CHAPTER V

PHYSICAL CHEMISTRY OF DETERGENCY

 CONTENTS

Detergency Process

5.1.1 Chemistry of Surfactants

5.1.2 Role of Surfactants in Detergency

5.1.3 Soil Remova1

Detergency of Oily Soil

5.2.1 Kinetic Picture of Oily Soil Removal

5.2.2 Interrelation of Detergency Parameters

5.2.3 Effect of Builders on Surfactant

Efficacy

5.2.4 Effect of Hater-hardness on Surfactant

Efficacy

Detergency of Particulate Soil

5.3.1 Detailed Picture of Surfactant

Adsorptions

5.3.2 Mechanism of Particulate Soil Removal

5.3.3 Effect of Particle Size on Soil Removal

Aqueous Soiling

References
 126

5*1 Detergency Process

Substrate, soil and surfactant form a detergency

system. The three components in the system interact in

aqueous medium,* Since surfactants can be adsorbed at

interfaces, fibre-sozl interface is displaced by the

formation of fibre-surfactant and soil-surfactant

interfaces.

2
McBam described the detergency process by the

equation,

Fabric-Dirt + Surfactant Fabric-Surfactant

+ Dirt-Surfactant Eq.5.1

This eguilibrium can be broken down into three

processes, namely,

Dirt + Surfactant Dirt-Surfactant

Fabric + Surfactant Fabric-Surfactant

Fabric-Dirt Fabric + Dirt

Addition of these three equilibria leads to the

overall detergency process mentioned above.

5.1.1 Chemistry of Surfactants

A surface active agent or surfactant may be

defined as a substance, which even in low concentration,

markedly reduces surface tension of the solvent.

Chemical analysis reveals that a surfactant molecule is

 127

made up of a hydrophilic and a hydrophobic component.

Such a combination of a -/rater-soluble segment with an

oil-soluble segment in a single system makes the compound

surface active.

The nolar structure of a surfactant molecule is

represented by a symbol having a long tail for the hydro-

phobic component and a head f^r the hydrophilic group.

The surfactants are classified according to the electric

charge carried by tboir ions in aqueous solutions. Thus*

they are called anionic, cationic, non-ionic and

amphoteric.

The surfactants are described by several physico­

chemical parameters. These are turbidity point, water

count, bydrophile-lipoohile balance and critical micelle

concentration. The turbidity point is understood to be

the temperature at which the solution of a surfactant is

at its cloudiest. The water count is determined by

establishing how many milliliters of water must be added

to a solution of 1 gram of the substance in 30 ml dioxane

benzene (96s4) in order to produce lasting cloudiness.

The water or oil-solubility of a surfactant,

especially ethylene oxide adducts, depends on whether

the lipophilic segment or the hydrophilic chain predomi­

nates in the molecule. When the former segment predomi­

nates, the compound is oil-soluble. When the latter one

 128

is Greater, it is water-soluble. When both the segments

balance out, the compound is soluble in both oil and

water. Thus, the solubility of the surfactant is

represented by a non-dimensional number between 0 and 20.

This designation is called the hydro oh ile-1 ipo~>hi le

balance (H.L.3.). The specific function of a surfactant

can ba determined from its K.L.3. value, as given in

Table 5.1,

TTBLE 5.1

USE OF 3URFACT?iNTS FROM THE H.L.3. VALUE

Range of H.L.B. Value Application

,3.5-5 K/0 emulsifier

7-9 Wetting agent

8-18 0/W emulsifier

13 - 15 Detergent

15 - 18 Solubilizing agent

. 3
Me B a m suggested that surfactant molecules m

agueous solution undergo demonstrable structural changes

which indicated agglomeration of molecules to form

aoigreoatss of regular dimensions. These were called

"micelles” . Critical micelle concentration (cmc) is

defined as tho point of intersection of lines extrapolat­

ing the measured properties of the solution from below and

above the region,in which a rapid change of slope is

 129

observed. In the solution,.an equilibrium is established

between ions and micelles. Research workers have

sugcested various shapes of the micelles, for example,

4 . 5 . . 6 . 7
lamellar , spherical , cylindrical , disc-like , etc.

Micellar size is determined by the micellar molecular

weight which depends upon the size of the hydrocarbon

chain. Micelles of anionic surfactants possess molecular

weight in the range of 10,000-30,000. The measurement of

micelle formation, micellar structure, and the practical

importance of critical micelle concentration values have

8
been discussed by Harris.

