Basic of Colloidal Phenomena

Basics of
Colloidal Phenomena
June 30, 2011

Hyung-Gual. Kim
AP Care Chemical Technology
1
Contents
Part I
1. Surface tension and Surfactants
2. Basic Properties and Functions of Surfactants
Part II
3. Classification of Surfactants
4. Applications
2
Surface tension and Surfactants
Colloid
Surface and Interface Chemistry
A colloid is a substance microscopically dispersed evenly throughout another substance.
A colloidal system consists of two separate phases: a dispersed phase (or internal phase)
and a continuous phase (or dispersion medium).
The dispersed-phase particles have a diameter of between approximately 5 and 1000
nanometers. [Wikipedia]
3
Colloid
Classification of Colloid Dispersion
Continuous
Dispersed Phase Application
Phase
Liquid Aerosol, Fog, Mist, Hair Spray

Gas
Solid Aerosol, Smoke
Gas Foam
Liquid Liquid Emulsion, Milk, Mayonnaise
Solid Blood, Pigmented Ink
Gas Styrofoam
Solid Liquid Gellatin
Solid Solid Sol
4
Surface Tension
Surface tension is a property of the
surface of a liquid
Surface Tension = Force / Length = dyne / Cm
= Energy / Area = dyne * Cm /Cm2
Water to be spherical Surface energy, surface stress or surface free energy
5
Surface Tension
Surface tension of pure liquids

T (C) (dynes/cm)
Water 20 72.5
Water 25 72.0
Bromobenzene 25 35.8
Benzene 20 28.9
Benzene 25 28.2
Toluene 20 28.4
n-Octanol 20 27.5
Chloroform 20 27.1
Carbon tetrachloride 20 26.9
n-Octane 20 21.8
Ethyl ether 20 17.0
6
The actions of Surfactants
Oil
r ing
r Water
Sti
Oil Without surfactant
Water
Stirring
With surfactant
7
What are Surfactants ?
Definitions of Surfactants
Surface-Acive Agent, Surfactant, Amphiphilic Molecule
Chemicals which they have a hydrophilic and a hydrophobic group in its molecule at
once, adsorb the surface or interface, and change the surfacial or interfacial properties
dramatically.
A hydrophobic part; Water disliking A hydrophilic part; Water liking

The hydrophobic part is a long The hydrophilic part could be anionic
hydrocarbon chain (could be also branched) (SO3-), cationin (R3N+) or simply a polar
group
8
Definitions of Surfactants
Variables: Variables: Variables:

Length of Carbon Chain: Ethoxylation: Type :
-> Lauryl (C12): -> R-(OCH2CH2)n- - Organic or
- Inorganic
CH 3CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2-- Charge :
-> Anionic (~ 69%) Charge / Valence :
-> Stearyl (C18): - Mono
Carboxylate: -COO-
CH 3CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2-- - Di
Sulfate: -O-SO 3- Size (Hydrated)
Alkyl Branching:
-> Methyl Branching (Synthetic): Sulfonate: -SO 3-
Binding force
CH 3 Phosphate: -O-P(OH)O2-
|
-> Cationic (~ 10%)
CH 3CHCH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2--
Quat. Ammonium: -NR 3+
(effectively "shortens" chainlength)
Unsaturation: -> Nonionic (~ 20%)
Alcohol: -OH
-> Oleyl (Natural):
CH 3CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH=CHCH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2-- -> Amphoteric (Zwitterionic) 1%
Size :
(also "shortens" chainlength)
-> Steric Bulk
-> Alpha-Olefin (Synthetic):
-> Hydration
CH 3CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH=CH--
Secondary Polar Functionalities:
Aromatic Nucleus: -> Hydroxyl
-> Dodecylbenzene: -> Carboxylic Acids
CH 3CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2- -- -> Esters
Purity of Chainlength -> Amides
-> Ethers 9
Non Surfactants
Acetone added to water will reduces the surface tension.

