

I73.0

13.0

025.8

2G

oo

dLi

nen

II59.6

62.3

352.6

3E

xcelle

nt

Lin

en

II77.2

03.4

172.0

6E

xcelle

nt

Lin

en

/(C

/PE

T)

59.0

42.1

129.0

4V

ery

go

od

Lin

en

/(C

/PE

T)

66.7

71.8

030.3

6V

ery

go

od

2Li

nen

I67.6

23.9

253.5

6E

xcelle

nt

Lin

en

I76.8

34.1

130.1

4V

ery

go

od

Lin

en

II66.4

53.4

064.7

5E

xcelle

nt

Lin

en

II77.5

24.9

589.7

0E

xcelle

nt

Lin

en

/(C

/PE

T)

64.0

92.8

935.8

1V

ery

go

od

Lin

en

/(C

/PE

T)

68.8

32.5

839.1

1V

ery

go

od

Pla

sma

treatm

en

t:A

PD

BD

pla

sma;

po

wer

sup

ply

with

20,0

00

Hz

freq

uen

cy,

50

Wan

dan

ou

tpu

to

f5

kV/2

0m

A,

for

30

seco

nd

s.N

2p

lasm

a-t

reate

dsa

mp

les

was

follo

wed

by

dye

ing

with

Dye

1(C

.IR

eact

ive

Vio

let

5,�¼

560).

O2

pla

sma-t

reate

dsa

mp

les

was

follo

wed

by

dye

ing

with

Dye

2(C

.I.B

asi

cR

ed

24,�¼

500).

K/S

:co

lor

stre

ng

th,

UP

F:

UV

Pro

tect

ion

fact

or.

(NC

):n

itro

gen

con

ten

t(%

);(C

C)*

:ca

rbo

xyl

con

ten

t(m

eq

.CO

OH

/100

gfa

bric

s),

wet:

wett

ing

time.


values, regardless of the used substrate, (v) the extent of improvement indye uptake, depth of shade as well as UV-protection is determined bythe nature of the substrate as well as its extent of modification and post-reactive dyeing, and (vi) presence of copper in the dye structure exerts aconsiderable enhancement in its ability to absorb the harmful UV-raysthereby adding to or improving the UV-Protection functionality of thetreated substrates [5].

On the other hand, the data in Table 2 show that; (i) pretreatment of theused substrates with oxygen plasma is accompanied by introducing polarfunctional groups, especially the –COOH groups, to the fiber thereby actingas active dye sites for the used basic dye along with increasing thehydrophilicity of the surface [20], (ii) the uptake of the dye as well asthe extent of fixation, expressed as K/S values, are determined by the typeof the substrate, physical and chemical changes on its surface as well as thedye concentration, and K/S values of the obtained dyeings followedthe decreasing order linen II> linen I> linen/(C/PET), (iii) increasingthe dye concentration up to 2% owf results in a significant improvement inK/S values along with a remarkable improvement in UV-protectionfrom UV-B radiation (up to UPF>50—excellent protection—as in caseof linen II dyeings, and up to UPF>30 or 39—very good protection as incase of linen/(C/PET) and linen I dyeings respectively), and (iv) theoutstanding improvement in UV-blocking properties of the obtained basicdyeings reflects the dramatic reduction in UV-radiation transmission due tothe higher UV-absorbance of the chemical structure of the used dyemolecules along with better extent of interaction with plasma-treatedsubstrates.

Metal Salts

As far as the changes in the extent of improvement in UV-protectionproperties of the treated substrates as a function of the type of substrate aswell as the type and concentration of metal salt, Table 3 reveals that: (i)post-treatment of the O2 plasma-treated substrates with the nominatedmetal salts is accompanied by an increase in the metal content of the treatedsubstrates as well as in their UPF values, regardless of the used substrate,(ii) the extent of improvement in the UPF values is determined by: thetype of substrate, i.e., number location and availability of its active sites,e.g., –OH and –COOH groups, ability to pickup, retain, interact and to formstable metal chelates between its functional groups and metal ions, the kindof metal ion, i.e., molecular size, location and extent of distribution ontoand/or within the plasma-treated substrate as well as its affinity and ability


Tab

le3

.E

ffe

ct

of

oxy

ge

np

lasm

aan

dsu

bse

qu

en

ttr

eatm

en

tw

ithm

eta

lsa

ltso

nth

eU

Vp

rote

ctio

np

rop

ert

ies

of

line

n-c

on

tain

ing

fab

ric

s.

Co

nce

ntr

atio

n

0.0

05

mo

le/L

0.0

1m

ole

/L

UP

FU

PF

Me

tal

salt

Typ

eo

fsu

bst

rate

sM

eta

lco

nte

nt

(%)

Va

lue

Pro

tect

ion

cate

go

ryM

eta

lco

nte

nt

(%)

Va

lue

Pro

tect

ion

cate

go

ry

No

ne

(pla

sma-t

reate

d)

Lin

en

I–

13.4

5N

ot

rate

ab

le–

13.4

5N

ot

rate

ab

leLi

nen

II–

30.5

6V

ery

go

od

–30.5

6V

ery

go

od

Lin

en

/(C

/PE

T)

–11.8

6N

ot

rate

ab

le–

11.8

6N

ot

rate

ab

leZ

n-

Lin

en

I0.0

84

19.2

8G

oo

d0.1

28

24.1

0G

oo

dLi

nen

II0.1

37

30.0

0V

ery

go

od

0.1

65

38.9

9V

ery

go

od

Lin

en

/(C

/PE

T)

0.1

03

18.5

2G

oo

d0.1

10

23.2

5G

oo

dC

a-

Lin

en

I0.0

58

23.2

4G

oo

d0.0

83

29.7

3V

ery

go

od

Lin

en

II0.0

79

38.6

1V

ery

go

od

0.0

99

40.0

5E

xcelle

nt

Lin

en

/(C

/PE

T)

0.0

66

22.5

6G

oo

d0.0

88

26.5

9V

ery

go

od

Cu

-Li

nen

I0.0

84

30.8

7V

ery

go

od

0.1

22

35.0

0V

ery

go

od

Lin

en

II0.1

38

56.8

2E

xcelle

nt

0.2

15

62.0

7E

xcelle

nt

Lin

en

/(C

/PE

T)

0.1

15

29.1

6V

ery

go

od

0.1

45

33.8

9V

ery

go

od

Zr-

Lin

en

I0.0

68

26.5

5V

ery

go

od

0.1

39

30.3

5V

ery

go

od

Lin

en

II0.1

21

40.3

3E

xcelle

nt

0.3

01

43.7

8E

xcelle

nt

Lin

en

/(C

/PE

T)

0.0

71

27.0

2V

ery

go

od

0.1

49

29.3

0V

ery

go

od

Pla

sma

treatm

en

t:A

PD

BD

pla

sma;

po

wer

sup

ply

with

20,0

00

Hz

freq

uen

cy,

50

Wan

dan

ou

tpu

to

f5

kV/2

0m

A,

for

30

seco

nd

s.Tre

atm

en

tco

nd

itio

n:

meta

lsa

lt0.1

,0.2

M/L

,n

on

-io

nic

wett

ing

ag

en

t2

g/L

;w

et

pic

ku

p80%

(ow

f);

dry

ing

at

80/1

0m

inu

tes,

follo

wed

by

aft

er

wash

ing

tore

mo

veexc

ess

an

du

ntr

eate

dm

eta

lsa

lt.


to interact with the functional groups of the modified substrate according tothe following Equation [5]:

S

Substrate

O2 -plasma SOxygen plasma treated substrate

Complex structure

COOH + [ S COO]2M + 2H+M2+

+(1)Metal

cation

as well as the ability of the formed complex structure to absorb and/or blockthe hazardous UV-B radiation [5,6] thereby giving rise to higher UPF-valuesand better UV-protection, (iii) for a given set of treatments, the improvementin the UV-protection of the treated samples shows the following trends:linen II> linen/(C/PET)¼Linen I, keeping the metal salt constant, andCu-acetate>Zr-oxy chloride>Ca-acetate>Zn-acetate>None, keepingthe substrate constant, and (iv) the higher the metal salt ion concentration thebetter are the UPF-values.