5.1.2 Role of Surfactants in Detergency

Two important characteristics of surfactants which

enhance their detergent action, are (a) tendency to adsorb

at interfaces and (b) ability to form micelles. These

capabilities combine in an effective detergency to provide

for wetting, displacement of soils and suspension of the

soil removed, /accumulation of surfactants at fibre-soil

interface increases surface excess and consequently

decreases the interfacial tension. This relation is

9
described by the Gibbs adsorption equation ,

C dY* 1 dyr _
r RT * dc = RT dine * aq' 5,2

where G is the concentration of surfactant solution,

V the interfacial tension and rr the surface pressure of

the film of adsorbed surfactant molecules.

 130

The Gibbs equation describes physical adsorption

which involves van der WasIs forces. The process is

reversible and an equlibriura exists between the surfactant

molecules adsorbed at interferes and those dissolved in the

bulk solution.

'5.1.3 Soil Removal

Soil removal process is described, by the term

'’detergency”. Detergency of a surfactant means its

special property of enhaneina the cleaning power of a

liquid. The process is accomplished by a combination of

effects involving adsorption at interfaces, alteration of

interfacial tensions and surface charqes and emulsifica­

tion.

There are two categories of soil-liquid (oily) and

solid (particulate) soil. Their physicochemical

characteristics are different. The soil removal mechanisms

for oily soils and particulate soils are different.

Adhesion of both types of soils is mainly by van der Waals

forces.^ Adhesion by electrical forces is usually much

weaker, especially after the soil and substrate have been

wetted by the aqueous solution, and is more significant

for particulate soils than for o i ^ soils.

5.2 Detergency of Oil-^ Soil

Removal of oily soil is accomplished mainly by

11 — 13
”rolling-up” mechanism. During this process, the
 131

contact angle of oil on fibre increases from 0° (film) to

180 (clroo) which is removed by the hydraulic currents.

The step-wise nrocess is shown schematically in Fig.5.1.A.

In the deterc’an-' system, there are three phases in

contact with one-anothers fibre, oily soil and aqueous

surfactant solution. The situation is shown schematically

in Fig. 5.1.3. The equilibrium contact-angle 9 is given

by Young's expression

T f a - ~VpF
Cos 9 E g . 5.3.
Ya o

The presence of surfactant that can absorb at the

fibre-agueous interface decreases the interfacial tension

VfA which increases the value of 9 and facilities the

removal of liquid soil,

Extensive microscopic observations documented by

photomicrographs * have confirmed preferential wetting

and rolling-up as the major mechanism for the removal of

. . 11 .
oily soils. Adam found that the size of oil globules

was between 20 and 120 microns in diameter.

Schwartz‘S showed that if the contact angle is 180°

the oily soil will be completely displaced from the fibre.

If the contact angle is more than 90° but less than 180°,

the soil will' not be displaced spontaneously but can be

removed by hydraulic forces. When the contact angle is

less than 90°, at least a small portion of the oily soil

 \

F1G.5.1.A: ROLLING UP MECHANISM (CONTACT

. ANGLE 0 INCREASES 0 °-H 8 0 °)

FIG.5.1.8:FORCES IN THE FIBRE-OIL-AQUEOUS

SOLUTION SYSTEM
 132

will remain attached to the fibre, even in the presence

of hydraulic forces.

It is to be noted that this explanation may be the

reason of higher soil accumulation of crosslinked cotton

fabrics than the untreated one as observed earlier in

Sections 4.6 and 4.7. The crosslinked cotton fabrics

being less hydrophilic discourses the diffusion of

agueous surfactant solution. As a result the contact

ancle of oil on fibre may not increase more than 90°, and

a significant portion of the oily soil is left on the

fabrics at each soiling-washing cycle. Thus, the cross­

linked fabrics accumulate the soil. On the other hand,

untreated cotton fabric being more hydrophilic facilitates

diffusion which makes the contact angle more than 180° and

removes soil almost completely. Therefore, the untreated

cotton fabric does not build-up oily soil as is evident

from the horizontal position of the line (Fig. 4.8).

