Tharwat F.

Tadros

Applied Surfactants Appliedand Surfactants Principles Applications

Principles and Applications

A ut ho r P r of . D r. T ha rw a t F . Ta dr os 8 9 N as h Gr ove L ane W ok i ngh am B er ks h i r e R G40 4H E U ni ted K i ngd om

9 Th i s b oo k w as c a ref u l ly pr o du c ed . Neve rth el es s , au th o r a nd p u b l i s h er do not w arra nt th e i nf or mati o n c ont ai ned th er ei n to be fr ee o f er ro rs . R ead er s are ad vi se d to k eep i n mi nd th at s ta tements , d ata, i l l u s tr ati on s, p ro c ed u ral d eta i ls o r oth er i tem s may i nad ver tentl y b e i nac c u r ate.

Li b rar y of Con g ress Card No . : Ap pl i ed fo r Bri ti sh Li b rar y Cat al og u in g - in - P u bl i cati o n D ata : A c ata lo g u e r ec or d for th i s b oo k i s avai l ab l e fr om th e B ri ti s h L i b rar y

Bi bl i og ra ph i c i n for ma ti on p u bl i sh ed b y D i e D eu tsch e B ib l io th ek Di e Deu ts c h e Bi b l i oth e k l i s ts th i s pu b l i c ati o n i n th e D eu ts c h e Nati o nal b i bl i o gr a e; d etai l ed b ib l i og r ap h i c da ta i s avai l a bl e i n t h e In terne t at h h ttp : //d nb . dd b .d ei

8 20 05 WI L EY- V CH V erl ag Gm bH & C o. KG aA, We i nh ei m A ll r i g h ts re se rved (i nc l u d i ng th os e of t rans l ati on i n oth e r l ang u ag es ). No pa rt o f th i s bo ok may be rep r od u c ed i n any for m b y p h oto pr i nti ng , mi c ro l m, or any oth er means no r tr ans mi tt ed or tr ans l ated i nto mac h i ne la ngu ag e w i th o u t w r i tten p er mi s s i on f ro m th e p u b l i s h ers . R egi s te re d na mes , tr ade mar ks , etc . u s ed i n th i s b oo k, eve n w h en no t s p ec i c al l y mar k ed as s u c h , are not to b e c o ns i de red u np r otec t ed by l aw .

Pr i nted i n th e F ed er al R ep u bl i c o f Ger many Pr i nted on a c i d- fr ee pa pe r

Co mp o si ti on A s c o Typ es ette rs , H ong K ong P ri n tin g S tra u s s Gmb H, M or l enba c h Bo okb i n di n g L i tg es & Do pf Bu c h b i nde rei Gmb H , Hep p enh ei m IS BN- 13 : 9 78 - 3- 52 7- 3 06 29 - 9 IS BN- 10 : 3 - 52 7- 30 62 9- 3

VII

Contents
Preface XIX 1 Introduction 1 1.1 General Classi cation of Surface Active Agents 2 1.2 Anionic Surfactants 2 1.2.1 Carboxylates 3 1.2.2 Sulphates 4 1.2.3 Sulphonates 4 1.2.4 Phosphate-containing Anionic Surfactants 5 1.3 Cationic Surfactants 6 1.4 Amphoteric (Zwitterionic) Surfactants 7 1.5 Nonionic Surfactants 8 1.5.1 Alcohol Ethoxylates 8 1.5.2 Alkyl Phenol Ethoxylates 9 1.5.3 Fatty Acid Ethoxylates 9

1.5.4 Sorbitan Esters and Their Ethoxylated Derivatives

(Spans and Tweens) 10 1.5.5 Ethoxylated Fats and Oils 11 1.5.6 Amine Ethoxylates 11 1.5.7 Ethylene OxidePropylene Oxide Co-polymers (EO/PO) 11 1.5.8 Surfactants Derived from Mono- and Polysaccharides 12 1.6 Speciality Surfactants Fluorocarbon and Silicone Surfactants 13 1.7 Polymeric Surfactants 14 1.8 Toxicological and Environmental Aspects of Surfactants 15 1.8.1 Dermatological Aspects 15 1.8.2 Aquatic Toxicity 15 1.8.3 Biodegradability 16 References 16 2 Physical Chemistry of Surfactant Solutions 19 2.1 Properties of Solutions of Surface Active Agents 19 2.2 SolubilityTemperature Relationship for Surfactants 25 2.3 Thermodynamics of Micellization 26
App li e d Su r fa c tan ts: Pr i nc i pl e s an d App li c a ti ons . Th ar w at F . Tad ro s Co p yri g h t 8 20 05 W IL EY- VC H Ver l ag G mbH & C o . K GaA , Wei nh ei m IS B N: 3- 5 27 -3 06 29 - 3