Nano-TiO2

As far as the variation in UV-protection capacity, expressed as UPF-values, of the treated fabric samples as a function of type of substrate, plasmagas, as well as post-treatment with colloidal TiO2, the data in Table 4 signify

Table 4. Effect of plasma and subsequent treatment withnano-TiO2 on the UV-protection of linen containing fabrics.

UPF evaluation

Treatment sequenceType of

substratesMetal

content (%) UPF Classification

Untreated Linen I – 12.64 Not rateableLinen II – 28.22 Very good

Linen/(C/PET) – 10.92 Not rateableNano-TiO2 no plasma treatment Linen I 0.623 21.51 Good

Linen II 0.699 40.19 ExcellentLinen/(C/PET) 0.465 48.26 Excellent

N2–plamsa! nano-TiO2 Linen I 0.646 38.90 Very goodLinen II 0.726 54.41 Excellent

Linen/(C/PET) 0.762 65.34 ExcellentO2–plamsa! nano-TiO2 Linen I 0.635 30.92 Very good

Linen II 0.710 47.46 ExcellentLinen/(C/PET) 0.659 57.94 Excellent

Plasma treatment: APDBD plasma; power supply with 20,000 Hz frequency, 50 W and an output of5 kV/20 mA, for 30 seconds.Treatment condition: colloidal TiO2 2 g/L, wet pick up 80% (owf); drying at 80�C/10 minutes, curing at150�C/3 minutes.


that: (i) the enhancement in the UPF values is determined by the sequence oftreatment, i.e., nitrogen plasma followed by subsequent treatment with nanoTiO2>oxygen plasma followed by subsequent treatment with nano-TiO2> treatment with nano-TiO2>untreated, (ii) this reflects the positiveimpact of the plasma pretreatment on modifying the surface hydrophilicity,creating porous surface structure by etching as well as introducing newaccessible functional groups, i.e., –NH2 or –COOH groups, therebyincreasing the extent of picking up and anchoring nano-TiO2 on the fabricsurface, via coordination, which could be simplified by the following tentativemechanism [19,20,24].

Plasma

Substrate

PaddingTiO2-loaded substrate

ThermofixingModified substrate + Nano-TiO2

Modified substrate

Active speciesO– O•O2 O* O*

S

M SCOOH

OC CO

CO

(3)

O

O

Surface

modification

(2)

(4)

(iii) the variation in the UPF values of the treated fabric samples reflects thedifferences among these substrates in: weight, thickness, fiber chemistry,extent of changes in fiber surface chemistry and morphology as well as typeand amount of functional groups, introduced by plasma treatment, andaccessible to attach nano-TiO2 directly to the fabric surfaces via coordina-tion, i.e., amount of loaded nano-TiO2, (iv) the remarkable improvement inthe UPF-values as well the UV-protection capacity, especially in caseof using linen II and linen/(C/PET) substrates, confirms the outstandingUV-blocking function of the anchored nano-TiO2 mainly through its highUV-absorption capacity [25,26].Figures 2 and 3 present the SEM of linen and linen/(C/PET) with or

without TiO2 thin film and also illustrate the effect of plasma pre-treatmenton the surface of the post-treated samples with TiO2. It is clear that pre-treatment with plasma followed by post-treatment with TiO2 in nano formgives a homogenous and uniform film, regardless of the used gas. On the otherhand the homogeneity of the formed films is governed by the nature of plasmagas and follows the decreasing order: N2 plasma pre-treatment followed byTiO2 sol gel treatment>O2 plasma pre-treatment followed by TiO2 sol geltreatment>TiO2 sol gel treatment without plasma pre-treatment.


Antibacterial Functions

Cellulose-based textiles can support the growth of microorganismsthrough acting as nutrients and energy sources under certain conditions.Contamination by microorganisms such as some harmful species of bacteriaand fungi has negative impacts not only on the user, e.g., infection,transmission of diseases, bad odor, etc., but also on the textile productitself, e.g., quality deterioration, staining, discoloration, etc. Antibacterialagents either inhibit the growth (biostatic) or kill (biocidal) the micro-organisms [7–9,27,28].

This part is directed toward enhancing the antibacterial properties oflinen-containing fabrics via plasma pre-treatment, for surface modification,followed by subsequent treatment with selected active agents such

(a) (b)

(c) (d)

FIGURE 2. SEM of treated linen II with TiO2 sol gel using different sequence oftreatment: (a) Untreated substrate, (b) TiO2 sol gel without plasma pretreatment,(c) N2 plasma pretreatment followed by TiO2 sol gel, (d) O2 plasma pretreatmentfollowed by TiO2 sol gel.


as antibiotics, quaternary ammonium salt, ionic dyestuffs, metal salts ormetal/metal oxides in nano form, to cope with the high demand forantimicrobial textiles. Results obtained along with their appropriatediscussion follow.

Antibiotics

As far as the change in antibacterial activity, expresses as zone ofinhibition, of the treated substrates as a function of type of substrate,plasma gas, as well as type and concentration of antibiotic, against gramnegative (G –ve) and gram positive (G þve) bacteria, the data obtained inTable 5 signify that the antibacterial function of the treated substratesis determined by: (i) the sequence of treatment: plasma treatment followedby post-treatment with antibiotic> treatment with antibiotic�none,regardless of the used antibiotic and the treated substrate, (ii) type

(a) (b)

(c) (d)

FIGURE 3. SEM of treated linen/(C/PET) with TiO2 sol gel using different sequenceof treatment: (a) Untreated substrate, (b) TiO2 sol gel without plasma pretreatment,(c) N2 plasma pretreatment followed by TiO2 sol gel, (d) O2 plasma pretreatmentfollowed by TiO2 sol gel.


Tab

le5

.E

ffe

ct

of

pla

sma

follo

we

db

ysu

bse

qu

en

ttr

eatm

en

tw

ithan

tibio

tics

on

the

an

tibac

teri

al

ac

tivity

of

line

n-c

on

tain

ing

fab

ric

s.