The small amounts of oily soils are probably removed

by solubilization. In this mechanism, spherical micelles

of surfactant with their hydrophobic tails towards inside

carry the oily soil within them away from the fibre

surface. The extent of solubilization of oily soil

depends unon chemical structure of the surfactant, its

. ■ . 17
concentration and temperature of washing.
 133

5.2.1 Kinetic Picture of Oily Soil Removal

l£
Vaughn et al recognized long back that-oil

removal is a rate process and it follows first-order

. . 19
kinetics. Loeb et al reported that the amount of mixed

soil removed increases linearly with the log of washing

. , 20
time. Kissa reported that the rate of oily soil

removal defends upon (a) the rate of spontaneous soil

release and (b) the rate of soil release by mechanical

work. This means that the former rate depends upon the

surface energy of the substrate whereas the latter one

depends upon the energy applied externally to the wash

system.

In case of the spontaneous soil release, the

process occurs in three successive steps i Firstly, an

induction period, during which water diffuses into the

substrate without,soil removal. Secondly, a rapid soil

release period, during which diffusion of water and

removal of soil are fast. Thirdly, a final period of

20 21
nearly constant soil removal. *

Spontaneous release of lubricating oil from cotton

and crosslinked cottpn fabrics under mild washing

conditions is shown in Fig. 5.2. Cotton fabric being

more hydrophilic facilitates faster diffusion of water

and consequently faster rate of soil removal as is evident

from the slope of the second period. On the other hand,

 o
o
_ jc EX.
o
cr>
O
co
SLINKCD

o
cs.
(1^0% ) N 0 ilN 3 1 3 d UOS
Q- —^

O
<x>
UNTREATEO

J__ 1 i..1—L
_

tr>
oo
0.5 1.0 10
WASHING TIME (T, M in u te )

FIG. 5.2; SPONTANEOUS OILY SOIL RELEASE FROM UNTREATE

a
AND CROSSLINKED COTTON FABRICS
 134

x the crosslinked fabric being less hydrophilic allows

slower diffusion of water and the slower rate of soil

removal. The untreated cotton fabric'requires less time

>

to reach the final plateau. The crosslinked one needs

longer time for the same, The figure also illustrates

that the crosslinked cotton fabric retains oily soil to' a

higher degree than the untreated one.

«*

5.2.2 Interrelation of Detergency Parameters

There are six general variables affecting

detergencys

a. Surfactant type and. concentration

b. Time

c. Agitation

d. Temperature,

e. Water hardness

f. Soil redeposition

Comparative evaluation of soil release of various

fabrics requires a standard detergency test. A standard

test should permit optimum soil release. The surfactant

concentration determines the lowering of interfacial

tension, the agitation provides mechanical energy and

the temperature provides thermal energy to remove the

soil. However, the time of washing allows a certain

extent of interaction of the three factors.

Teraotometer, the washing machine used in the

 135

present studies, allows variation of all the four

variables. Its chain driven mechanism ensures uniform

speed. The temperature of the washing bath can be

controlled unto an accuracy of + 0.5°C. Since the in­

built timer is accurate ucto minutes, a separate stop­

watch can be used to ensure accuracy upto seconds.

The mechanical work performed by the washing

machine can be controlled in the range of 0-120 rpm.

absolute measurement of the work involved is not possible,

however, not necessary to evaluate the effect on a

comparative basis. In order to set-up a scale of work for

the Tergotometer, it was assumed that the work done by the

machine is directly proportional to the square of the rpm

within a limited ranae. Aith this concept, an arbitrary

force scale was established ranging from 1-15.

The effects exerted by each individual variables

were studied by varying one particular parameter and

keeping the others constant preferably at low levels.

The effect of surfactant concentration on soil

removal is reported-in Fig. 5.3. A log-log plot of the

concentration against soil removal is linear upto the

critical micelle concentration of the surfactant. At this

concentration, micelles are formed and hence the

22 23
surfactant shows optimum efficiency of soil removal. *

Similarly, the effect of time of washing, agitation

 136

and temperature are shown in Figs. 5.4, 5.5 and 5.5,

respectively.

In all the four figures mentioned above, soil

removal trends of untreated and crosslinked cotton

fabrics are the same. However, less soil is removed from

the cposslinked fabric a3 compared to the untreated

fabric. It is also evident that the straight-line

relationships are obeyed upto certain extent of the

factor concerned. For the linear portion of the straight-

line the slope can be measured; • Table 5.2 lists the

values of slope for each individual straight-line. Hie

data suggest that the slope value is constant -(0.20 + 0.01)

for the four variables.

