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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1

but in the comb compound the functional groups can be larger than two [2].Silicone polymers can be constructed in 3 ways A) Comb A) Comb: CH3 CH3 Si O CH3 ( CH3 Si O CH3 ) 50 ( CH3 Si O R ) 10 CH3 Si CH3 CH3 B) Terminal C) Multifunctional B) Terminal: CH3 R Si O CH3 ( CH3 Si O CH3 CH3 ) 50 Si CH3 R M* M* C) Multi functional: CH3 R Si O CH3 ( CH3 Si O CH3 ) 50 CH3 ( Si O R ) 5 CH3 Si CH3 R 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). This great degree of freedom of rotation gives very effective screening of the polar Si–O backbone by methyl groups in its entire configuration. 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. resulting in low intra molecular forces with the following consequence: /opt/scribd/conversion/tmp/scratch19923/44641014.doc 2 .

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. 3. a full body is achieved along with improved elasticity. /opt/scribd/conversion/tmp/scratch19923/44641014. which is durable to repeated washings. Advantages: The silicones impart a finish with unique quality. The fabric becomes soft with good handle. Carboxy modified silicones: It can be used in conjunction with epoxy and amino modified silicones and can improve the feel of nylon fabrics. Dimemethylpolysiloxane: Improves the water repellency without affecting its breath ability. 2. The finish also provides excellent sewing properties.  Effective lubrication of fibre due to poor surface interaction between silicone covered fiber [3]. Low crystalline melting points  Low glass transition temperature  Low viscosities  Low temperature co-efficient of viscosity. wrinkle recovery and heat and stain resistance. 4. It needs low curing temperature than dimethylpolysiloxane. 5]. Methylhydrogenpolysiloxane: Gives better softness and water repellency to the fabric than dimethylpolysiloxane. 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. 1. Epoxy modified silicones: This impact an enhanced softness and smooth feel to the fabric apart from tear resistance.doc 3 .  Low surface tensions (hydrophobic character).g.

The micro emulsion have particle size less than 1/4 th the wavelength of light and are translucent to clear in appearance. better durable press properties. Silicone Micro emulsion-based Softeners – Micro emulsion technology. 6. Hence the silicone remains emulsified eliminating the occurrence of free silicone oil that can spot the fabric. 8. The micro emulsion technology has enhanced the shear and chemical stability of the treatment bath. These softeners due to its size deposit on the fibre surface and give surface lubricity and enhanced surface smoothness to the fabric. recently has ushered in a wide range of premium softeners. 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.5. Hydrophillic modified silicones: This by its hydrophillicity reduces the kinetic friction between the fibres of the fabric. increased stretch and recovery of knitted fabrics and durability to laundering. As the assessment of the performance of a softener is qualitative and the /opt/scribd/conversion/tmp/scratch19923/44641014. It is milky white to translucent in appearance.doc 4 . which has been commercialized. Amino modified silicones: Apart from tear resistance it imparts an enhanced softness and smooth feel to the fabric. Mercapto modified silicones and amido modified silicones: Used in making car polish cloth and furniture polish napkins respectively. Polyethene modified silicones: They possess low coefficient of friction and are hence used as lubricants for fabrics. The smaller size also helps in better penetration so that it is less of a surface treatment and more of an internal softener. 7. These softeners based on amino silicones impart a combination of useful properties like improved hand. Silicone Macro emulsion-based Softeners: these softeners have a bigger particle size as compared to that of micro emulsion softener.

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. All the fabrics treated with the softeners had an improved softness. Product-D: A special economical macro-emulsion softener for cotton. Product-B: A micro – emulsion softener. and is compatible with organic softeners and cross-linking agents. which imparts excellent softness and handle to the fabric. Product-E: A reactive micro-emulsion silicone softener. The experimental details of the same are given below: Experimental Details Material: Single jersey RFD knit for evaluation of whiteness Index. Product-H: A especially developed micro-emulsion based softener with non-yellowing properties. polyester and their blends. Product-C: A micro-emulsion softener for both natural and synthetic fibres. Friction and Drape coefficient.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. Product-F: A new generation polysiloxane softener for both cotton and polyester. 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. Softeners Studied: Product-A: A new generation of shear stable nano silicone softener which can be used by both exhaust and padding. which imparts excellent inner softness and lubricity. Product-G: A macro-emulsion based softener for natural and synthetic fibres (bulk trials being conducted). 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.doc 5 . but the softness and /opt/scribd/conversion/tmp/scratch19923/44641014.