Cip

roD

oxy

ZI

(mm

)Z

I(m

m)

Tre

atm

en

t

N2

pla

sma

tre

ate

dsu

bst

rate

Nitr

og

en

con

ten

t(%

)Gþ

veS

.au

reu

sG�

veE

.c

oli

O2

pla

sma

tre

ate

dsu

bst

rate

Nitr

og

en

con

ten

t(%

)Gþ

veS

.au

reu

sG�

veE

.c

oli

Un

treate

dLi

nen

I–

no

zon

en

ozo

ne

Lin

en

I–

no

zon

en

ozo

ne

Lin

en

II–

no

zon

en

ozo

ne

Lin

en

II–

no

zon

en

ozo

ne

Lin

en

/(C

/PE

T)

–n

ozo

ne

no

zon

eLi

nen

/(C

/PE

T)

–n

ozo

ne

no

zon

eA

ntib

iotic

treatm

en

t(w

itho

ut

pla

sma

pre

treatm

en

t)(1

%o

wf)

Lin

en

I0.2

114

12

Lin

en

I0.1

413

10

Lin

en

II0.3

416

15

Lin

en

II0.1

414

11

Lin

en

/(C

/PE

T)

0.2

415

13

Lin

en

/(C

/PE

T)

0.1

617.5

13

Pla

sma

treatm

en

tfo

llow

ed

An

tibio

ticp

ost

-tre

atm

en

tat

con

c.(%

ow

f)o

f:

1Li

nen

I0.3

416

15

Lin

en

I0.1

415

11

2Li

nen

II0.3

917

16

Lin

en

II0.1

616.5

12

Lin

en

/(C

/PE

T)

0.3

816.5

15

Lin

en

/(C

/PE

T)

0.1

819

14

Lin

en

I0.3

718.5

18

Lin

en

I0.1

717

13.5

Lin

en

II0.4

421

19

Lin

en

II0.1

919

15

Lin

en

/(C

/PE

T)

0.4

118

17

Lin

en

/(C

/PE

T)

0.2

221

17

Pla

sma

treatm

en

t:A

PD

BD

pla

sma;

po

wer

sup

ply

with

20,0

00

Hz

freq

uen

cy,

50

Wan

dan

ou

tpu

to

f5

kV/2

0m

A,

for

30

seco

nd

s.P

ost

treatm

en

tw

ithan

tibio

tics:

Oxy

gen

AP

DB

D-t

reate

dsa

mp

les

were

po

st-t

reate

dw

ithD

oxy

myc

inan

tibio

tic,

1%

an

d2%

(ow

f);

L/R

:1/2

0;

pH

9,

65�

Cfo

r3

ho

urs

.N

itro

gen

AP

DB

D-t

reate

dsa

mp

les

were

po

st-t

reate

dw

ithC

ipro

floxa

cin

1%

an

d2%

(ow

f);

L/R

:1/2

0;

pH

3;

65�C

for

1h

ou

r.Z

I:zo

ne

of

inh

ibiti

on

,in

cub

atio

ntim

e:

24

ho

urs

.


of substrate: linen II> linen I> linen/(C/PET) in case of using N2

plasma followed by subsequent treatment with Ciprofloxacin, or linen/(C/PET)> linen II> linen I in case of using O2 plasma followed bysubsequent treatment with Doxymycin, (iii) concentration of the antibiotic,i.e., the higher the antibiotic content onto/within the treated substrate, thebetter is the antibacterial efficiency of the antibiotic-loaded substrates,and (iv) kind of bacteria, i.e., G þve> G �ve bacteria regardless of theused substrate.The differences in antibacterial functionality among the used substrates

reflects the variation in their: physico-chemical properties, extent ofmodification by plasma-treatment, ability to interact bind and/or entrapthe antibiotic onto and/or within the treated substrates, in addition tothe extent of antibiotic release/leach out from the fiber surface andtherefore a difference in the extent of diffusion into agar, i.e., difference ineffectiveness [7–9,27–29].A tentative mechanism for the interactions among plasma-treated

substrates and the nominated antibiotics may be represented as:

(6)

S NH2 + CiproCiprofloxacin

COOHH+ Modified substrate loaded

with ciprofloxacin (7)

Modified substrate loadedwith Doxymycin

O2 -plasma S COOH +

Substrate

+ Doxy

Doxymycin

NOH

_S + N2-plasma S NH2 (5)

The remarkable improvement in the antibacterial function of theantibiotic-loaded substrates reflects the positive role of the leached outantibiotic in damaging the cell membranes, denaturing of proteins anddisrupting the cell structure [27,30]. The extent of improvement is governedby the molecular size, its ability to penetrate the cell membrane of bacteriaand inhibit their reproductive enzymes [27,30].On the other hand, the data in Table 5 clarify that the inactivation

efficiency of G þve bacteria (S. aureus) was better than that of G �vebacteria (E. coli) reflecting the differences between the aforementioned typesin the cell wall structure, amenability to destruction and disruption, as wellas in response for inactivation [7–9,31].Images from a SEM of plasma-treated and plasma-treated followed

by subsequent antibiotic loading are presented Figure 4(a)–(d). It isclear that the deposition of the antibiotics onto the substrate surface,however, there is no visible difference between the films in both antibioticsFigure 4(b) and (d).


Choline Chloride

For a given set of treatment conditions, Table 6 shows that: (i) theantibacterial activity of the treated fabric samples follows the decreasingorder: O2 plasma treatment followed by subsequent treatment with cholinechloride>O2 plasma treatment�none, (ii) the extent of improvement isgoverned by the extent of modification of the treated substrates and followsthe order: linen/(C/PET)> linen II> linen I, (iii) inactivation performancedepends on the type of bacteria, i.e., G þve>G –ve, regardless of the usedsubstrate, and (iv) the positive impact of the used cationic quaternaryammonium salt, i.e., choline chloride, loaded onto the negatively chargedactive sites (–COOH groups), most probably due to its detrimental effects onmicroorganisms such as damaging of cell membranes, denaturing of proteinsand disruption of cell structure [27,32,33], and (v) O2 plasma alone slightly

(b)

(d)(c)

(a)

FIGURE 4. SEM of plasma treatment and plasma pretreatment followed by posttreatment with different antibiotics for linen II: (a) N2 plasma pretreatment, (b) N2

plasma pretreatment followed by post treatment with Cipro antibiotic, (c) O2 plasmapretreatment, (d) O2 plasma pretreatment followed by post treatment with doxyantibiotic.


improves the antibacterial effect of the treated fabric samples throughcreating active species along with introducing new functional groups ontothe substrate thereby acting as a barrier against bacteria and/or damagingthe cell wall or alter cell membrane permeability [34].

Ionic Dyeing

As far as the variation in the antibacterial functions of the plasma-treatedpost-dyed fabric samples, Table 7 shows that: (i) pre-treatment with nitrogenor oxygen plasma results in enhancing the hydrophilicity of the treatedsamples (<1 second) along with generating new active sites onto the fabricsurface (–NH2 or –COOH groups respectively), (ii) postdyeing with Reactiveviolet 5 or Basic Red 24 dye respectively is accompanied by a significantimprovement in both the extent of coloration, expressed as K/S values, aswell as in the antibacterial efficiency, expressed as RPC% for reactivedyeings or zone of inhibition for basic dyeings, (iii) the extent ofimprovement in K/S values is governed by type of substrate, its nitrogenor carboxyl content as well as the nature of dye and its concentration,(iv) the higher the dye concentration is, the higher the depth of shade and thebetter the antibacterial effect, regardless of the used dye, reflectingthe positive impact of Cu-component of the reactive dyeings on inhibitionof the active enzyme centers, i.e., inhibition of metabolism which is essentialfor cell survival [10,27], or the positive effect of quaternary ammonium

Table 6. Effect of oxygen plasma followed by subsequent treatment with cholinechloride on the antibacterial activity of linen-containing fabrics.