. ?4
Bacon and Smith' reported that keeping the degree

of soil removal and temperature constant, any two of the

three factors (concentration, force and time) were

inversely proportional to each other. In other words,

under constant conditions, the product of any two of the

three factors was constant over the linear region of the

straight-line.

If s represents per cent soil removals c, concen­

tration of surfactant? f, relative mechanical forces

t, time of washing and h, temperature of washings then

 UNTREATED
SOIL REMOVED (°/

0 i____________ i.......... I 1 1 1 i : j I___

0 I 1-0 50
SURFACTANT CONCENTRATION , m o le s/litre x 10

- |G. 5-3: EFFECT OF SURFACTANT CONCENTRATION

_

ON SOIL REMOVAL
/
SOIL REMOVED (% o w f)

FlG .b t F F E C ’ OF TIME ON SOIL REMOVAL

 ( %owf )
S0(L r em o v ed

REMOVAL
SOIL REMOVED (% o w f)

TEMPERATURE (h,°C )
FIG.5-6--EFFECT OF TEMPERATURE ON SOIL REMOVAL
 137

log s a log k^ + n^ lag c

. . nl
. . S > ss k^c

C.2
klc

Similarly,

k2f0*2 ,

k 3t0,2s

0 .2
and s *Ah

Therefore, at a given degree of soil removal, a

weneralized formula can be written as

s = k (cfth)^*2

. s * k (cfth)n , Sq. 5.4.

Here„ k and n are constants. They depend upon the

physicochemical nature of the three components substrates,

soil and surfactant. The constant k incorporates the

individual constants.

5.2.3 Effect of Builders on Surfactant Sfficacy

The nonsurfactann additives present in a detergent

formulation are called 'builders”. Some of the builders

used are listed in Table 5.3

A typical inorganic builder, sodium tripoly-

phosphate (STPP) was evaluated for its soil removing

efficacy along with low concentration of surfactant.

 138

table 5.2

SLOPE VALUES FROM FIGS. 5,3-5.6

Variable Slope
Untreated fabric Crosslinked
fabric

Concentration 0.20 0.20

Time 0.20 0.21
Agitation 0.21 0.19
Temperature 0.19 0.21

TABLE 5.3

CLASSIFICATION OF BUILDERS USED IN FORMULATED DETERGENTS

Alkali Salts

- Carbonates
- Silicates
- Phosphates
- Borates

Alkali Hydroxides

Inorganic Salts
Sulphates

Hydrophilic Polymers
Carboxymethyl Cellulose
Polyvinyl alcohol
- Polyvinyl oyrrolidone

Metal-ion Sequestering Agents

- Ethylenediamine tetraacetate
Ni t r i lot ri acet a te
 139

Fig. 5.7 shows soil removal with the increasing concentra­

tion of STPP. It is evident that the builder improves

determent action of the surfactant.

Builders perform the following functions!

(a) They lower the cmc of the surfactant thereby

makinc it more effective at lower concentration.

(b) They convert fatty-acid soils into corresponding

26
soaps facilitating removal of other soils

present.

(c) They precipitate polyvalent cations in the

. 27
washing bath.'

(d) They disperse particulate soils by increasing

their negative charge,

28
Scott reported that the performance of a builder

deoends upon the pH of the washing bath, the valence of

the added cation, and its degree of ionization.

Some builders are used for special purposes. For

example, sodium silicates are used to prevent corrosion

of aluminium parts in washing machine. h detailed study

. . 29
on the builder action is presented by Niven.

5*2.4 affect of Water-hardness on Surfactant Efficacy

Laboratory studies of soil removal involves use

of distilled water, which is nontechnically termed as

FIG. 5.7: EFFECT OF SODIUM TRIPOLYPHOSPHATE
ON SOIL REMOVAL

I ___ l ___ 1____ J____ 1____ l____ 1_:__ 1____

0 • 100 200 . 300 400
WATER-HARDNESS (p p m M g + ) >

FIG.5-8 • EFFECT OF WATER-HARDNESS ON SOIL

REMOVAL
 140

soft water. However, the city water containing poly­

valent cations, mainly Ca++ and mg+ + , is called hard

water. The local city water contains hardness of two

ranaes, namely, 95-110 and 250-330 pom of Mg++.

