STRUCTURE- FUNCTIONAL RELATIONSHIP IN SILICONE SOFTENERS

By: Dr. Ruma Chakrabarti, Kavita Krishnamurthy, Kumaraguru College of Technology,

A.Vignesh, Hohenstein India Pvt Ltd, Coimbatore-India

Abstract: Silicones find wide application in textile finishing. Silicone based emulsions and

softeners impart softness and smoothness which is unique and unparalleled by any other

group of softeners. The basic silicone backbone can be modified by the help of introducing

various functional groups to customize its end use according to specific requirements. This

work studies the effect of various functional groups and particle size of the emulsion on its

performance with respect to friction coefficient, Whiteness Index, Drape Coefficient, and

also by SEM.

Key Words: Silicone, Rochow Process, dimethyl polysiloxane, frictional properties,

Scanning electron microscope (SEM), drape coefficient.

Introduction: The science of silicon has its origin in nature. Sand or silica, which is the fine

residue of quartz rock, is made up of the two most abundant elements in the earth’s crust,

oxygen and silicone.

Silicone is obtained by the thermal reduction of quartz with carbon.

SiO2+C 1700°C Si + CO2 ---------- (1)

The Silicone produced from equation (1) is a solid metallic material and has to be crushed

into powder of particle size ranging from 100-350 nm for reaction in the Rochow process.

Now these crushed silicones are used in the preparation of silicone compounds to make

products from which silicones may be derived[1].

SILICONE STRUCTURE

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Silicone polymers can be constructed in 3 ways

A) Comb B) Terminal C) Multifunctional

A) Comb:

CH3 CH3 CH3 CH3

CH3 Si O ( Si O ) 50 ( Si O ) 10 Si CH3

CH3 CH3 R CH3

B) Terminal:

CH3 CH3 CH3

R Si O ( Si O ) 50 Si R

CH3 CH3 CH3

M* M*

C) Multi functional:

CH3 CH3 CH3 CH3

R Si O ( Si O ) ( Si O )5 Si R
50

CH3 CH3 R CH3

The functional differences between the comb and the terminal structures are the difference in

the number of substituents, which is limited to two in the terminal type (two at each end), but

in the comb compound the functional groups can be larger than two [2].

PROPERTIES OF SILICONE

The long Si-O and Si-C bonds reduce steric conflicts between methyl groups of neighboring

silicone atom that would otherwise occur and allow unusual freedom of rotation (low energy

barrier) about the Si–O and Si–C bonds. This great degree of freedom of rotation gives very

effective screening of the polar Si–O backbone by methyl groups in its entire configuration,

resulting in low intra molecular forces with the following consequence:

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  Low crystalline melting points

 Low glass transition temperature

 Low viscosities

 Low temperature co-efficient of viscosity.

 Low surface tensions (hydrophobic character).

 Effective lubrication of fibre due to poor surface interaction between silicone covered

fiber [3].

Advantages: The silicones impart a finish with unique quality, which is durable to

repeated washings. The fabric becomes soft with good handle, a full body is achieved

along with improved elasticity. The finish also provides excellent sewing properties,

wrinkle recovery and heat and stain resistance. They are also versatile and can be

applied to all kinds of textiles from natural to synthetic and woven to hosiery and if

required it can be used on yarn and threads too [4, 5].

Effect of Functional groups on Performance Properties: The surface properties imparted

to the fabric by silicones depend upon the nature of the organic functional groups that are

incorporated in the structure of silicones molecule for e.g.

1. Dimemethylpolysiloxane: Improves the water repellency without affecting its breath

ability.

2. Methylhydrogenpolysiloxane: Gives better softness and water repellency to the fabric

than dimethylpolysiloxane. It needs low curing temperature than dimethylpolysiloxane.

3. Epoxy modified silicones: This impact an enhanced softness and smooth feel to the

fabric apart from tear resistance.

4. Carboxy modified silicones: It can be used in conjunction with epoxy and amino

modified silicones and can improve the feel of nylon fabrics.

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5. Hydrophillic modified silicones: This by its hydrophillicity reduces the kinetic friction

between the fibres of the fabric.

6. Mercapto modified silicones and amido modified silicones: Used in making car

polish cloth and furniture polish napkins respectively.