Ethanol added to water will imporves the wetting properties.
Practically any organic soluble product will gives increased foam to water.
Low molecular weight polyacrylates will improve the dispersion properties
of aqueous solutions to clay or calcium carbonate.
Sodium hydroxide solution is an excellent detergent in some applications.
For examples of reduction in surface tension
Acetone C12EO5
Concentration Surface Tension Concentration Surface Tension
20% 42dyne/cm 0.0004% 48dyne/cm

50% 30dyne/cm 0.004% 31dyne/cm
10
Basic Properties of Surfactants
The addition of surfactants will change the following properties of water.
The changed properties of water
1. Reduction of surface and interfacial tension

2. Solubilization
3. Wetting
4. Foaming
5. Dispersion
6. Detergency
7. Emulsification
11
Effects of Surfactants
Adsorption Controls physical phenomena which are characteristic of surfaces
Foaming Emulsifying
Wetting Dispersing
Micelles Controls physical phenomena which are characteristic of the bulk solution
Viscosity
Solubility (or
Solubilisation Rheology)
Micelle aggregation Can affect surfactant properties
Emulsion stability
Foam stability
Detergency
12
Surface Tension
Adsorption ; Adsorb the surface or interface and change their properties dramatically
Reduce the tension of Surface or Interface

(1) Air / Liquid
Oil or
(2) Liquid / Liquid Air
(3) Solid / Liquid (Air)
Water
Surfactants Water
13
Characteristics by Structure of Surfactants
Adsorption
Change the Electric Charge of the Particle Change the Hydrophobicity or Hydrophilicity
of the Surface of Solid
W a te r o r Water or
+ + + + + Air Air
Hydrophobic Solid Hydrophobic Solid
Water or Water or
- - - - - Air Air
Hydrophobic Solid Hydrophilic Solid
14
Overview of Aggregate Types

Dilute Solution Concentrated Solution
"Particles" Liquid Crystal Phases Crystal Phases
Monolayer at
Air-Water
Interface
Cylindrical
Micelles
(random) Anhydrous
Crystal
Hexagonal
Phase
(Middle)
Unorganized Vesicles H2O H2O H2O H2O
Monomers
H2O H2O H2O H2O
Spherical
Micelles Crystal
Lamellar Phase
Planar Bi-Layers (Neat) Hydrate
Increasing Surfactant Concentration in Water 15

Kraft Point
Solubility in water
; Surface active properties are high when solubility is poor.
The Krafft Point

; In ionic surfactants, solubility increases dramatically above a certain temperature.
Solubility
Tk Krafft points
Compound Tk ( C)
C12H25SO3Na 38
C12H25SO4Na 16
C12H25O(C2H4O)3SO3Na <0
Temperature
16
Critical Micell concentration
cmc Detergency
Conductivity
Changes in some physical
properties of an aqueous solution

Amount
Surface tension containing surfactants
Interfacial tension
Concentration
17
Surfactant Behavior & CMC
CMC of typical surfactants
CMC
Surfactants Temperature
(mole/l) X 10-3
Na Laurylate 25 36
Na Palmitate 70 3.8
Na Lauryl Sulfate 40 8.6
Na Lauryl Sulfonate 40 11.4
Na Do-decyl benzene Sulfonate 60 1.2
DSDMAC 25 0.34
Nonyl phenyl EO (10) 25 0.075
18
Cloud Point
The Cloud Point

; In nonionic surfactants, solubility decreases dramatically above a certain temperature.
The solubility of polyoxyethylanated nonionics is due to hydrogen bonding.
There is no cloud point for polyhydroxyl nonionics.
Solubility
HOH
Cloud points
Hydrogen acceptor CH CH O
2 2 HOH
CH2CH2 Compound Tk ( C)
O CH2CH2OH
HOH C12H25(OC2H4)4OH 6
HOH
C12H25(OC2H4)5OH 32
C12H25(OC2H4)6OH 52
C12H25(OC2H4)7OH 59
19
Cloud Point
The cloud points of 1% aqueous solutions of POE alkyl ether

Carbon Number moles EO Cloud point
6.0 64.9
8.5 81.7
8 10.1 90.8
12.0 97.8
15.0 100 <
6.0 35.0
8.0 58.5
12
10.0 83.5
12.4 92.1
8.0 44.1
9.6 60.7
10.0 66.2
18
11.8 84.3
14.3 92.7
21.1 100 <
20
Wetting effect
Wetting ; The solid has been wetted with the liquid, when a gas/solid interface is
replaced with a liquid/solid interface.
Water Mercury
Glass Glass
Solid surfaces have a Critical Surface Tension (CST)
Without Surfactants (73) With Surfactants (< 32)

Glass (> 73) Wettable Wettable
Polystyrene (32) Cannot be wetted Wettable
21
Emulsification
Emulsion ; Dispersing one liquid into another
Types of emulsion
(1) O/W emulsion
(2) W/O emulsion
(3) W/O/W emulsion
(4) O/W/O emulsion
O/W emulsion W/O emulsion
Water Water Oil
Oil
22
Emulsification
According to emulsion drop size Opaque(Macro)
[m]
> 400nM
50 Macro emulsion
Milky
10
5 Nanoemulsion
2
1 < 400nM
0,5 PIT emulsion Bluish