The effect of water hardness on the efficiency of

surfactant to soil removal is shown in Fig. 5.8. In hard

water, the surfactant efficiency is reduced and the soil-

removal is hindered. Soil removal becomes difficult in

water'possessing hardness more than 150 ppm of Mg++.

During washing, adsorption of the cations onto the

soil and substrates takes place. This results into a

decrease in their negative electric potentials, which

facilitates soil redeposition and hinders further soil

, 30
removal.

Polyvalent cations can act as linkages between

(a) fabric and soil, thus promoting soil redeposition,

and (b) soil and hydrophilic portion of ionic surfactant,

thus increasing interfacial tensions at fibre-solution

and soil-solution interfaces and resisting wetting and

. 31
rolling-up of soil. adsorption of these ions on

dispersed particulate soil can reduce its electrical

potentials and cause them to recleposit onto the fibres.

anions present in -the bath may precipitate at

high concentrations of polyvalent cations. These

precipitates can be considered one kind of "soil”

 141

32 33
producing deleterious effects. ' -
1

5*3 Detergency of Particulate Soil

cfemovsl of particulate soil takes place in two

stepst (a) Totting of fibre-soil interface and

(b) adsorption of surfactant at fibre-soil interface.

The wetting reduces adhesion of solid particle to the

fibres. The presence of water forms electrical double

layers at the fibre-solution and particle-solution

interfaces. Since these double layers possess similar

electric charges repulsion takes place between the soil

and fibre. This mutual repulsion, when superimposed on

the preexisting van der WasIs attraction, causes

reduction in adhesion.

The process of detachment of particulate soil

from fibre surface and the work associated therein can be

explained by two models depending upon the geometry of

. 34 35
the interfaces.' ’ The plate-plate model is applicable

to two parallel interfaces in which the soil particles

are assumed to adhere to the fabric surface with plane

faces. The plate-sphere model is applicable to soil

i

particles having spherical shape and curved surfaces in

contact with the plane surface of the fibre. However,

the.actual geometry of the adhesion of real particles

and fibres is much more complicated. Therefore, the

soil removal behaviour of such system can be better

described by both the models depending upon the type of

 142

the fraction of zones of contact.

The wetting of the fibre (F) or the particle (F)

by the bath (B) can be given by spreading coefficients,

S_jp and Sgp respectively, where

SBF = “ Y fB " 'Xa B , Eg. 5.5,

and

BP
/'•PA - f>PB AB Eg. 5,6

Here, the subscripts FA, AB and PA refer to the

fibre-air, air-bath and particle-air interfaces,

respectively.

If the spreading coefficient is positive, then

spreading occurs spontaneously$ if not. mechanical work

must be done to wet the surface completely. Adsorption

of surfactant from the washing bach at the fibre-bath or

particle-bath interface reduces Y f 3 or anc1 thereby

increases the tendency to wet the soil and fibre. If the

fibre or the soil is hydrophobic, Y d /* or would be

loxf, hence, mechanical work is reguired to wet them.

Adsorption at fibre-solution and particle-solution

interfaces reduces the work reguired to remove particle

from fibre. The work of adhesion (Wa ) indicating the

free energy change can be given by

Wa .= YpB + Y^B - Y^p , Eg. 5.7 .

 143

, ^ , s'
adsorption of surfactant can reduce ana 'fpB

with consequent decrease in the work required to remove

the particle from the substrate.

The reduced wor^ of adhesion between soil and

fibre caused by, adsorption onto them of surfactant

molecules, the reduced vari der Waals attraction resulting

from hydration of hydrophilic groups oriented towards the

bath and the increased electrostatic repulsion caused by

\

the increase in zeta potential of soil and fibre all

facilitate separation of soil from fibre in presence of

mechanical work,

5,3,1 Detailed Picture of Surfactant adsorption

. 36
Cuming and Schulman studied the interaction of

barium sulfate suspension with sodium dodecjdL sulfate.

The adsorption process involved two steps. Firstly, the

chemisorption of dodecyl sulfate anion with the tail

oriented outward. This reduced che negative charge on

the surface to near zero. Then a.second layer of sodium

dodecyl sulfate molecules was adsorbed with the heads

oriented toward the water. This increased a neqative

charge on the surface,

■The configuration of the adsorbed surfactant

molecules has been investigated by X-ray diffraction

using bentonite clay. The configuration depends upon

the type and nature of the surfactant. For example,

 144

anionic surfactant molecules were found adsorbed

. 37
perpendicular to the plane of the clay lamellas.

