Dispersions in liquids: suspensions,
emulsions, and foams
ACS Short Course
April 6 - 7, 2013
New Orleans, LA
Ian Morrison
Lecturer, Harvard University
ian@seas.harvard.edu
Ian Morrison© 2010
Bibliography
Primary text:
Morrison, I.D.; Ross, S. Colloidal dispersions: Suspensions, emulsions, and foams; John
Wiley & Sons: New York; 2002.
Also suggested:
Adamson, A.W.; Gast, A.P. Physical chemistry of surfaces; 6th ed.; John Wiley & Sons:
New York; 1997.
Allen, T. Powder sampling and particle size measurement; Elsevier: New York; 2003.
Becher, P., Emulsions: Theory and practice, 3rd ed.; Oxford University Press: New York;
2001.
Butt, H.-J.; Graf, K.; Kappl, M. Physics and chemistry of interfaces; Wiley-VCH:
Weinheim; 2006.
Conley, R.F. Practical dispersion: A guide to understanding and formulating slurries;
VCH Publishers: New York; 1996.
de Gennes, P.-G., Brochard-Wyart, F.; Quéré, D. Capillarity and wetting phenomena ;
Springer : New York ; 2004.
Derjaguin, B.V. Theory of stability of colloids and thin films; Johnston, R.K.. Trans.;
Consultants Bureau: New York; 1989.
Dickenson, E.; McClements, D.J.; Advances in Food Colloids; Chapman & Hall: New
York; 1996.
Elimelech, M.; Gregory, J.; Jia, X.; Williams, R.A. Particle Deposition and Aggregation;
Measurement, modeling, and simulation; Butterworth-Heinemann: London; 1995.
Exerowa, D.; Kruglyakov, P.M. Foam and foam films; Elsevier Publishing: New York;
1998.
Goodwin, J. Colloids and interfaces with surfactants and polymers; John Wiley & Sons:
New York; 2004.
Gregory, J. Particles in water; CRC Press: Boca Raton, FL; 2006.
Holmberg, K.; Jonsson, B.; Kronberg, B.; Lindman, B. Surfactants and polymers in
aqueous solution, 2nd ed.; John Wiley & Sons: New York; 2003.
Hunter, R.J. Foundations of colloid science, 2nd ed.; Oxford University Press: New York;
2001.
Jenson, W.B. The Lewis acid-base concepts; John Wiley & Sons: New York; 1980.
Kissa, E. Dispersions: Characterization, testing, and measurement; Marcel Dekker: New
York; 1999.
Napper, D.H. Polymeric stabilization of colloidal dispersions; Academic Press: New
York; 1983.
Nelson, Jr., R.D. Dispersing powders in liquids; Elsevier Publishing: New York; 1988.
McClements, D.J. Food emulsions: Principles, practice, and techniques, CRC Press:
Boca Taton, FL; 1999.
Myers, D. Surfaces, interfaces, and colloids: Principles and applications, 3rd ed.; WileyVCH: New York; 2006.
Myers, D. Surfactant science and technology, 3rd edition; Wiley-Interscience: New York;
2006.
Norde, W. Colloids and interfaces in life sciences; Marcel Dekker: New York; 2003.
Ott, J.-E.; Brandreth, D.A. Small particles technology; Plenum Press: New York; 1998.
Pashley, R.M.; Karaman, M.E. Applied colloid and surface chemistry; John Wiley &
Sons: New York; 2004.
Povey, M.J.W. Ultrasonic techniques for fluids characterization; Academic Press: New
York; 1997.
Rosen, M.J. Surfactants and interfacial phenomena, 3rd ed.; John Wiley & Sons: New
York; 2004.
Stein, H.N. The preparation of dispersions in liquids; Marcel Dekker: New York 1996.
Takeo, M. Disperse systems; Wiley-VCH; New York; 1999.
Whitten, T.A. (with P.A. Pincus) Structured fluids: Polymers, colloids, surfactants;
Oxford University Press: New York; 2004.
Williams, RA.; de Jaeger, N.C., Eds. Advances in measurement and control of colloidal
processes; Butterworth-Heinemann: Boston; 1991.
Williams, RA., Ed. Colloidal and surface engineering: Applications in the process
industries; Butterworths: Oxford; 1992.
Ian Morrison ©2008
Bibliography
Course lectures
Course lectures Section Topic
Starting
slide
Preferred order
1
1
Surfactant science and technology
3
2
Steric stabilization
59
3
Electrostatic stabilization
83
4
Emulsion technology
103
5
Foam technology
131
6
Wetting and adhesion
163
7
Particle sizing techniques
197
8
Particle charge and rheology
219
9
Processing dispersions
235
10
Bibliography
251
x
11
Scaling relations
253
x
12
Surfactant companies
261
x
Ice Cream
Ice cream is a:
• Foam
F
off air
i b
bubbles,
bbl
• Stabilized with small oil
drops,
• In a matrix that is
is,
• An emulsion of more oil
drops
• And a suspension of ice
crystals,
• In a continuous phase of
surfactants,
su
acta ts, micelles,
ce es,
and solutes in water
• In a sugar cone.
