Detergency of Surfactants

Introduction
Cleaning process is a very complex process; No surfactants by self can clean a surface; Detergency this term, when applied to a surfactants, means the special property it has of enhancing the cleaning power of a liquid. Detergency a combination of effects involving adsorption at interface, alteration of interfacial tension, solubilization, emulsification, and the formation and dissipation of surface charges; Detergency involving mechanical action, biochemical action, and fabric softening.

Mechanisms of the cleaning process

1. (1) (2) Three elements in cleaning process The substrate (the surface that is to be cleaned) Hard surface glass , metals, and etc Soft surface fabric , fiber The soil (the material that is to be removed from the substrate in the cleaning process) Liquid soils oil or fat Solid soils black carbon, dust, and etc (3) The bath or cleaning solution.

2. Force between substrates and soils (1) Mechanical force soft & porous substrates, particle diameter r of the particles , then force, r < 100nm, then difficult to wash off (2) Electrostatic force surface potentail wool/water= - 48mV cotton/water= - 38mV Soil ++ silk/water= - 1mV cation bridge - polyvalency ions
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2. Force between substrates and soils (1) Mechanical force soft & porous substrates, particle diameter r of the particles , then force, r < 100nm, then difficult to wash off (2) Electrostatic force surface potentail wool/water= - 48mV Soil cotton/water= - 38mV ++++ silk/water= - 1mV --------------cation bridge () - polyvalency ions Electrostatic force > Mechanical force
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(3) Chemical force polar soils proteins , fats , oxides etc Hydrogen bond and electrovalent bond (4) Van Der Waals force interactions between polar & polar or polar & non-polar or non-polar & non-polar Two cleaning process: removal of the soil from the substrates suspension of the soil in the bath and prevention of its redeposition 3. Removal of the soil from the substrates It not cover the removal of soil by mechanical work, or chemical reagents (e.g. bleaches, reducing agents) or enzymes

(1) Removal of liquid soil roll-back or roll-up (a) Young equation: SO = SB- BO Cos Cos = (SB- SO)/BO SO , Cos , , then roll-up SB , Cos , , then spreading

(b) Roll-up force R:

Initial state: R = (SO-SB) + BOCos , < 0, < 90 ,Cos > 0 R= + BO Cos = 0 , force balance If surfactants is added and only adsorbed on interface S/B and O/B, then SB , OB , then > 0, < 90, BOCos > 0, R > 0, force imbalance, roll-up and , > 90, > 0, BOCos < 0, R = 0, anew force balance

(c) Three kinds of roll-up Complete removal Spontaneously roll-up = 180 e.g. anionics: only S/B,O/B By mechanism work 90< <180 e.g.nonionics: S/B,O/B,S/O Incomplete removal SO < SB , Cos > 0 < 90

Complete removal of oil droplets from substrate

Rupture and incomplete removal of large oil droplets from substrate

(2) Removal of solid soil (A) Mechanism (a) Liquefiable soil roll-up (b) Particulate soil Wetting of the substrate and the soil particles by the bath Spreading coefficient particles SB/P=PV- PB- BV > 0 substrates SB/S=SV- SB- BV > 0 Additive pressure gap capillary P = LVCos/R Adhesion of solid soil WSP= SB+ PB- SP > 0

(B) Potential curve DLVO theory V=VA+VR A state adsorbed state B state transition state C state separating state Esoil removal - energy barrier of soil removal Ere-soiling- energy barrier of re-soiling

4. Suspension of the soil in the bath and prevention of re-deposition (1) Solid particulate soil: formation of electrical and steric barrier (2) Liquid oily soil (a) Solubilization C > CMC Ionic surfactants C < CMC (only adsorption) Nonionic surfactants C > CMC (adsorption and solubilization) (b) Macro-emulsification

5. Dry cleaning hydrocarbon or chlorinated hydrocarbon (1) Thickness of electrical double layer is very thin (very low dielectric constant) low electrical barrier (2) Surfactants are probably adsorbed with polar head oriented toward the substrate and soil high steric barrier

3. Detergents
1. Composition of detergents (1) Surfactants enhancing the cleaning power (2) builders increasing the efficiency and effectiveness of surfactants as detergents and supplement their beneficial effects on soil removal (3) Other auxiliary agent

2. The relation of the chemical structure of the surfactant to its detergency (1) Effect of soil and substrate hydrophilic head oriented toward the bath or substrates (a) Oily soil hydrophobic substrates (e.g. polyester, nylon) POE hydrophilic substrates (e.g. cotton, wool) negative charge at neutral or alkaline pH anionics > nonionics (partly hydrogen bond) > cationics (b) Particulate soil anionics > nonionics > cationics

(2) Effect of the hydrophobic group of the surfactants extent and orientation of adsorption (efficiency of adsorption) ; solubility in bath. (a) R, surface activity; R, solubility e.g. carboxylate: the optimum Rn Used temperature: 38C R12~ R14; 55 C R16 Counter ion: valence number , Rn Hardness of water , Rn (b) Straight > branching chains

(3) Effect of the hydrophilic group of the surfactant (a) Anionics (b) Nonionics (c) Zwitterionic surfactants 3. Builders chelation , buffering, dispersion (1) Sodium tripolyphosphate (Na5P3O10 STPP) (a) Chelation power of Ca++Water 102 CaCO3 mg/g STPP 468 CaCO3 mg/g Polyacrylate (PAA) 466 CaCO3 mg/g

(b) Alkaline buffering power pH adjusting Water neutralizing 0.15 ml 0.1M NaOH aq. STPP neutralizing 5.20 ml 0.1M NaOH aq. PAA neutralizing 4.60 ml 0.1M NaOH aq. (c) Dispersing power dispersion of particles Water dispersing 8.0 ppm Mn STPP dispersing 13.0 ppm Mn PAA dispersing 11.0 ppm Mn Disadvantage : pollute environment (2) Zeolite molecular sieve NaOAl2O3 nSiO2H2O A type : Al2O3: SiO2(mole) = 1.3 - 2.4

(a) Mechanism Ion exchange power of Ca++exchange 300mg CaCO3/g Coprecipitation with soil Safety (b) Disadvantage Low rate of exchange No dispersibility (3) Other builders Polyacrylate Polymaleate

4. Other auxiliary agents (1) Bleacher peroxide , sodium perborate, sodium percarbonate etc (2) Fluorescent bleachng agent adsorption 300400nm ultraviolet radiation radiation 400-500nm visible light (3) Enzyme protease, amylase, lipase, cellulase (4) Finishing agents - antistatic agents, anti-bacterial agents, softening agents

5. Standard washing powder Surfactants Builder (STPP) Sodium silicate Sodium carbonate Sodium sulfate CMC

15% 17% 10% 3% 18% 1%