’•'Jheroas, cationic surfactant molecules were found

38
adsorbed parallel to the plane.

The Langmuir adsorption isotherm describes the

adsorption of surfactants:

x abc__
Eq, 5 . 8 t
m = 1 + bC ’

where x is the gram of adsorbed surfactant per gram cf

solid adsorbent m. C is the equilibrium surfactant

concentration and a and b are constants.

The equilibrium constant K for the distribution of

surfactant between solid surface and solution is given by

X . = _2L_ZJ2— * Eg, 5.9,

usoln

where Csoln is the concentration of surfactant in solution.

This would reveal the free energy change

A G = - RTlnK , Sq, 5.10.

For positive adsorption, concentration of surfactant

on solid will be greater than that in solution resulting in

. g
a decrease m free energy. Adsorption isotherms of sodium
39
dodecyl sulfate on soil pigments of different types are

shown in Fig. 5.9. Similarly, some sorption isotherms of

39
sodium dodecyl sulfate on different fibres are shown m

Fig. 5.10. The soil and the fibre of our interest are
 AOSORPTION ( m ol**/cm ) * 10

, !

F IG .5 .9 : AOSORPTION OF SODIUM DODECYL

SULFATE ON DIFFERENT SOLIDS

EQUILIBRIUM CONCENTRATION (m o l* s /lilr .f x1<J3

FIG. 5 .1 0 : SORPTION OF SODIUM DODECYL

SULFATE ON DIFFERENT T E X T IL E
FIBRES
 145

iron oxide and cotton. It is evident from the figures

that the isotherms have levelled off ip the vicinity of

the critical micelle concentration of the surfactant.

5.3.2 Mechanism of Particulate Soil Removal

The soil removal mechanisms for oily soils and

particulate soils are different. Release1of particulate

soil is not dependent on the hydrophilicity of the fibre

but on the location of the particle and its adhesion to

the fibre surface.

The extent and rate of soil removal from fabrics

depends upon nature and maanitude of the soil retaining

forces. If the forces are very weak, the soil removal

rate is proportional to the difference of soil concentra­

tion between the fabric surface and the wash liquor.

Under this condition, the removal process is essentially

a mass transfer process.^ When the soil retaining

forces are appreciable, which is usually the case, the

process becomes more complex. Soil retention forces were

theoretically estimated by Lange4 '*' on the assumption that

they are of London - van der Waals type. This assumption

42
was qualitatively supported by Durham. -A review
. . . . . 43
concerning the topic is given by Harris.

The amount of particulate soil retained on washed

. . . 44
fabrics, cw » is a function of soiling conditions. ' When
 146

washing conditions are constant

ew = kru (sts )^’^ , Egi 5.il»

whore k r is the retention coefficient, s is the amount of

soil (% owf) supplied for soiling, ts the soiling time,

and u the rotational speed of the soiling device,

indicating the input of kinetic energy.

Samples of cotton fabric, soiled with ferric oxide

in the Accelerator or in the FIRA tumbler, were washed in

the Tephotometer under identical washing conditions. The

^ *

reflectance of the washed fabrics was measured and the

fabric analysed for the ferric oxide content. The soil

content of fabrics, which were soiled by the Accelerotor

and washed, increased with the increasing scruare root of

the amount of soil supplied for soiling in accordance with

Sg. 5.11 (Fig. 5.11). Soiling values W calculated from

the reflectance data of washed fabrics, increase also

. . 0.5
linearly with s , and consequently correlate linearly

with the soil content determined by analysis.

However, the soil content of fabric samples soiled

in the FIRA tumbler is not linearly related to the square

root of the amount of soil supplied for soiling (Fig.5.12).

A log/log plot of data shown in the Ficrure 5.12 revealed

that the cw values had the expected slope (0.21)', but the

r<l values had the slope 0.42. A difference between slopes

indicates that ;'J and values are no longer linearly

related
FIG. 5-11: RELATIONSHIP BETWEEN SOILING AND
DETERGENCY OF PARTICULATE SOIL
FIG. *5.12 .* RELATIONSHIP BETWEEN SOILING AND
DETERGENCY OF PARTICULATE SOIL IN
p r e s e n c e o f f a t t y Ma t e r ia l
 147

The washed samples were examined by the scanning

electron microscope to see the particle location and

distribution on fibres after washing. Fig;. 5.13 shows

that the residual soil particles on the samnie, which had

been soiled by the AcceLerotor and washed, are discretely

distributed. Whereas, the soil particles on the sample

which had been soiled in the FIRA tumbler and washed

remain in a stats of agerraaation (Fig. 5.14).