Ian Morrison© 2010
Etymology
English
Greek
Latin
oil
water
solvent
both
flow
affinity
lack-of-affinity
nature
science
lipohydrolyoamphiamphi
rheo-philic
-phobic
-pathic
p
-logy
oleoaquasolvo-
hydrophilic
lipophilic
lyophilic
hydrophobic
lipophobic
lyophobic
amphipathic
amphiphilic
Ian Morrison© 2010
English meanings are not literal
translations
translations.
Technical terms (neologisms)
are formed by combinations of
these words.
words
rheology = science of flow
=
=
=
=
=
=
=
=
with affinity for water
with affinity for oil
with affinity for the solvent
lack of water affinity
lack of oil affinity
lack of affinity for the solvent
combining both natures (oil and water understood)
with affinity for both (oil and water understood)
Lecture 1: Surfactants
3
S f t t science
Surfactant
i
and
d ttechnology
h l
Dispersions in liq
liquids:
ids ssuspensions,
spensions
emulsions, and foams
Ian Morrison© 2010
Common surfactant molecules
Sodium dodecylsulfate
Cetyl trimethyl ammonium bromide
Tweens
Aerosol OT
• PEO20 sorbitan monolaurate – Tween 20
• PEO20 sorbitan monopalmitate – Tween 40
• PEO20 sorbitan mono
mono-oleate
oleate – Tween 80
• PEO20 sorbitan tristerate – Tween 65
• PEO20 Sorbitan trioleate – Tween 85)
Lecithin
C12EO5
Witten Fig.
Fig 7.1
71
Ian Morrison© 2010
Lecture 1: Surfactants
4
Oil-soluble
Oil
soluble surfactants
Reactions with fatty acids:
• Sorbitan monolaurate – Span 20
• Sorbitan monopalmitate – Span 40
• Sorbitan mono-oleate – Span 80
• Sorbitan tristerate – Span 65
• Sorbitan trioleate – Span 85
Sorbitan mono-oleate (Span 80)
O
Solsperse 17000
S
O
O
(O
O
O
)n N
N
O
S
O
O
O
Polyisobutylene succinimide
Ian Morrison© 2010
Lecture 1: Surfactants
5
Instruction Bulletin No. 1
How to use your ATLAS HLB kit
W.C. Griffin, “Classification of surface-active agents by “HLB”, J. Soc. Cosmetic Chemists, 1, 311, 1949
.
The Spans
p
and
Tweens and blends
are recommended
standards.
10 gms emulsifier
95 gms oil
MixedMixed
95 cc water
pH adjusted
Mixed
Sit 24 hours
Chem Service, Inc. West Chester, PA.
Ian Morrison© 2010
Lecture 1: Surfactants
8
Examples of matching HLB values to application needs
mixing unlike oils together
– use surfactants with HLB
HLB’s
s of 1 to 3
making water-in-oil emulsions
– use surfactants with HLB’s of 4 to 6
wetting
gp
powders into oils
– use surfactants with HLB’s of 7 to 9
making self emulsifying oils
– use surfactants with HLB’s of 7 to 10
making oil-in-water emulsions
– use surfactant blends with HLB’s of 8 to16
making detergent solutions
– use surfactants with HLB’s of 13 to 15
for solubilizing oils ( micro-emulsifying ) into water
– use surfactant blends with HLB’s of 13 to 18
www.stephen-herman.com/week_03_08_notes.ppt
Ian Morrison© 2010
Lecture 1: Surfactants
9
Surfactant adsorption reduces total energy
At the air/liquid interface:
And the solid/liquid interface:
Lowers surface tension.
Stabilizes dispersions.
p
Different surfactants will be adsorbed at differnent interfaces to different degrees!!
Ian Morrison© 2010
Lecture 1: Surfactants
New page
Adsorption at liquid surfaces
Air-water surface
Strong
adsorption,
substantial
lowering of
surface tension.
Ian Morrison© 2010
Air-oil surface
Oil-water interface
Little adsorption,
little lowering of
surface tension.
tension
Strong
adsorption,
substantial
lowering of
interfacial
tension.
Lecture 1: Surfactants
13
Adsorption at solid surfaces
The surfactant must be soluble in the liquid!