Z I (mm)

Treatment Substrates

Carboxyl content(meq.COOH/100 g

fabrics)Nitrogen

content (%)G þve

S. aureusG �veE. coli

O2 plasma Linen I 12.7 – 2 2.5Linen II 26.22 – 2.4 3

Linen/(C/PET) 20.4 – 3 5O2 plasma

choline chlorideLinen I – 0.21 3.5 2.0

Linen II – 0.31 5 3Linen/(C/PET) – 0.35 9 6

Plasma treatment: APDBD oxygen plasma; power supply with 20,000 Hz frequency, 50 W and an output of5 kV/20 mA, for 30 seconds.Choline chloride (2 g/L); non-ionic wetting agent (2 g/L); pH 9; wet pick up of 80%, dried at 120�C for 10minutes.The treated samples were then thoroughly washed.ZI: zone of inhibition, incubation time: 24 hours.


Tab

le7

.E

ffe

ct

of

pla

sma

tre

atm

en

tan

dsu

bse

qu

en

td

yein

go

nth

ean

tibac

teri

al

ac

tivity

of

line

n-c

on

tain

ing

fab

ric

s.

Dye

1D

ye2

Dye

con

c.(%

ow

f)R

PC

%Z

I(m

m)

N2

pla

sma

tre

ate

dsu

bst

rate

K/S

Gþ

veS

.au

reu

sG�

veE

.c

oli

O2

pla

sma

tre

ate

dsu

bst

rate

K/S

Gþ

veS

.au

reu

sG�

veE

.c

oli

Un

treate

dLi

nen

I–

––

Lin

en

I–

––

Lin

en

II–

––

Lin

en

II–

––

Lin

en

/(C

/PE

T)

––

–Li

nen

/(C

/PE

T)

––

–O

nly

pla

sma

treatm

en

tLi

nen

I(N

C0.2

0,

wet<

1se

con

d)

–9.2

15.6

Lin

en

I(C

C12.7

,w

et<

1se

con

d)*

––

–

Lin

en

II(N

C0.2

8,

wet<

1se

con

d)

–13.3

23.9

Lin

en

II(C

C26.2

2,

wet<

1se

con

d)*

––

–

Lin

en

/(C

/PE

T)

(NC

0.1

8,

wet<

1se

con

d)

–11.4

20.5

Lin

en

/(C

/PE

T)

(CC

20.4

,w

et<

1se

con

d)*

––

–

Pla

sma

treatm

en

tfo

llow

ed

by

dye

ing

at

con

c.(%

ow

f)o

f:

0.5

Lin

en

I1.5

310.0

28.0

0Li

nen

I1.5

45

3

Lin

en

II1.3

623.5

42.8

7Li

nen

II1.7

58

5Li

nen

/(C

/PE

T)

1.0

512.5

31.7

0Li

nen

/(C

/PE

T)

0.9

64

21

Lin

en

I2.5

918.0

435.5

1Li

nen

I3.0

08.5

5Li

nen

II2.3

331.8

555.9

7Li

nen

II3.4

110

7Li

nen

/(C

/PE

T)

2.1

121.6

545.2

3Li

nen

/(C

/PE

T)

1.8

08

42

Lin

en

I3.9

233.2

78.1

6Li

nen

I4.1

110

8Li

nen

II3.4

044.4

485.0

3Li

nen

II4.9

511

9Li

nen

/(C

/PE

T)

2.8

938.8

981.5

2Li

nen

/(C

/PE

T)

2.5

89

6

Pla

sma

treatm

en

t:A

PD

BD

pla

sma;

po

wer

sup

ply

with

20,0

00

Hz

freq

uen

cy,

50

Wan

dan

ou

tpu

to

f5

kV/2

0m

A,

for

30

seco

nd

s.N

2–p

lasm

a-t

reate

dsa

mp

les

was

follo

wed

by

dye

ing

with

Dye

1(C

.IR

eact

ive

Vio

let

5,�¼

560).

O2–p

lasm

a-t

reate

dsa

mp

les

was

follo

wed

by

dye

ing

with

Dye

2(C

.I.B

asi

cR

ed

24,�¼

500).

K/S

:co

lor

stre

ng

th,

RP

C%

:re

du

ctio

np

erc

en

tin

bact

eria

cou

nt;

ZI:

zon

eo

fin

hib

itio

n;,

incu

batio

ntim

e:

24

ho

urs

.(N

C):

nitr

og

en

con

ten

t(%

);(C

C)*

:ca

rbo

xyl

con

ten

t(m

eq

.CO

OH

/100

gfa

bric

s),

wet:

wett

ing

time.


group-component of the basic dyeings on disrupting the cytoplasmicmembranes of bacteria thereby resulting in the breakdown of the cell[33,35,36], and (v) the inactivation efficiency of G –ve bacteria, i.e., E. coli,was higher than that of G þve bacteria, i.e., S. aureus in case of using thereactive dyeings, and the opposite hold true in case of using the basicdyeings, which may be discussed in terms of differences in: cell wallstructure, response to inactivation, survival of bacteria as well as inhibitionmechanism [31].

Metal Salts

For a given set of O2 plasma and subsequent treatments with Cu-acetate,Zn-acetate or Zr-oxy chloride conditions, the data in Table 8 reveal that: (i)after treatment of the pre-activated fabric samples, with nominated saltsresults in an enhancement in their metal contents along with an outstandingimprovement in their antibacterial abilities, (ii) the extent of improvement isgoverned by the type of the substrate, i.e., surface properties, number andlocation of the generated hydrophilic groups (–COOH groups) onto itssurface, ability of pick-up and accessibility to react with metal salt to bindthe metal ions to the after-treated fabric surface, as well as the type ofmetal ions, i.e., Zn>Zr>Cu, as well as its ability to bind to specific sites inthe DNA in the bacteria cells thereby inactivating and killing bacteria[10,27,37], (iii) the antibacterial activity of the after-treated fabric samplesfollows the decreasing orders: linen/(C/PET)> linen II> linen I, keepingthe other parameters constant, and Zn-loaded substrate>Zr-loadedsubstrate>Cu-loaded substrate � plasma-treated substrate, keepingother parameters fixed, (iv) the slight improvement in the antibacterialproperties of O2 plasma-treated fabric samples may be attributed tothe generated –COOH groups onto the fabric surface that could inhibit thegrowth of bacteria [38], (v) the higher is the concentration of metal salt, thehigher are the loaded-metal ions and the antibacterial efficiency, expressedas RPC%, and (vi) inactivation efficiency of G –ve bacteria (E. coli) wasmuch higher than that of G þve bacteria (S. aureus) which may beattributed to the higher response of G –ve bacteria for inhibition andinactivation under the given treatment and evaluation conditions [31].