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. namely Product-D. The fibre strands look smoother due to the lubricating property of the softener giving a smoother feel. The comparative study of the microscopic structure with the scanning electron microscope (SEM) as illustrated in Fig1-3 of the unfinished fabric. and the measurement is done under D65 illuminant. CIE whiteness index is (AATCC Test Method 110-1995) most commonly used for textiles. Yn = 0. like alicyclic modified amino silicone. The equation for WI is as follows: W.the feel imparted by Product-C.doc 6 . The application of the range of silicone softeners on RFD knit fabrics as depicted in /opt/scribd/conversion/tmp/scratch19923/44641014. The microscope shows detailed 3-dimensional images with a much higher magnification as compared to light microscope. As the electron beam hits the specimen. = Y+ 800(Xn – X) + 1700(Yn –Y) Where.3138. secondary electrons are knocked from the surface.I. 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. for D 65/10 Xn = 0. and the final image is built from the number of electrons emitted from each spot. 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. Product-B and Product-D were found to be better than the other products. amido or piperidine modified amino silicone reduce the yellowing tendency without hampering the feel of the fabric. the fabric finished with a conventional macro-emulsion based softener. which is a standard representation of outdoor daylight. The sample is placed in a vacuum tunnel and a electron gun emits high energy electrons. 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. Modifications.

The dynamic friction between fabric to fabric was determined as one moved over the other under a specific normal load. An uneven and rugged surface has a higher frictional coefficient. the particle size.doc 7 . and hence. and Figure 4. which imparts surface lubrication were more effective in this case i.Table 1. these softeners can be readily applied on white textile substrates.) Friction Coefficient: The fabric-to-fabric friction coefficient was determined by an attachment to the Instron Tensile Tester. and the frictional coefficient is a measure of the surface properties of the substrate..e for the improvement of the friction properties. Surface lubricity assumes a greater significance as far as lowering of the frictional coefficient is concerned as depicted in Figure 5. illustrates the whiteness index of the fabric after the application of the softener as compared to the unfinished fabric. 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. This phenomenon when translated onto the fabric properties means that the fabric feels rough and abrasive when touched. The results shows no significant detrimental effect of the softener on the whiteness index of the fabric. Whiteness Index of RFD Knitted Fabric with Different Silicone Finishes /opt/scribd/conversion/tmp/scratch19923/44641014. the softeners. 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. viscosity etc. emulsifying system. Table 1: Softness. and the results indicate that all the softeners lowered the friction coefficient as compared to the unfinished fabric. the amine content. 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. (without fear of yellowing at a later date . As we are well aware that the performance of a silicone softener depends on many factors like.

4: Effect of Softners on Whiteness Index /opt/scribd/conversion/tmp/scratch19923/44641014.doc 8 .Finishing Agent Unfinished Product-A Product-B Product-C Product-D Product-E Product-F Product-G Product-H Softness Rating 9 6 1 2 4 7 8 5 3 Whiteness Index (CIE) 86 79 77 79 82 79 84 80 85 Figure.

85 78 /opt/scribd/conversion/tmp/scratch19923/44641014.5: Effect of Softners on the Friction Co-efficient of Knits Whiteness Index 82 Figure-2: Effect of 0.8 76 9 74 .Figu 88 86 84 Figure.doc fficient 0.9 80 0.

doc .6: Effect of Softners on Drape coefficient of RFD Knits Figure-3: Effect 38 36 34 Drape Co-efficient 32 30 28 26 24 10 Figure 1: SEM Study of Unfinished Cotton Knits /opt/scribd/conversion/tmp/scratch19923/44641014.Figure.

5. Journal of Surfactant and Detergent. “Silicone Emulsions and Surfactants”. “Silicone Antifoaming Agents”. Special Issue. Journal of Surfactant and Detergent. 20. etal “The Marvel of Silicones in Textiles”. Bhute R.. Colourage.Bajaj P(1971). Padubidri S(1992).doc 11 . Colourage. 39(July). 4.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. (2000). 2. 75. “Silicone Emulsions and Surfactants”.S. Lenick AJ. Journal of Scientific and Industrial Research. “Chemistry of Organosilicon Polymers and their Importance in Textile Technology”. 30(5) /opt/scribd/conversion/tmp/scratch19923/44641014. 20(3). (1971). 229-236. 387-392. (2000). 3(2). . 3. 3(3).. Lenick AJ.

doc 12 ./opt/scribd/conversion/tmp/scratch19923/44641014.

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