7. Polyethene modified silicones: They possess low coefficient of friction and are hence

used as lubricants for fabrics.

8. Amino modified silicones: Apart from tear resistance it imparts an enhanced softness

and smooth feel to the fabric.

Silicone Macro emulsion-based Softeners: these softeners have a bigger particle size

as compared to that of micro emulsion softener. It is milky white to translucent in

appearance. These softeners due to its size deposit on the fibre surface and give surface

lubricity and enhanced surface smoothness to the fabric.

Silicone Micro emulsion-based Softeners – Micro emulsion technology, which has

been commercialized, recently has ushered in a wide range of premium softeners. These

softeners based on amino silicones impart a combination of useful properties like

improved hand, better durable press properties, increased stretch and recovery of knitted

fabrics and durability to laundering.

The micro emulsion have particle size less than 1/4 th the wavelength of light and are

translucent to clear in appearance. The micro emulsion technology has enhanced the

shear and chemical stability of the treatment bath. Hence the silicone remains emulsified

eliminating the occurrence of free silicone oil that can spot the fabric. The smaller size

also helps in better penetration so that it is less of a surface treatment and more of an

internal softener.

To evaluate the performance of the softeners we have selected eight different

commercially available softeners of both micro and macro emulsion range with different

functionalities. As the assessment of the performance of a softener is qualitative and the

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 evaluation may vary from person to person hence the performances were evaluated not

only in terms of the feel but also quantitatively in terms of Whiteness Index, Friction and

Drape coefficient. Scanning electron microscopy was used to study the effect of the

application of these softeners on the various performance properties and also its effect on

individual fibres on a microscopic level. The experimental details of the same are given

below:

Experimental Details
Material: Single jersey RFD knit for evaluation of whiteness Index.
Softeners Studied:
Product-A: A new generation of shear stable nano silicone softener which can be used
by both exhaust and padding.
Product-B: A micro – emulsion softener, which imparts excellent inner softness and
lubricity.
Product-C: A micro-emulsion softener for both natural and synthetic fibres, and is
compatible with organic softeners and cross-linking agents.
Product-D: A special economical macro-emulsion softener for cotton, polyester and their
blends.
Product-E: A reactive micro-emulsion silicone softener, which imparts excellent softness
and handle to the fabric.
Product-F: A new generation polysiloxane softener for both cotton and polyester.
Product-G: A macro-emulsion based softener for natural and synthetic fibres (bulk trials
being conducted).
Product-H: A especially developed micro-emulsion based softener with non-yellowing
properties.
Application: The Softeners were applied on the fabric by Pad-Dry method on a
laboratory padding machine with a pickup of 70% and drying temperature of 160°C.

Fabric Softness: The softness of the samples were evaluated by means of the fabric feel

and a qualitative relative ranking amongst them were given as depicted in Table 1 & 2.

All the fabrics treated with the softeners had an improved softness, but the softness and

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 the feel imparted by Product-C, Product-B and Product-D were found to be better than

the other products.

Scanning electron microscopy (SEM) Analysis: The scanning electron microscope

differs from the conventional light microscope by the fact that it creates magnification by

electrons instead of light waves. The microscope shows detailed 3-dimensional images

with a much higher magnification as compared to light microscope. The sample is placed in

a vacuum tunnel and a electron gun emits high energy electrons. As the electron beam hits

the specimen, secondary electrons are knocked from the surface, and the final image is

built from the number of electrons emitted from each spot. The comparative study of the

microscopic structure with the scanning electron microscope (SEM) as illustrated in Fig1-3

of the unfinished fabric, the fabric finished with a conventional macro-emulsion based

softener, namely Product-D, and fabric treated with a micro-emulsion softener Product-C

clearly indicates an improved smoothness and lubrication of the fibres as compared to that

of the unfinished fabric. The fibre strands look smoother due to the lubricating property of

the softener giving a smoother feel.