Ag, TiO2, or ZrO Nanoparticles

For a given set of pre- and post-treatment conditions, Table 9 showsthat: (i) post-loading of the used nano Ag, Ti2, ZrO onto the plasma-treated substrates is accompanied by a remarkable improvement in theirantibacterial properties, (ii) the extent of improvement is governed by


Tab

le8

.E

ffe

ct

of

oxy

ge

np

lasm

aan

dsu

bse

qu

en

ttr

eatm

en

tw

ithm

eta

lsa

ltso

nth

ean

timic

rob

ial

ac

tivity

of

line

n-c

on

tain

ing

fab

ric

s.

Co

nce

ntr

atio

n

0.0

05

mo

le/L

0.0

1m

ole

/L

RP

C%

RP

C%

Me

tal

salt

Typ

eo

fsu

bst

rate

sM

eta

lco

nte

nt

(%)

Gþ

veS

.au

reu

sG�

veE

.c

oli

Me

tal

con

ten

t(%

)Gþ

veS

.au

reu

sG�

veE

.c

oli

No

ne

(pla

sma

treate

d)

Lin

en

I(C

C12.7

)*–

4.0

10.0

–4.0

10.0

Lin

en

II(C

C26.2

2)*

–9.5

19.0

–9.5

19.0

Lin

en

/(C

/PE

T)

(CC

20.4

)*–

6.0

13.0

–6.0

13.0

Zn

-Li

nen

I0.0

84

26.0

65.4

80.1

10

41.6

776.5

8Li

nen

II0.1

37

41.4

91.0

80.1

65

76.4

494.5

7Li

nen

/(C

/PE

T)

0.1

03

30.9

87.2

60.1

28

56.3

489.0

0C

u-

Lin

en

I0.0

84

15.4

452.9

10.1

22

30.5

363.0

0Li

nen

II0.1

38

31.1

170.2

40.2

15

60.0

284.8

2Li

nen

/(C

/PE

T)

0.1

15

20.0

465.2

30.1

45

48.4

273.0

8Z

r-Li

nen

I0.0

68

20.9

458.2

90.1

39

36.5

271.3

0Li

nen

II0.1

21

36.6

080.9

10.3

01

66.6

790.2

5Li

nen

/(C

/PE

T)

0.0

71

26.5

679.5

20.1

49

51.6

981.7

6

Pla

sma

treatm

en

t:A

PD

BD

pla

sma;

po

wer

sup

ply

with

20,0

00

Hz

freq

uen

cy,

50

Wan

dan

ou

tpu

to

f5

kV/2

0m

A,

for

30

seco

nd

s.Tre

atm

en

tco

nd

itio

n:

meta

lsalt

0.1

,0.2

M/L

,n

on

-io

nic

wett

ing

ag

en

t2

g/L

;w

et

pic

ku

p80%

(ow

f);

dry

ing

at

80/1

0m

inu

tes,

follo

wed

by

aft

er-

wash

ing

tore

mo

veexc

ess

an

du

ntr

eate

dm

eta

lsa

lt.(C

C)*

:ca

rbo

xyl

con

ten

t(m

eq

.CO

OH

/100

gfa

bric

s);

RP

C%

:re

du

ctio

np

erc

en

tin

bact

eria

cou

nt,

incu

batio

ntim

e:

24

ho

urs

.


Tab

le9

.E

ffe

ct

of

pla

sma

follo

we

db

ysu

bse

qu

en

ttr

eatm

en

tw

ithn

an

op

art

icle

so

nth

ean

timic

rob

ial

ac

tivity

of

line

n-c

on

tain

ing

fab

ric

s.

Na

no

-TiO

2N

an

o-Z

rON

an

o-A

g

RP

C%

RP

C%

RP

C%

Tre

atm

en

tse

qu

en

ceT

ype

of

sub

stra

teM

eta

lco

nte

nt

(%)

Gþ

veS

.au

reu

sG�

veE

.c

oli

Me

tal

con

ten

t(%

)Gþ

veS

.au

reu

sG�

veE

.c

oli

Me

tal

con

ten

t(%

)Gþ

veS

.au

reu

sG�

veE

.c

oli

Un

treate

dLi

nen

I–

0.0

0.0

–0.0

0.0

–0.0

0.0

Lin

en

II–

0.0

0.0

–0.0

0.0

–0.0

0.0

Lin

en

/(C

/PE

T)

–0.0

0.0

–0.0

0.0

–0.0

0.0

N2–p

lasm

atr

eatm

en

tLi

nen

I–

9.2

15.6

–9.2

15.6

–9.2

15.6

Lin

en

II–

13.3

23.9

–13.3

23.9

–13.3

23.9

Lin

en

/(C

/PE

T)

–11.4

20.5

–11.4

20.5

–11.4

20.5

O2–p

lasm

atr

eatm

en

tLi

nen

I–

4.0

10.0

–4.0

10.0

–4.0

10.0

Lin

en

II–

9.5

19.0

–9.5

19.0

–9.5

19.0

Lin

en

/(C

/PE

T)

–6.0

13.0

–6.0

13.0

–6.0

13.0

Nan

o–p

art

icle

sn

op

lasm

atr

eatm

en

tLi

nen

I0.6

23

21.5

140.8

00.3

13

31.2

756.9

90.0

08

60.7

762.5

1

Lin

en

II0.6

99

44.6

658.4

40.3

51

50.1

165.9

70.0

14

63.5

571.4

5Li

nen

/(C

/PE

T)

0.4

65

54.4

470.7

00.2

56

61.1

181.9

50.0

22

65.2

589.3

5N

2–p

lam

san

an

o-p

art

icle

sLi

nen

I0.6

46

54.0

266.5

70.3

11

61.3

676.9

60.0

13

64.3

680.3

7Li

nen

II0.7

26

69.5

376.9

40.3

59

70.8

880.9

80.0

19

73.7

786.7

3Li

nen

/(C

/PE

T)

0.7

62

83.0

489.4

40.4

83

79.6

391.5

70.0

29

86.8

597.3

1O

2–p

lam

san

an

o-p

art

icle

sLi

nen

I0.6

35

45.1

663.5

50.3

44

51.1

772.2

40.0

31

61.8

575.5

5Li

nen

II0.7

10

63.8

872.3

10.4

46

70.4

481.1

20.0

51

73.2

084.4

4Li

nen

/(C

/PE

T)

0.6

59

70.3

985.6

20.3

51

75.1

188.3

80.0

47

82.4

093.8

8

Pla

sma

treatm

en

t:A

PD

BD

pla

sma;

po

wer

sup

ply

with

20,0

00

Hz

freq

uen

cy,

50

Wan

dan

ou

tpu

to

f5

kV/2

0m

A,

for

30

seco

nd

s.Tre

atm

en

tco

nd

itio

n:

nan

op

art

icle

s:2g

/L,

wet

pic

ku

p80%

(ow

f);

dry

ing

at

80�C

/10

min

ute

s,cu

ring

at

150�C

/3m

inu

tes.