Thus, the FIRA tumbler, as a soiling device, fails

to correlate particulate soil detergency with the soiling

conditions. This may be attributed to the mechanism of

tumbler soiling which is a two-step process (Chapter III).

The felt cub s used to transfer soil on test samples were

found to contain wool-wax in a larae cmantity (Chapter IV).

Since the wax crets deposited along with the particulate

soil on the sample, the -adhesion of the soil particles is

45
affected. Schott' concluded that a thin layer of oily

soil between particle and fibre markedly affects a d h ’.eion.

It is, therefore, important to know the effect of such a

film on adhesion strenrth. between particles and fibres

and on the rate of seil removal. In this respect, the

. . 45
following conclusions derived by Fort et al on

detergency of multi-conoonent fatty soils are useful!

(a) A polar soil component increases the detergent

solubility in the soil films thereby facilitating

removal of the soil-complex.

FIG.5.13: RESIDUAL SOIL PARTICLES ON FABRIC
(SOILED BY THE ACCELEROTOR
AND WASHED) (900X)

FIG.5.14: RESIDUAL SOIL PARTICLES ON FABRIC

(SOILED BY THE FIRA TUMBLER
a n d w a s h e d ) (9o o x )
 148

(b) Hydrophilic carbon is removed easily from polyester

film than hydrophobic carbon in the presence of fat.

(c) An easily removable fatty soil carried the

particulate soil on the surface off with it. If the

particulate soil were easier to remove than fat,

then the presence of the fatty,soil retards the

removal of the particulate soil. In such a case the

fat acts as an adhesive and binds the particulate

soil to the surface.

5.3.3 Effect of Particle Size on Soil Removal

Referring to eqn. 5.11, the amount of particulate

soil retained after washing depends also on the nature of

soil and fibre and the construction of the fabric. In this

regard the particle size of the soil is an important factor.

The adhesion, and location of particles is affected by their

particle size. , The extant of soiling of fabric depends

upon 'the relative amount of small particles in particulate

soil (Chapter IV). The model particulate soil (ferric

oxide) consists of small particles of narrow range.

However, the natural particulate soil usually consists of

particles of various sizes.

The extent of residual soil on the washed fabric

is a function of the difficulty of soil removal indicated

by the soilinc? value W. Table 5.4 shows that when the

washing conditions are same, the amount of soil retained

 149

TABLE 5.4

EFFECT OF PARTICLE-SIZE ON SOIL REMOVAL

Particle r a m e Foiling Value F

of.washed fabric
Untreated Crosslinked

150 - 75 0.058 0.035

75 - 50 0.094 0.058

50 - 40 0.195 0.090

10 - 2 0.450 0.133

after washing increases with decreasing particle size.

The effect is similar for untreated as well as crosslinked

cotton fabrics.

In the detergency of particulate soil, the force

exerted hydrodynamically on the particle is probably more

important. The velocity gradient of a liquid flowing past

a solid surface decreases essentially to zero as the

39 . . .
surface is approached more closely. The situation is

shown schematically in Fio.* 5.15, The larger particle

extends to zones of hiaher streaming velocity and provides

larcrer area of attack. Consequently, the larger particle

is attached by a stronger hydrodynamic force than the

smaller one. In other words, fine- particles are difficult

to remove.

5.4 Aqueous Soiling

Removal of soil in a closed washing bath is a

\
 150 -

reversible process. The soil which has once been removed

from a fabric d u r i m washing can precipitate/deposit

back onto that or accompanying substrate. This phenomenon

is known as soil redeoosition and sometimes wet soiling.

Repeated cycles of laundering involving soil redeposition

make a gradual discolouration of white garment turnincr it

grey.

It has been said that soil redeposition was not a

. r .7
problem with pure soaps.* Built synthetic detergents

became popular owing tc their low prices. However, they

promoted the problem of soil redeposition.

When a wet fabric is inserted in a wash bath

containing a stable suspension of soil, it takes up a

certain amount of the soil. The deposition of the soil

on the fabric depends uoon the surface characteristics of

the soil and fabric and on the nature of the medium.