0,2
10-1
Brownian
Micro emulsion Translucent motion
Effect Microemulsion
increase 10nm~100nM
10-2
Micellar solutions
Transparent
Molecular solutions
10-3 23
Dispersion
Dispersion ; Suspensions of finely divided solids in some liquid medium
Repulsion curves
Dispersal of a solid in a liquid Total repulsion energy
Potential energy of interaction, V

1. Wetting the powder
Distance between particles, H
2. Breaking up the particle clusters
3. Prevention of reaggregation
of the particles
24
Dispersion ; Prevention of reaggregation
Electrostatic forces Steric interaction
-
-- - -
- Particle - Particle
-
- - - --
-
-- - -
- Particle - Particle
-
- - - --
25
Emulsification, Dispersion
Stokess Law
g Q d2
V=
18
v = Sedimentation rate
g = Gravity constant
Q = Difference of apparent density of pearlescent concentrate
and density of formulation
d = Diameter of pearlescent particles
= Viscosity of formulation
26
Detergency
Detergency ; Special property it has of enhancing the cleaning power of a liquid
Detergency
1. Wetting
1. Wetting the soiled substrate
2. Adsorption
2. Removal of the soil from the substrate
3. Emusification
3. Suspension of the soil and prevention of its
4. Solubilisation
redeposition
5. Dispersion
Rolling up mechanism
Oil
Substrate
27
Chemical Structure of Surfactants & Their Property
Properties of Surfactants by Chemical Structure
Type of Hydrophobic Group : Alkyl Length

Un saturated Alkyl group
Type of Hydrophilic Group : Ionic nature
Hydrophilicty
Hydrophilic Property (HLB) : Hydrophilic/Liphophilic Balance
Molecular Shape : Location of Hydrophilic group
Side Chain
Molecular Weight : Polymeric Surfactant
Flocculating effect
28
Hydrophilic Lipophilic Balance (HLB)
HLB value can be calculated roughly from their structural group (Griffin, 1954).
Griffin's method (non-ionic surfactant, Atlas Chemical co.)
MW of hydrophilic part
HLB = 20 X ---------------------------------------
MW of nonionic Surfactant
For example, in the case of Lauryl alcohol 7EO.
CH3(CH2)10CH2(OCH2CH2)7OH
MW H
HLB Value = 20 X
MWL + MWH
325
= 20 X = 13.1
169 + 325
29
Hydrophilic Lipophilic Balance (HLB)

Experimental value is more accurate.
HLB value is just a rough guideline to select right emulsifier.
HLB value
0 5 10 15 20
Emulsifying Penetrating effect

effect (W/O) Solubilizing effect
Defoaming
effect Detergency
Emulsifying effect (O/W)
Lauryl alcohol 7EO.

Penetrating effect
Detergency
Emulsifying effect (O/W)
30
Classifications
of
Surfactants
31
Classifications of Surfactants
Scheme of Raw Materials for Surfactants
Fat and Oils Crude Oil, Natural Gas
Ethylene n-Paraffins
Fatty Acid
Fatty Acids Glycerine Ethylene Oxide
Methyl Esters
-Olefins i-Olefins
Alkanol Fatty Fatty Acids

Amines n-Alkanols Oxoalcohols sec-Alkanols Alkylaryls
Amides Alcohols (Paraffin Oxidation)
-Sulfo Fatty Acid Olefin Alkane

Soaps Soaps
Methyl Esters Sulfonates Sulfonates
Alkyl Ammonium Alkyl Sulfates Alkyl Sulfates Alkylbenzene Sulfonates

Alcohol Ethoxylates
Salts Alkyl Ether Sulfates Alkyl Ether Sulfates Alkylphenol Ethoxylates
32
Surfactant type
Classification by ionic type
Anionic, Cationic, Nonionic and Amphoteric Surfactants
Classification by usage
Washing, Foaming, Anti-foaming, Emulsifying, Dispersing, Penetrating,

Wetting, Solublizing, Polishing, Lubricating, Softening, Anti-static,
Disinfecting.
Classification by structure
Typical Hydrpphobic, Hydrophilic Group
33
Surfactant classification by ionic type
Examples from
Cognis Porfolio
Anionic FAES
(TEXAPON / STANDAPOL )
Amphoteric + Betaine
(DEHYTON / VELVETEX )
Nonionic APG (PLANTACARE )
Cationic + Esterqu. (DEHYQUART )
34
Anionic Surfactants ; Typical Surfactatns

Ion Type Name Structure
Linear Alkylbenzene Sulfonate (LAS)
R SO 3 Na
-Olefin sulfonate (AOS) RCH CHCH2SO3Na