RP

C%

:re

du

ctio

np

erc

en

tin

bact

eria

cou

nt,

incu

batio

ntim

e:

24

ho

urs

.


the type of nanoparticles, i.e., nano-Ag>nano-ZrO>nano-TiO2>none,the sequence of treatment, i.e., N2–plasma! loaded with nanomaterial>O2–plasma! loaded with nano material> treatment withnano material> treatment with plasma � untreated, as well as the typeof substrate, i.e., linen/(C/PET)> linen II> linen I, keeping other para-meters constant, (iii) G �ve bacteria (E. coli) was more heavily inactivatedand damaged than G þve bacteria (S. aureus) regardless of the type of nano-material, which reflects the difference between two types in the structure ofthe cell wall as well as sensitivity to plasma-pre-treatment alone or inconjunction with post-treatment with nano materials [39], (iv) all samplestreated with N2 or O2 plasma had a substantial improvement in theirwettability (<1 second) along with a new active site (–NH2 or –COOHgroups respectively) that could bind the metallic nanoparticles to the treatedfabric surface, (v) the outstanding antibacterial properties of nano-Ag-loaded substrates most probably due to the negative effect of thesenanoparticles on the cellular metabolism along with inhibiting the cellgrowth [40–42], (vi) the remarkable improvement in the antibacterialefficiency of TiO2-loaded fabrics suggests that TiO2 nanoparticles may notonly act as a photo catalytic bacterial agent but also as a protective shieldagainst the formation of biofilms [43], (vii) the strong antibacterial activityof ZrO-loaded substrate can be discussed in term of its photocatalyticactivity via the generation of reactive oxygen species, e.g., OH�, HO�2, H2O2

etc in presence of UV and water, from the surface of ZrO nanoparticles,having the ability to inhibit the bacterial growth along with disinfection ofbacterial cells, i.e., photocatalytic inactivation [44,45], and (viii) thevariation in the antibacterial properties upon using the aforementionednano-particles could be discussed in terms of differences among them: in theparticle size, metal content on the loaded substrate, extent of fixation,location, extent of distribution as well as surface area of nanoparticles ontothe fabric surface, bactericidal action along with their bactericideperformance [42,46].

On the other hand, the fiber surface of the nanoparticles-loadedfabrics were observed by SEM micrographs (Figures 5–7). SEM imagesshow that the thin layer produced by N2 plasma pre-treatmentwas smoother and more homogenous than in case of O2 plasma pre-treatment or without plasma pre-treatment regardless of the usednanoparticles.

Durability to Wash

The data in Table 10 signify that: (i) increasing the washing cycles up to 15consecutive cycles, according to the AATCC method 124-1996, has


practically no or slight effect, as in case of UV-protection category, and/ora negative impact on antibacterial functions, and (ii) the extent of retainingthe gained functional properties is determined by the degree of modifi-cation of the treated fabric surfaces, its hydrophilic functional groups, theextent of interaction with and fixation of the active ingredient along withlocation and extent of distribution of these loaded ingredients onto thefabric surface.

CONCLUSIONS

In order to impart functional properties on linen-based textiles, pre-treatment with oxygen or nitrogen plasma, for surface modification alongwith introducing –COOH or –NH2 groups to the fiber surface, followed by

(b)

(c) (d)

(a)

FIGURE 5. SEM of treated linen I with TiO2 sol gel using different sequence oftreatment: (a) Untreated substrate, (b) TiO2 sol gel without plasma pretreatment,(c) N2 plasma pretreatment followed by TiO2 sol gel, (d) O2 plasma pretreatmentfollowed by TiO2 sol gel.


subsequent treatments with proper dyestuffs, metal salts, certain metal ormetal oxides in nano form, quaternary ammonium salt or proper antibioticswere studied. Results obtained led to the following conclusions: Pre-treatment with nitrogen-plasma followed by subsequent reactive dyeingresults in: enhancement in surface hydrophilicity, creation of –NH2 groups,improvement in picking up the used dye as well as subsequent fixation alongwith an outstanding UV-protection properties of the obtained dyeings.Oxygen plasma followed by subsequent basic dyeing of the treated sub-strates results in obtaining basic dyeings with higher depth of shades alongwith remarkable UPF values. The higher the dye concentration, the betterare the depth of shade and the UV-protection capacity. Post-treatmentof plasma-treated substrates, with metal salts results in a significantimprovement in UPF values of treated samples, and the extent of

(c) (d)

(a) (b)

FIGURE 6. SEM of treated linen II with Ag nano particles using different sequence oftreatment: (a) Untreated substrate, (b) Ag nano particles without plasmapretreatment, (c) N2 plasma pretreatment followed by Ag nano particles, (d) O2

plasma pretreatment followed by Ag nano particles.


improvement is determined by the type of substrate, i.e., linen II> linen/(C/PET) � linen I, and the kind of metal salt, i.e., Cu-acetate>Zr-oxychloride>Ca-acetate >Zn-acetate>None. Subsequent treatment ofoxygen-or nitrogen plasma pre-treated substrates, with nano-TiO2 leads tohigher extent of UV protection. Post-treatment, of plasma-treated substrates,with the nominated two antibiotics results in a significant improvement intheir antibacterial properties, and the extent of enhancement is determined bytreatment sequence, type and concentration of antibiotic as well as the type ofsubstrate. O2 plasma followed by subsequent choline chloride finish enhancesthe antibacterial functions of the treated substrates against the used G þveand G –ve strains. O2 plasma followed by basic dyeing or N2 plasmatreatment followed by reactive dyeings is accompanied by a significantincrease in the antibacterial ability of the obtained dyeing reflecting the

(a) (b)

(c) (d)

FIGURE 7. SEM of treated linen II with ZrO nanoparticles using different sequenceof treatment: (a) Untreated substrate, (b) ZrO nano particles without plasmapretreatment, (c) N2 plasma pretreatment followed by ZrO nano particles, (d) O2

plasma pretreatment followed by ZrO nanoparticles.


Tab

le1

0.

Eff

ec

to

fw

ash

ing

on

the

reta

ine

dfu

nc

tion

al

pro

pe

rtie

so

fse

lec

ted

line

nII

fab

ric

sam

ple

s.

An

timic

rob

ial

act

ivity

UV

-pro

tect

ion

UP

F(C

ate

go

ry)

(RP

C%

)o

r(Z

Im

m)

Gþ

veG

–ve

Tre

atm

en

tco

nd

itio

ns

0C

ycle

15

Cyc

le0

Cyc

le1

5C

ycle

0C

ycle

15

Cyc

le

N2–p

lasm

a!

React

ive

dye

ing

(2%

ow

f)64.7

5(e

xcelle

nt)

55.0

2(e

xcelle

nt)

44.4

%*

35%

85.0

3%

78.0

%O

2–p

lasm

a!

Basi

cd

yein

g(2

%o

wf)

89.7

0(e

xcelle

nt)

78.2

3(e

xcelle

nt)

11**

7.8

9.1

6.2

O2–p

lasm

a!

Cu

-ace

tate

(0.0

1m

ole

/L)

62.0

7(e

xcelle

nt)

56.3

0(e

xcelle

nt)

60.0

%*

51.0

%84.8

%75.2

%Z

r-o

xych

lorid

e(0

.01

mo

le/L

)43.7

8(e

xcelle

nt)

38.6

(very

go

od

)66.7

%*

60.0

%90.3

%81.9

%Z

n-a

ceta

te(0

.01

mo

le/L

)38.9

9(v

ery

go

od

)30.1

2(v

ery

go

od

)76.4

%*

69.3

%94.6

%83.8

%O

2–p

lasm

a!