Distribution of ferric oxide between cotton poplin and

different media is shown in Fig. 5.16. Maximum soil

deposition is observed in pure water as the medium.

Moreover, the particles are found aggregated. The

deposition is reduced ^hen aqueous surfactant solution is

used. The deposition is further reduced when sodium

carborymethyl cellulose (CMC) is incorporated in the

surfactant solution. The particles are having primary

particle size and they are discretely distributed on the

fabric.
. FIG-5-16 • DISTRIBUTION OF FERRIC OXIDE BETWEEN
LIQUOR AND FIBRE
 151

48
Ross et al showed that the deposition of graphite

onto cotton fabric follows the Schultz-Hardy rule of

colloidal stability.. They confirmed that the primary

causes of soil redeposition in usual launderina are

(a) the presence of polyvalent cations in hard water, and

(b) the introductioh of high concentration of sodium ion

by the built dotercrent.

. 49-
Niewenhuis proposed the following probable

mechanisms of CMC actions

(a) The structure of cellulose and CMC are closely

related.

(b) The carboxyl groups, on CMC and on cellulose have

similar position in relation to one another.

(c) CMC is adsorbed on the soil and on the fibres,

and carboxyl groups give neoative charge to them.

The carboxyl groups also bind a large quantity of

water through hydration.

(d) The adsorbed CMC creates a repulsion between the

soil and the fibre.

(e) CMC is ineffective on noncellulosic fibres (since

lack of adsorption) to inhibit radeposition.

5 0 -5 2
Several workers have reported that CMC

increases negative intarfacial potentials between soil

and fibre. This supports the proposed action of CMC.

 152

53 . . .
Search et al explained mechanism of wet soiling

on the basis of surface energy of the substrate. This

mechanism (Fia. 5.17) is based on the concept that in wet

soiling, a oiament becomes attached to a fibre by dis­

placement of water from the surfaces of both fibre and

the particle. When the m o m e n t becomes attached to the

fibre, a oigment-fibre interface is formed at the expanse

of water-fibre and water-pigment interface. It is well-

known that a spontaneous process is accompanied by a

decrease in free enercry. Therefore, the sum of inter­

facial tensions of water-fibre and water-pigment inter­

faces must be greater than the interfacial tension of

niament-fibre interface.

When the fibre surface is finished the surface

eneraies are changed and therefore aqueous soiling is

affected. Cotton fabric samples, crosslinked with

different concentrations of DMDHSU were soiled in

different aaueous media. The amount of ferric oxide

deposited on each sample was analyzed. The data on

ferric oxide content of fabrics actainst the nitrogen-

content of the fabric are plotted in Fig. 5.18. It is

evident that degree of soiling in agueous medium

decreas.'-s with the increase'in degree of crosslinking

of cotton fabric. In other words, cotton fabric cross-

linked with DMDHSU without softeners resists aqueous

soiling. " The tr'end is similar in presence of surfactant

 - ---- — PIGMENT - 1— — —

- — — WATER ,— • L- . —.
. ' \
/ / / / / / / / / / , FIBRE ' / / / / / / / / A / /
'
r .r w a te r-fib re j

"T w ater^pigm ent J!

WATER

PIGMENT
“ 7 ^77777777^777777777777

T w a te r-fib re 4-Y w a te r-p ig m e n t > ^ p ig m e n t-fib re

FIG .5.1?: MECHANISM OF WET SOILING

FERRIC OXIDE ('/. o w f )

NITROGEN CONTENT OF CR05SLINKED FABRIC

(°/o mole owf) j

FIG.5.18: AQUEOUS SOILING BEHAVIOUR OF COTTON

FABRIC CROSSLINKED WITH DIFFERENT
CONCENTRATION OF DMDHEU
 153

and CMC in the aqueous hath.

The mechanism of wet soiling of ferric oxide is

reported to he due to embedding of hydrophilic pigment

, 54
particles in the surface coating on the fibres. The

amount of soil deposited is shown to decrease with

increasing hardness of polymers used for coating.

h comprehensive review on soil redeposition is

. . 55 55
given by Davis and also by Bearch and Peper.

Thus, the net result of detergency process

(Egn. 5.1) is obtained considering two opposite

processes,, namely, soil removal and soil redeposition.

The extent of soil removal depends primarily upon the

physicochemical parameters of the three components in

mutual interaction, i.e., substrate, soil and

surfactant
 154

5.5 References

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