Anionic
Surfactants
Alkyl Sulfate (FAS) R OS O 3 N a
Alkyl Ether Sulfate (FAES) RO(CH2CH2O)nSO3Na
Secondary Alkane Sulfonate (SAS) R1 CH R2

SO3Na
Soap
RCOONa
Methyl Ester Sulfonate (MES) R1 CH R2

SO3 Na
35
Anionic Surfactant
Basic Surfactants in Shampoo

FAES
(TEXAPON / STANDAPOL )
Purpose is to clean and provide a stable foam.
Emulsify, suspend, disperse and remove dirt and sebum
Sodium (or ammonium) laureth sulfates (SLES / ALES)
Most widely used surfactants for shampoos on a global basis.
CH3(CH2)11O(CH2CH2O)2-3SO3-Na+
Ammonium lauryl sulfate (ALS) is popular in the USA.
CH3(CH2)11OSO3-NH4+
36
Anionic Surfactant
Counter ion effect of FAS/FAES
Solubility
Sodium Ammonium MEA TEA
W
B
O
E
R Viscosity Response
S
S TEA MEA Ammonium Sodium T
T
Mildness
Sodium Ammonium MEA TEA
37
Anionic Surfactant
EO effect of FAES
Foam
4EO 3EO 2EO 1EO
W B
O E
R Viscosity
Viscosity Response
Response
S
S 4EO 3EO 2EO 1EO
T
T
Mildness
Mildness
1EO 2EO 3EO 4EO
38
Anionic Surfactant
Effects of Alkyl Chain Length in Surfactants
Impact of the alkyl chain length of LAS Impact of the alkyl chain length of LAS
100 100
Cleaning performance(%)
Cleaning performance(%)
50 50
8-10 10-12 11-12 10-13 13 12-14 100 80 50 20 0 %LAS

0 20 50 80 100 %NP10
Soil: Triglyceride, carbon black, gasoline Soil: Coray 34 (mineral oil, naphthene basis
Substrate: PVC Substrate: PVC
Formulation: 0.1% LAS + 0.03% STP Formulation: 0.1% (LAS + NP10) + 0.03% STP
39
Anionic Surfactant : Soap
Structure of soap
O
CH3(CH2)nCONa
Soap is a generic name for the alkali metal salt of a carboxylic acid derived from animal fats
or vegetable oils.
Sumerians, who inhabited the region between the Tigris and Euphradis rivers, had already
produced soap in 2500 B.C.
Characteristics
1. Widely produced and used in very large volume.
2. It is an excellent detergent.
3. Raw materials independent of the price and availability of petroleum.
4. Biodegrades very readily.
5. Toxicology well known.
40
Anionic Surfactants
Properties of Anionic Surfactants
Have been used since so long ago
Variety of hydrophilic groups
Can be used in hard water (except soaps)
Salts of Sulfuric esters are relatively stable against alkali,
but, easy to be decomposed by acid
Good foaming, cleansing and detergency
Relatively High HLB value
41
Cationic Surfactant
Distearyldimethyl AmmoniumChloride R1 CH3
(DDAC) N Cl
R2 CH3
Cationic CH3
Surfactants N
Imidazolium Salt R1 CH3 OSO 3
N
CH2 CH2 OCR2
O
O
Ester-Containing Quaternary R1COCH2CH2 CH2CH2OH
Ammonium Salt (EQ) O N Cl

R2COCH2CH2 CH3
42
Cationic Surfactant
Synthesis of Typical Surfactants

Cationic Surfactants
C H3
R N + CH3Cl
C H3
Alkyldimethyl Amine Methyl Chloride
C H3
Quaternarization
R N C H3 Cl
C H3
Alkyltrimethyl Ammonium Chloride
43
Cationic Surfactant
What is TEA based EQ ?
CH2 CH2OH CH2 CH2OCOR

ROOH + N CH2CH2OH N CH2 CH2OCOR
CH2CH2OH CH2 CH2OCOR
+ (CH3)2 SO4
CH2CH2OH +
ROCOCH2CH2 N CH2CH2OCOR CH3SO4-
CH3
44
Cationic Surfactant
Monoalkyl quaternaries Dialkyl quaternaries Trialkyl quaternaries
+ + +
CH3 CH3 RR
- - RR - N - CH
-
RR - N - CH
3 Cl R - N - RR
R Cl 3 Cl
CH3 CH3 RR
Laurtrimonium Chloride Quaternium 18 Tricetylmonium Chloride