Whiteness Index (WI): Whiteness is the measurement of light reflectance across all

wavelengths of light comprising the full visible spectrum. Whiteness index gives a single

number referencing the relative degree of whiteness. CIE whiteness index is (AATCC Test

Method 110-1995) most commonly used for textiles, and the measurement is done under

D65 illuminant, which is a standard representation of outdoor daylight. The equation for WI

is as follows:

W.I. = Y+ 800(Xn – X) + 1700(Yn –Y)

Where, for D 65/10 Xn = 0.3138, Yn = 0.3309
The drying conditions and the amino groups in the silicone softener may cause yellowing
due to the formation of azo and azoxy compounds formed by the oxidation of the amino
groups. Modifications, like alicyclic modified amino silicone, amido or piperidine modified
amino silicone reduce the yellowing tendency without hampering the feel of the fabric.
The application of the range of silicone softeners on RFD knit fabrics as depicted in

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 Table 1, and Figure 4, illustrates the whiteness index of the fabric after the application of
the softener as compared to the unfinished fabric. The results shows no significant
detrimental effect of the softener on the whiteness index of the fabric, and hence, these
softeners can be readily applied on white textile substrates, (without fear of yellowing at a
later date .)
Friction Coefficient: The fabric-to-fabric friction coefficient was determined by an
attachment to the Instron Tensile Tester. The dynamic friction between fabric to fabric
was determined as one moved over the other under a specific normal load. As we are
well aware that the performance of a silicone softener depends on many factors like, the
particle size, emulsifying system, the amine content, viscosity etc., and the frictional
coefficient is a measure of the surface properties of the substrate. An uneven and rugged
surface has a higher frictional coefficient. This phenomenon when translated onto the
fabric properties means that the fabric feels rough and abrasive when touched. Surface
lubricity assumes a greater significance as far as lowering of the frictional coefficient is
concerned as depicted in Figure 5, and the results indicate that all the softeners lowered
the friction coefficient as compared to the unfinished fabric, the softeners, which imparts
surface lubrication were more effective in this case i.e for the improvement of the friction
properties.
Drapability: As far as the drapability of the fabric is concerned as shown in Figure 6 the
nano-emulsion and micro-emulsion based softeners like Product-A, Product-B show
better drapability values as compared to the macro-emulsion based softeners, which is
due to the fact that the nano and micro-emulsions due to their small size are able to reach
areas in the fibre that are not accessible to conventional softeners with normal particle
size and so can penetrate to the fibre core resulting in improved inner softness and
enhanced inter and intra fibre lubrication. Whereas the drapability of macro-emulsion
based softeners is lower as due to their bigger size these softeners are unable to
penetrate to the fibre core.

Table 1: Softness, Whiteness Index of RFD Knitted Fabric with Different Silicone Finishes

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 Finishing Agent Softness Whiteness
Rating Index (CIE)
Unfinished 9 86
Product-A 6 79
Product-B 1 77
Product-C 2 79
Product-D 4 82
Product-E 7 79
Product-F 8 84
Product-G 5 80
Product-H 3 85

Figure- 4: Effect of Softners on Whiteness Index

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 Figu
88

86

84

Figure- 5: Effect of Softners on the Friction Co-efficient of Knits

Whiteness Index
82

Figure-2: Effect of
80
0.9

78
0.85

76
0.8
fficient

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74
 Figure- 6: Effect of Softners on Drape coefficient of RFD Knits

Figure-3: Effect

38

36

34
Drape Co-efficient

32

30

Figure 1: SEM Study of Unfinished Cotton Knits

28

26

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 Figure 2: SEM Study of Cotton Finished with a Macro emulsion Softener

Figure 3: SEM Study of Cotton Finished with a Micro emulsion Softener

References:
1. Padubidri S(1992), etal “The Marvel of Silicones in Textiles”, Colourage, Special Issue, 39(July),
75.
2. Lenick AJ, (2000), “Silicone Emulsions and Surfactants”, Journal of Surfactant and Detergent,
3(3), 387-392.
3. Lenick AJ, (2000), “Silicone Emulsions and Surfactants”, Journal of Surfactant and Detergent,
3(2), 229-236..
4. .Bajaj P(1971), “Chemistry of Organosilicon Polymers and their Importance in Textile
Technology”, Colourage, 20(3), 20.
5. Bhute R.S., (1971), “Silicone Antifoaming Agents”, Journal of Scientific and Industrial Research,
30(5)

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