Nan

o-T

iO2

47.4

6(e

xcelle

nt)

41.2

0(e

xcelle

nt)

63.9

%*

59.0

%72.3

%69.9

%N

2–p

lasm

a!

Nan

o-T

iO2

54.6

1(e

xcelle

nt)

48.0

3(e

xcelle

nt)

69.5

%*

62.3

%76.9

%68.6

%O

2–p

lasm

a!

Nan

o-Z

rO–

–70.4

%*

65.8

%81.1

%76.2

%N

2–p

lasm

a!

Nan

o-Z

rO–

–70.9

%*

66.2

%81.0

%75.6

%O

2–p

lasm

a!

Nan

o-A

g–

–73.2

%*

68.1

%84.4

%78.2

%N

2–p

lasm

a!

Nan

o-A

g–

–73.8

%*

67.6

%86.7

%80.4

%O

2–p

lasm

a!

Do

xy(2

%o

wf)

––

19**

16.2

15

11.5

N2–p

lasm

a!

Cip

ro(2

%o

wf)

––

21**

18.4

19

16.1

*RP

C%

:%

red

uct

ion

perc

en

tin

bact

eria

cou

nt,

**Z

I:zo

ne

of

inh

ibiti

on

.


positive impact of quaternary ammonium group (in the used basic dye), orCu–component (in the used reactive dye). O2–plasma followed by subsequenttreatment with selected metal salts is accompanied by loading the metalions onto the treated fabric surfaces, which could in turn upgrade theirantibacterial ability significantly. Loading of nano size metal or metaloxides onto O2– or N2–plasma-treated substrates brings about a remark-able improvement in their bacterial inactivation efficiency, andthe enhancement in their efficiency is governed by, type of plasma gas, typeof substrate, mode of action of the loaded nano metal or metal oxides, aswell as sensitivity of the tested G þve and G –ve bacteria to the treatedsubstrates. These smart options for imparting UV-protection and/orantibacterial functions on the linen-containing fabrics are very simple andapplicable.

REFERENCES

1. Fakin, D., Golob, V., Kleinschek, K.S. and Marechal, A.M. (2006). SorptionProperties of Flax Fibers Depending on Pretreatment Processes and theirEnvironmental Impact, Textile Research Journal, 76: 448–454.

2. Fakin, D., Golob, V., Kreza, T. and Marechal, A.M. (2005). Ultrasound in thePretreatment Processing of Flax Fibers, AATCC Review, September: 61–65.

3. Ibrahim, N.A., El-Hossamy, M., Hashem, M.M., Refai, R. and Eid, B.M.(2008). Novel Pretreatment Processes to Promote Linen-containing FabricProperties, Carbohydrate Polymer, 74(4): 880–891.

4. Ibrahim, N.A., Allam, E.A., El-Hossamy, M.B. and El-Zairy, W.M. (2007).UV-protective Finishing of Cellulose/Wool Blended Fabrics, Polymer-plasticTechnology & Engineering, 46(9): 905–911.

5. Ibrahim, N.A., Refai, R., Youssef, M.A. and Ahmed, A.F. (2005). ProperFinishing Treatment for Sun Protective Cotton-containing Fabrics, Journal ofApplied Polymer Science, 97: 1024–1032.

6. Ibrahim, N.A., Refai, R., Youssef, M.A. and Ahmed, A.F. (2005). NewApproach For Improving UV-protecting Properties of Woven Cotton Fabrics,Polymer-plastic Technology & Engineering, 44: 919–930.

7. Gouda, M. and Ibrahim, N.A. (2008). New Approach for Improving AntibacterialFunction to Cotton Fabric, Journal of Industrial Textile, 37(4): 327–339.

8. Ibrahim, N.A., Aly, A.A. and Gouda, M. (2008). Enhancing the AntibacterialProperties of Cotton Fabrics, Journal of Industrial Textile, 37(1): 203–212.

9. Ibrahim, N.A., Gouda, M., El-Shafei, A.M. and Abdel-Fatah, O.M. (2007).Antimicrobial Activity of Cotton Fabrics Containing Immobilized Enzymes,Journal of Applied Polymer Science, 104(5): 1754–1761.

10. Ibrahim, N.A., Abo-Shosha, M.H., El-Shafei, A.M., Abdel Fatah, O.M.and Gaffar, M.A. (2006). Antibacterial Properties of Ester-crosslinkedCellulose-containing Fabrics Post Treated with Metal Salts, Polymer-plasticTechnology & Engineering, 45(6): 719–727.


11. Daoud, W.A. and Xin, J.H. (2004). Low Temperature Sol Gel ProcessedPhotocatalytic Titania Coating, Journal of Sol-gel Science and Technology, 29:25–29.

12. Raveendran, P., Fu, J. and Wallen, S.L. (2006). A Simple and ‘‘Green’’ Methodfor the Synthesis of Au, Ag, and Au–Ag Alloy Nanoparticles, Green Chemistry,8: 34–38.

13. Choi, H., Bide, M., Phaneuf, M., Quist, W. and LoGerfo, F. (2004). Dyeing ofWool with Antibiotics to Develop Novel Infection Resistance Materials forExtracorporeal End Use, Journal of Applied Polymer Science, 92: 3343–3354.

14. Duff, D.G. and Sinclair, R.G. (1989). Giles’s Laboratory Course in Dyeing,4th edn, p. 73, The Dyers Company Publications, London, UK.

15. Vogel, A.I. (1975). Elementary Practical Inorganic Chemistry, Part 3,Quantitative Inorganic Analysis, 2nd edn, p. 652, Longman, London.

16. Paul, G.C., Reinhardt, R.M. and Reid, J.D. (1953). Preparation of Soluble Yarnsby the Carboxymethylation of Cotton, Textile Research Journal, 23(10): 719–726.

17. Australian-New Zealand Standard AS/NZS 4399-1996: Sun Protective ClothingEvaluation and Classification.

18. Gorensek, M. and Sluga, F. (2004). Modifying the UV-blocking of PolyesterFabric, Textile Research Journal, 74: 469–474.

19. Sun, D. and Stylios, G.K. (2005). Investigating the Plasma Modification ofNatural Fibre Fabrics—the Effect on Fabric Surface and Mechanical Properties,Textile Research Journal, 75: 639–644.

20. Wong, K.K., Tao, X.M., Yuen, C.W.M. and Yueng, K.W. (2000). Effect of Plasmaand Subsequent Enzymatic Treatment of Linen Fabrics, Journal of the Society ofDyers and Colourists, 116: 208–214.

21. Wong,K.K., Tao,X.M., Yuen,G.W.M. andYeung,K.M. (1999). LowTemperaturePlasma Treatment of Linen, Textile Research Journal, 69(11): 846–855.

22. Sun, D. and Stylios, G.K. (2004). The Effect of Low Temperature PlasmaTreatment on the Scouring and Dyeing Processes of Natural Fibers, TextileResearch Journal, 74: 751–756.

23. Sharma, D.K. and Singh, M. (2001). Effect of Dyeing and Finishing Treatmentson Sun Protection of Woven Fabrics—a Study, Colourage Annual, 48: 69–74.