Tallowtrimonium Chloride Distearyldimonium Chloride
Behentrimonium Chloride
Cetrimonium Chloride
R = Alkyl
45
Properties of Cationic Surfactants
Incompetible with anionic surfactants
Aqueous solution is generally acid
Hair conditioner and Fabric softener
Anti-startic property
Conditioning property by Hydrophobic Group
Good adsorption to charged surface
46
Properties of EQ type Cationic Surfactants
Readily biodegradable
Skin mildness
Dry and comfortable feeling, not greasy
Good re-wetting
Good antistatic performance
No corrosion problem for manufacturing
Environmental frendly under aearobic and anaerobic conditions
Low aquatic toxicity
Easy to handle products & economical simple manufacturing process
Performance in hair conditioners comparable or better than classical quaternaries
47
Nonionic Surfactant : Typical Surfactants
Alkyl Ethoxylate (AE) RO(CH2 CH2 O)nH

Nonionic C H3
Surfactants
Alkyldimethyl Amine Oxide (AO) R N O
C H3
CH2OH
Alkyl Poly Glucoside (APG) O R
O
OH
HO
OH n
O CH2 CH2 OH
Fatty Acid Akanol Amide (FAA)
RCON
CH2 CH2 OH
48
Nonionic Surfactant
Synthesis of Typical Surfactants
Nonionic Surfactants
CH2 CH2
ROH +
O
Fatty Alcohol Ethylene Oxide
NaOH
RO(CH2CH2O)nH
Fatty Alcohol Ethoxylate
49
Nonionic Surfactant
Fatty Alcohol Ethoxylates : General Property
Foaming at room temperature is generally higher for surfactants which have higher HLB.
While the best wetting performance is found near the cloud point (turbidity temperature).
This in accordance that the best surfactant performance is usually found just below the
cloud point (turbidity temperature).
Increasing EO-chain length:

Increases water solubility as evidenced by an increase in cloud point (trurbidity
temperature)
Increasing hydrophilie and wetting properties
Increases the degreasing ability
50
Nonionic Surfactant
Fatty Alcohol EO/PO Adducts : Product Overview

CH3
Principle Structure: CH3(CH2)nCH2(OCH2CH2)x(OCHCH2)yOH
Dehypon LS 24 / LS 36 / LS 45 / LS 54 / LS 64 / 2574
Performance Profile
low foaming at higher temperatures
sufficient antifoam capability
stable at acidic and moderate alkaline pH
51
Nonionic Surfactant
Fatty Alcohol EO/PO Adducts : General Property
A lot of applications require good detergency but low foaming properties.
By adding PO to the fatty alcohol ethoxylate the foam behaviour can be reduced,
also the wetting and emulsifing performance is reduced.
The alkalinity stability could be increased by increasing the PO-chain, but a higher
PO-grade leads to a lower bio-degradability of the surfactant.
To reach products with a high alkaline stability and good degradability n-butyl
endcapped fatty alcohol ethoxylates can be used, e.g. Dehypon LT 104 and
Dehypon LT 054.
52
Amphoteric Surfactant
C H3 O
Alkyl Betaine R N C H2C O
Amphoteric C H3
Surfactants
C H3
R N C H2C H2C H2S O3
Alkyl Sulfo Betaine
C H3
O
R CNH(CH2) 3N CH2CO2
Amido Propyl Betaine
O CH2CO2Na
Ampho Acetate RCN N
CH2CO2Na
OH
53
Amphoteric Surfactants
CH3 O
R N + C lC H 2 C ONa
CH3
Alkyldimethyl Amine Sodium Monochloro Acetate
CH3 O
R N CH2CO
CH3
Alkyl Betaine
54
Betaines
Reduction of Dermatological Irritation
Dehyton K
Texapon NSO
Texapon NSO /
Dehyton K
0 20 40 60 80 100
WAS 20 %; : Texapon NSO / Dehyton K 4:1
55
Properties of Betaines
Cationic and anionic property
Good Conditioning than anionic surfactants
Viscosity modifiers in FS and FES
Foam booster
Reduction of irritation by other surfactants
Compatible with all kinds of surfactants
Bacteriostatic effect
Cloud point reduction
56
Applications
General Formulations
for Personal & home care
57
Applications of Surfactants
Consumer Products Products
Detergents Laundry detergent, Fabric softener
Dishwashing agent
Cleaning agent Floors, Walls, Bathtubs, Toilets, Carpet
Personal products Bar soaps, Body shampoos,

Cosmetics,
Hair shampoos, Hair rinse, Hair dyes
Toothpaste, Mouthwash
58
Industrial Application Products