VIII Contents

Contents IX

4.3.3 Du 2.3.1 Nouys Kinetic Ring Aspects Method 2682 4.3.4 Drop 2.3.2Volume Equilibrium (Weight) Aspects: Method Thermodynamics 82 of Micellization 27 4.3.5 Spinning 2.3.3 Phase Drop Separation Method 83 Model 27 2.3.4References Mass Action 84Model 29 2.3.5 Enthalpy and Entropy of Micellization 30 5 Adsorption 2.3.6 Driving of Surfactants Force for and Micelle Polymeric Formation Surfactants 32 at the Solid/Liquid 2.3.7Interface Micellization 85 in Other Polar Solvents 33 5.1 Introduction 2.3.8 Micellization 85 in Non-Polar Solvents 33 5.2 Surfactant 2.4 Micellization Adsorption in 86 Surfactant Mixtures (Mixed Micelles) 34 5.2.1 Adsorption 2.4.1 Surfactant of Ionic Mixtures Surfactants with no on Net Hydrophobic Interaction Surfaces 34 86 5.2.2 Adsorption 2.4.2 Surfactant of Ionic Mixtures Surfactants with a on Net Polar Interaction Surfaces36 89 5.2.3 Adsorption 2.5 SurfactantPolymer of Nonionic Surfactants Interaction 91 39 2.5.1 Factors In uencing the Association Between Surfactant 5.3 Adsorption of Polymeric Surfactants at the Solid/Liquid Interface 93 and 5.4 Adsorption and Conformation of Polymeric Surfactants at Polymer 41 2.5.2Interfaces Interaction 96 Models 42 5.5 Experimental Measurement of Adsorption 2.5.3 DrivingMethods Force for for SurfactantPolymer Interaction 45 Parameters 2.5.4for Structure Polymeric of SurfactantPolymer Surfactants 102 Complexes 45 5.5.1 Amount 2.5.5 SurfactantHydrophobically of Polymer Adsorbed G Adsorption Modi ed Polymer Isotherms Interaction 102 45 2.5.6 Interaction Between Surfactants and Polymers with Opposite Charge 5.5.2 Polymer Bound Fraction p 106 5.5.3 Adsorbed Layer Thickness d and Segment Density (SurfactantPolyelectrolyte Interaction) 46 Distribution r(z) 107 References 50 5.5.4 Hydrodynamic Thickness Determination 110 3 Phase References Behavior 112 of Surfactant Systems 53 3.1 SolubilityTemperature Relationship for Ionic Surfactants 57 6 Applications 3.2 Surfactant of Surfactants Self-Assembly in Emulsion 58 Formation and Stabilisation 115 6.1 Introduction 3.3 Structure 115of Liquid Crystalline Phases 59 6.1.1 Industrial 3.3.1 Hexagonal Applications Phaseof 59 Emulsions 116 6.2 Physical 3.3.2 Micellar Chemistry Cubic of Emulsion Phase 60Systems 117 6.2.1 Thermodynamics 3.3.3 Lamellar Phase of Emulsion 60 Formation and Breakdown 117 6.2.2 Interaction Energies (Forces) Emulsion Droplets and 3.3.4 Bicontinuous Cubic PhasesBetween 61 3.3.5their Reversed Combinations Structures 118 62 6.3 Mechanism 3.4 Experimental of Emulsi Studies cationof 123 the Phase Behaviour of Surfactants 62 6.4 Methods 3.5 Phase of Emulsi Diagrams cation of Ionic 126 Surfactants 65 6.5 Role 3.6 of Phase Surfactants Diagrams in Emulsion of Nonionic Formation Surfactants 127 66 6.5.1 Role of Surfactants References in Droplet 71 Deformation 129 6.6 Selection of Emulsi ers 134 6.6.1 Hydrophilic-Lipophilic 4 Adsorption of Surfactants Balance at the (HLB) Air/Liquid Concept and 134 Liquid/Liquid 6.6.2 Phase Inversion Interfaces Temperature 73 (PIT) Concept 137 6.7 Cohesive 4.1 Introduction Energy Ratio 73 (CER) Concept for Emulsi er Selection 140 6.8 Critical 4.2 Adsorption Packing Parameter of Surfactants (CPP) 74 for Emulsi er Selection 142 6.9 Creaming 4.2.1 Gibbs or Sedimentation Adsorption Isotherm of Emulsions 75 143 6.9.1 Creaming 4.2.2 Equation or Sedimentation of State Approach Rates 145 78 6.9.2 Prevention 4.3 Interfacial of Creaming Tension Measurements or Sedimentation 80 147 6.10 Flocculation 4.3.1 Wilhelmy of Emulsions Plate Method 150 80 6.10.1 4.3.2 Mechanism Pendent ofDrop Emulsion Method Flocculation 81 150