24. Bozzi, A., Yuranova, T., Guasaquille, I., Laub, D. and Kivi, J. (2005). Self-cleaning of Modified Cotton Textiles by TiO2 at Low Temperature UnderDaylight Irradiation, Journal of Photochemistry and Photobiology, A: Chemistry,174: 156–164.

25. Yang, H., Zhu, S. and Pan, N. (2004). Studying the Mechanisms of TitaniumDioxide as Ultraviolet-blocking Additives for Films and Fabrics by an ImprovedScheme, Journal of Applied Polymer Science, 93: 3201–3210.

26. Xu, P, Wang, W. and Chem, S.L. (2005). UV-blocking Treatment of CottonFabrics by Titanium Hydrosol, AATCC Review, 5(6): 28–31.

27. Gao, Y. and Cranston, R. (2008). Recent Advances in Antimicrobial Treatmentsof Textiles, Textile Research Journal, 78(1): 60–72.

28. Kenawy, E., Worley, S.D. and Broughton, R. (2007). The Chemistry andApplications of Antimicrobial Polymers: A State-of-the Art Review,Bio-Macromolecular, 8: 1359–1384.


29. Holme, I. (2002). Antimicrobial Impact Durable Finishes, Inter Dyer, December:9–11.

30. Franklin, J. and Snow, G.A. (eds). (1981). Antiseptic, Antibiotics and the CellMembrane, In: Biochemistry of Antimicrobial Action, pp. 58–78, Chapman Hall,London.

31. Pal, A., Pehkonen, S.O., Yu, L.E. and Ray, M.B. (2007). PhotocatalyticInactivation of Gram-positive and Gram-negative Bacteria UsingFluorescent Light, Journal of Photochemistry & Photobiology, A: Chemistry,186: 335–341.

32. Son, Y.A. and Sun, G. (2003). Durable Antimicrobial Nylon-66 Fabric: IonicInteraction with Quaternary Ammonium Salts, Journal of Applied PolymerScience, 90: 2194–2199.

33. Kim, Y.H. and Sun, G. (2000). Dye Molecules as Bridges of FunctionalModifications of Nylon: Antimicrobial Functions, Textile Research Journal,70: 728–733.

34. Virk, R.K., Ramaswamy, G.N., Bourham, M. and Bures, B.L. (2004). Plasmaand Microbial Treatment of Nonwoven Fabrics of Surgical Gowns, TextileResearch Journal, 74: 1073–1079.

35. Donnel, G.M. and Russel, A.D. (1999). Antiseptics and Disinfections: Activity,Action, and Resistance, Clinical Microbiology Reviews, 12: 147–179.

36. Ma, M. and Sun, G. (2005). Antimicrobial Cationic Dyes, Part 3: SimultaneousDyeing and Antimicrobial Finishing of Acrylic Fabrics, Dyes and Pigments,66: 33–41.

37. Yates, H.M., Brook, L.A., Ditta, I.B., Evans, P., Foster, H.A., Sheel, D.W. andSteele, A. (2008). Photo-induced Self-cleaning and Biocidal Behaviour of Titaniaand Copper Oxide Multilayers, Journal of Photochemistry and Photobiology, A:Chemistry, 197: 197–205.

38. Yen, M.S., Chen, J.C., Hong, P.D. and Chen, C.C. (2006). Pore Structure andAnti-bacterial Properties of Cotton Fabrics Treated with DMDHEU-AA byPlasma Process, Textile Research Journal, 76: 208–215.

39. Lee, K., Paek, K., Yu, W. and Lee, Y. (2006). Sterilization of Bacteria, Yeastand Bacterial Endospores by Atmospheric-pressure Cold Plasma Using Heliumand Oxygen, Journal of Microbiology, 44: 269–275.

40. Perciral, S.L., Bowler, P.G. and Russell, D. (2007). Bacterial Resistance to Silverin Wound Core, Journal of Hospital Infection, 60: 1–7.

41. Klueh, U.K., Wagner, V., Kelly, S., Johnson, A. and Bryers, J.D. (2000).Efficiency of Silver-coated Fabric to Prevent Bacterial Colonization andSubsequent Device-based Biofilm Formation, Journal of Biomedical MaterialsResearch. Part B, Applied Biomaterials, 53: 621–631.

42. Yuranova, T., Rincon, A.G., Pulgarin, C., Laub, D., Xantopoulos, N., Mathien,H.J. and Kiwi, J. (2006). Performance and Characterization of Ag-cotton andAg/TiO2 Loaded Textiles During the Abatement of E. Coli, Journal ofPhotochemistry & Photobiology, A: Chemistry, 181: 363–369.

43. Daoud, W.A., Xin, J.H. and Zhang, Y.H. (2005). Surface Functionalization ofCellulose Fibers with TiO2-nanoparticles and their Combined BacterialActivities, Surface Science, 599: 69–75.


44. Qian, L. and Hinestroza, J.P. (2004). Application of Nanotechnology for HighPerformanceTextiles, Journal ofTextile&Apparel Technology&Management, 4: 1–7.

45. Yamamoto, O. (2001). Influence of Particle Size on the Antibacterial Activity ofZinc Oxide, International Journal Inorganic Materials, 3: 643–646.

46. Yadav, A., Prasad, V., Kathe, A.A., Ruj, S., Yadav, D., Sundaramoorthy, C.and Vigneshwaran, N. (2006). Functional Finishes in Cotton fabric Using ZincOxide Nanoparticles, Bulletin of Material Sciences, 29: 641–645.

BIOGRAPHY

Nabil Abd El Basset Ibrahim, born on April 11,1949 in El-Mansoura, Egypt, obtained his PhD inApplied Organic Chemistry (Textile Finishing) in1979. He is a Professor of Textile Chemistry andTechnology, Textile Research Division NRC(from 1990 to date) and was the Head of theTextile Research Division NRC (August 13, 2001to August 21, 2008). He has published over 180scientific papers in well-known internationaljournals dealing with textile chemistry and chemi-cal technology, pollution prevention and cleanerproduction in textile industry, applications of

biotechnology in textile wet processing, functional finishes of cellulose-basedtextiles for specific end uses, and application of nanotechnology in functionalfinishing of textiles. He has implemented more than 45 industrial projects andsupervised over 50 MSc and PhD theses. He has been an industrial andenvironmental editor, and eco-textile consultant for several projects sponsoredby foreign (EP3, SEAM, DANIDA, CIDA, FINIDA) and local organizations.He was awarded the NRC Prize in Chemistry, for Scientific Contribution andDistinction in Chemistry and its Applications (1996), ProfessorDrM.K. Tolba’sEnvironmental Prize (1998) for ‘The Best Applied Research for Protection ofAir, Water and/or Soil’, and State Prize of Distinction for AdvancedTechnological Science (2004). He was the Chairman of the 1st (March, 2004),2nd (April, 2005), 3rd (April, 2006) and 4th (April, 2007) InternationalConferences of the Textile Research Division (Textile Processing: State of Artand Future Developments), at NRC, Cairo Egypt. He was nominated bythe International Biographic Center (IBC) as a listee of the IBC LeadingScientific of the World 2008. He is one of the leading scientists and engineers ofOIC (Organization of Islamic Conference) Member States (COMSTECH’sStudy 2008).


Smart Options for Functional Finishing of Linen-containing Fabrics

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