Foods Milk, Ice cream, Mayonnaise
Pharmaceuticals Cream, Salves
Plant protection and pest control Insecticides, Herbicides
Agriculture Fertilizer
Textiles and fibers Cleaning, Bleaching, Dyeing
Chemical industry Extraction process
Plastic industry Emulsion polymerization
Paint, lacquers Dispersing
Cellulose and paper Cleaning, Dispersing
Leather and furs Cleaning, Emulsifying, Dyeing
Photographic industry Wetting, Dyeing
Metal processing Cleaning, Anticorrosion
Electroplating Cleaning
Adhesives Wetting
Road construction and building materials Emulsifying, Dispersing
Fire fighting Foaming
Mining and flotation Dispersing, Foaming
Oilfield chemicals Extraction process
59
General Components for Formulations
Ingredients Requirements
1. High cleaning performance

2. Surface protection
1. Surfactants 3. Residue free drying of the clean surface
2. Alkalis 4. Good skin compatibility
5. Easy handling/dosage
3. Complexing agents
6. Appropriate foaming behavior
4. Organic polymers 7. Pleasant odor during and after cleaning
5. Solvents 8. Human safety
9. Environmental safety
6. Microbicides
10.Sufficient storage stability
11.Attractive appearance
60
Typical Surfactants in Personal and Home Care
Name Structure
Linear Alkylbenzene Sulfonate (LAS) R SO 3 Na
-Olefin sulfonate (AOS) RC H C HC H 2 SO 3 Na
Alkyl Sulfate (AS) RSO 3 Na
Alkyl Ether Sulfate (AES) RO(C H 2 C H 2 O)nS O 3 Na
Soap RCOONa
Alkyl Ethoxylate (AE) RO(C H 2 C H 2 O)nH

C H3
Alkyldimethyl Amine Oxide (AO) R N O O C H2C H2O H
C H3 RC O N
Fatty Acid Akanol Amide (FAA) C H2C H2O H
61
General formulation ; Hair Shampoo
Ingredients Examples Concentration(%)
Basic Surfactants Laureth Sulfates, Sodium and/or Ammonium salts 15 ~ 20

Amonium Lauryl Sulfate, MAP, APG
Isethionate, Taurate.....
Co-Surfactants Cocamidopropyl Betaine, Coco Betaine, 2~5
Cocoamphoacetates,
Pearlizer/ Opacifier Waxes Glycol Distearate, Distearyl Ether, fatty alcohols 0.5 ~ 2
Conditioner - Cationics GHPTC, Polyquaternium 10 0.1 ~ 0.5
Conditioner - Silicon Dimethiconol, Dimethicone 0.5 ~ 2
Emollients Hydrogenated Polydecene, Glyceryl Oleate, 0.1 ~ 1
Dicaprylyl Ether, Lauryl Alcohol
Actives Panthenol, Aminoacids, fruit-waxes, UV-filters 0.1 ~ 1
Botanicals, Ceramides
Hydrotops q.s
Stabilizer Carbomer q.s
Preservatives, Dyestuffs, pH-Regulators, Fragrances
62
General formulation ; Hair Conditioner
Emulsifiers Fatty alcohol ethoxylates or alkylglucosides 1~3

Consistency factors Fatty alcohols, partial glycerides, 1~5
Esters of long chain fatty acids
Lipid layer enhancers Glyceryl mono Oleate 0.5 ~ 2
Emollients Silicones, paraffin oils 0.5 ~ 3
Active ingredients Protein derivatives, vitamins, herb and plant extracts, ... 0.5 ~ 1
Humactants Glycol derivatives as propylenglycol; glycerin 0.5 ~ 3
Cationic components Quaternary ammonium compounds 1~4
Stabilizers/polymeric derivatives Polymeric derivatives, (HEC, MC, MHPC) 0.1 ~ 0.5
Preservatives q.s
Dyestuffs q.s
pH-Regulators q.s
Fragrances q.s
63
General formulation ; Facial Cleansing foam
Soap Fatty acid: C12~C18 25 ~ 35

Alkali NaOH, KOH, TEA and etc. 3~7
Surfactant Acyl glutamate, Acyl taulate, POE - Alkyl Ether, MAP, 2~5
Emulsifier Nonionic 1~5
Emollient Fatty acid, Fatty alcohol, Lanoline derivative, Wax, 1~5
Jojoba oil, Olive oil and etc.
Humactant Sorbitol, PEG, 1,3-Buthylene Glycol, Propylene glycol, 10 ~ 20
POE - Glycol delivative
Stabilizer Polymer q.s
Scrub Polyethylene bead, Poly acrylate polymer Shell q.s
Chelating agent EDTA 0.01 ~ 0.2
Preservative q.s
Tricloson, Color, Perfume, Anti-oxidant q.s
64
General formulation ; Body Wash
Basic Surfactants Laureth Sulfates, Sodium and/or Ammonium salts 15 ~ 25

(or Soap) Amonium Lauryl Sulfate, MAP, APG
Isethionate, Taurate.....
Co-Surfactants Cocamidopropyl Betaine, Coco Betaine, 2~5
Cocoamphoacetates,
Pearlizer/ Opacifier Waxes Glycol Distearate, Distearyl Ether, fatty alcohols 0.5 ~ 2
Conditioner - Cationics Polyquaternium 0.1 ~ 0.5
Refattying Agent Glyceryl Oleate, Dicaprylyl Ether, Lauryl Alcohol 0.5 ~ 2
Actives Panthenol, Aminoacids, fruit-waxes, UV-filters 0.1 ~ 1
Botanicals, Ceramides
Humactant Glycol 2 ~ 10
Hydrotops q.s
Stabilizer Carbomer q.s
Preservatives, Dyestuffs, pH-Regulators, Fragrances
65
Dermatological compatibility of surfactants
Mucous Membrane of Eyes, Rabbit
D ehyton K
Texapon NSO
Texapon NSO /
D ehyton K
0 20 40 60 80 100
Irritation score
WAS 20 %;
Texapon NSO / Dehyton K 4:1
66
Compatibility (HET CAM)
FES / Co surfactant combinations
1,7
1 2 3
Sodium Laureth
1,5 1,54 2,2 2,2 2,2
Sulfate
1,45
[Q] relative irritation score
Cocamidopropyl
0,8 - 0,4
Betaine
1,3
1,25 Lauryl Glucoside - 0,8 0,4
1,1 up to up to up to
Aqua
100 100 100
0,9 ratio 3 : 1 3 : 1 3:0.5:0.5
pH value 6,5 6,5 6,5

0,7
1 2 3
all values in % AS
Products: Texapon NSO; Dehyton K; Plantacare 1200
67
General formulation ; Powder Detergent
Primary surfactants LAS, FAS, FAES 8 ~ 20

Secondary surfactants Fatty Alcohol Ethoxylate 1~5
Alkyl Polyglycoside (APG)
Soap Fatty Acid 0~3
Alkaline builders / buffers Na Carbonate, Na Silicate, NaOH 5 ~ 15
Filler Na Sulfate 10 ~ 20
Zeolite Zeolite 25 ~ 40
Enzymes Remove difficult soils / stains 0.1 ~ 2
Protease, Amylase,, Lipase, Cellulase..
Fluorescent Brighteners Impart brighter appearance; convert 0.1 ~ 0.5
Stilbene derivatives
Anti-redeposition agents Prevent soils from re-depositing 0.1 ~ 0.5
Polymers; PVP, CMC..
Preservative q.s
Color Protection agent q.s
Fragrance q.s
68
General formulation ; Manual Dishwash Detergent
Primary surfactants Provide flash foam & foam volume 10 ~ 20
LAS, FAS /FAES, AOS
Secondary surfactants Improves grease cutting, soil emulsification 5 ~ 10
APG, Alcohol Ethoxylates (LAE 9-11)
Foam stabilizers Improves foam stability, increases skin mildness 1~3
Cocamide DEA, Betaines, Amine oxides
Antibacterial agents Provides germ kill on hands 0.1 ~ 0.5
Triclosan, PCMX
Hydrotropes Ethanol, SXS, NaCl 1~5
Viscosity adjustment product stability q.s
Fragrance q.s
69
Manual Dishwash Detergent
Semi Automatic Plate Wash Test Method

Lard Test for Fat Redeposition
Test Method:
5 l water
water hardness: 16d
water temperature: 50C
Solution of the dish washing agent

1,0 g or 2,0 g / 5 l
Foam creation via circulation pump

for 30 seconds
70
Semi Automatic Plate Wash Test Method
Lard Test for Fat Redeposition
Cleaning of soiled plates with

automatical controlled
rotating brush
End of test: foam does not cover

the complete surface of the
cleaning solution
(until the foam breaks)
Determination of cleaning performance:

Count number of plates without fat drops
Count number of plates until foam breaks
71
Statistical Experiment Design Test-Formulation

12 % Anionic Surfactants (FES)
16 % Co-Surfactants: APG , CAPB, C9/11-FA+8EO
Plate test on Fat-Soil/ 50C - 16d - 0,2g/l
6,0-8,0 4,0-6,0
Number of plates Number of plates
8,0-10,0 6,0-8,0
until foam breaks without fat drops
10,0-12,0 8,0-10,0
FA %
0
12,0-14,0
16
10,0-12,0
FA %
EO
16
14,0-16,0 A2 A2
EO
12,0-14,0
16,0-18,0
14,0-16,0
18,0-20,0
A7 16,0-18,0
20,0-22,0 A7
8%
8%
8%
A6 A6 A9
8%
A9
A3 A3

% % 4
C1 G
4
G
16 2/1
/1
AP
AP
2
A4 A10 A4 A10
16 1
%
C
0%
0%
0%
A8 A1 A5 A8 A1 A5
0% 8% 16 % 0% 8% 16 %
CAPB CAPB
72
General formulation ; Fabric Softener
Sofetning Ingredients Cationic Surfactant, Ester Quaternary, 5 ~ 7 (Regular)

Imidazoline Quat, DDAC . 15 ~ 35 (Conc)
Emulsifier Nonionic Surfactant 0.5 ~ 2
Alkyl Ether, Sorbitan.
Stabilizer Glycol, Ethylene Glycol. Etc 2~5
Defoamer Silicone Defoamer 0.1 ~ 0.2
Preservative Isothiazoline. etc. 0.1 ~ 0.5
Additive Extract q.s
Aloe, Green Tea Extract
Silicone Silicone Copolyol 0~2
Viscosity Adjuster Electrolite 0 ~ 0.5
NaCl, CaCl2. etc
Color Dyestaff q.s
Perfume Perfume Compound q.s
73
Thank you
74

Basic of Colloidal Phenomena

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Basic of Colloidal Phenomena

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Basics of

June 30, 2011

1. Surface tension and Surfactants

2. Basic Properties and Functions of Surfactants

Surface and Interface Chemistry

A colloid is a substance microscopically dispersed evenly throughout another substance.

and a continuous phase (or dispersion medium).

The dispersed-phase particles have a diameter of between approximately 5 and 1000

Classification of Colloid Dispersion

Liquid Aerosol, Fog, Mist, Hair Spray

Surface tension is a property of the

Surface Tension = Force / Length = dyne / Cm

= Energy / Area = dyne * Cm /Cm2

Water to be spherical Surface energy, surface stress or surface free energy

Surface tension of pure liquids

Oil Without surfactant

Surface-Acive Agent, Surfactant, Amphiphilic Molecule

A hydrophobic part; Water disliking A hydrophilic part; Water liking

Variables: Variables: Variables:

Acetone added to water will reduces the surface tension.

For examples of reduction in surface tension

Concentration Surface Tension Concentration Surface Tension

20% 42dyne/cm 0.0004% 48dyne/cm

The addition of surfactants will change the following properties of water.

The changed properties of water

1. Reduction of surface and interfacial tension

Adsorption Controls physical phenomena which are characteristic of surfaces

Micelle aggregation Can affect surfactant properties

Reduce the tension of Surface or Interface

Hydrophobic Solid Hydrophobic Solid

Hydrophobic Solid Hydrophilic Solid

Overview of Aggregate Types

Unorganized Vesicles H2O H2O H2O H2O

H2O H2O H2O H2O

Increasing Surfactant Concentration in Water 15

The Krafft Point

properties of an aqueous solution

Surface tension containing surfactants

CMC of typical surfactants

Na Lauryl Sulfate 40 8.6

Na Lauryl Sulfonate 40 11.4

Na Do-decyl benzene Sulfonate 60 1.2

Nonyl phenyl EO (10) 25 0.075

The Cloud Point

The cloud points of 1% aqueous solutions of POE alkyl ether

Solid surfaces have a Critical Surface Tension (CST)

Without Surfactants (73) With Surfactants (< 32)

O/W emulsion W/O emulsion

Water Water Oil

0,5 PIT emulsion Bluish

Dispersion ; Suspensions of finely divided solids in some liquid medium

Dispersal of a solid in a liquid Total repulsion energy

Potential energy of interaction, V

Dispersion ; Prevention of reaggregation

Electrostatic forces Steric interaction

Properties of Surfactants by Chemical Structure

Type of Hydrophobic Group : Alkyl Length

Hydrophilic Lipophilic Balance (HLB)

Griffin's method (non-ionic surfactant, Atlas Chemical co.)

For example, in the case of Lauryl alcohol 7EO.

Hydrophilic Lipophilic Balance (HLB)

Emulsifying Penetrating effect

Emulsifying effect (O/W)

Lauryl alcohol 7EO.