Solid-water interface
Solid-oil surface interface
The adsorption is
g
driven byy both strong
tail/solid interaction
and entropy – the
hydrophobic effect.
Ian Morrison© 2010
The adsorption is
driven by strong
head group/solid
interaction.
Lecture 1: Surfactants
14
Micellization is a dynamic
y
process
p
If micellization is an equilibrium reaction:
KB ↔ BK
The law of mass action gives:
[ B ] = constant
[ BK ]
K
[ B ] = constant
[ BK ]
K
The value of K can be quite large;
for SDS it is about 64. The
equilibrium can look like a phase
change (an argument over many
years).
Adsorption and micellization are competing processes
processes.
Ian Morrison© 2010
Lecture 1: Surfactants
New page
Oil “surfactants” form inverse micelles
The micelle
Th
i ll
core is highly
p
polar.
The diameters
are 10’s
10 s of
nanometers.
Ian Morrison© 2010
Lecture 1: Surfactants
22
Solubilization above the CMC
Solubility of 2nitrodiphenylamine in aqueous
solutions of potassium laurate.
Solubilization of dye in water
withTriton X-100 versus
solubilization with acetone. McBain,
1950, Fig. 17.24, p. 264.
5
Solubility gL x 10
2
4
3
2
1
0
0
1
2
3
4
5
6
7
8
9
Percent potassium laurate
The solubility of gas
increases sharply after
micelles
i ll fform ((att th
the CMC)
CMC).
Ian Morrison© 2010
Lecture 1: Surfactants
23
Surfactants make dynamic
y
structures
The work by Janet Iwasa is licensed under a Creative
C
C
Commons AttributionNoncommercial-No Derivative Works 3.0 United States License.
Ian Morrison© 2010
Lecture 1: Surfactants
27
Surfactant “self-assembly”
y
(a) Spherical micelles with an interior composed
of the hydrocarbon chains and a surface of the
polar head g
p
groups
p (p
(pictured as spheres)
p
) facing
g
water. (b) Cylindrical micelles with an interior
composed of the hydrocarbon chain and a surface
of the polar head groups facing water. The crosssection of the hydrocarbon core is similar to that of
micelles. The micellar length is highly variable so
th
these
micelles
i ll are polydisperse.
l di
( ) Surfactant
(c)
S f t t
bilayers which build up lamellar liquid crystals
have for surfactant-water systems a hydrocarbon
core with a thickness of ca. 80% of the length of
two extended alkyl chains. (d) Reverse or
inverted micelles have a water core surrounded
by the surfactant polar head groups. (e) A
bicontinuous structure with the surfactant
molecules aggregated into connected films
characterized by two curvatures of opposite sign.
(f) Vesicles are build from bilayers similar to those
of the lamellar phase and are characterized by two
distinct water compartments.(Description from
Holmberg et al. Fig. 2.1, p. 40; Diagrams from
Evans et al., Fig. 1.6, pp 14-15).
Ian Morrison© 2010
Lecture 1: Surfactants
29
Kinetics in surfactant systems*
y
Transitions
T
iti
can be
b
between all phases.
Molecule
M
l
l entering
t i micelles
i ll microseconds
Micelles to molecules order of a minute.
Micelles to vesicles –
order of hours
*Gradzielski, Current Contents in Colloid & Interface Sci, 8, 337, 2003.
Ian Morrison© 2010
Lecture 1: Surfactants
35
The Krafft temperature
p
Krafft temperature is the
temperature at which surfactant
solubility equals the critical micelle
concentration. Above the Krafft
temperature surfactants for a
dispersed phase; below the Krafft
temperature they crystallize out of
solution as hydrated crystals
crystals.
(Evans, Fig. 1.3, p. 9)
Ian Morrison© 2010
Lecture 1: Surfactants
24
Surfactant p
phase diagram
g
((Three component)
p
)
Butanol
20
80
40
60
L2
60
40
Lα
80
20
L1
Water
H1
I1
20
40
60
80
Phase diagram of the E100P70E100–
butanol–water system at 25oC.
The tie-lines are represented by
g lines. L1 denotes the
full straight
water-rich (micellar) solutions
region, I1 the normal (“oil”-inwater) micellar cubic liquid
crystalline
t lli region,
i H1 the
th normall
hexagonal liquid crystalline
region, Lα the lamellar liquid
crystalline region, and L2 the
alkanol-rich solution region.
E100P70E100
Morrison, Fig. 13.21, p. 272.
Ian Morrison© 2010
Lecture 1: Surfactants
30
Surfactant(SDS)
(
) – Polymer
y
interaction
Polymer saturated
with surfactant.
Apparent CMC.
Onset of surfactant/polymer interaction.
Ian Morrison© 2010
Lecture 1: Surfactants
Holmberg et al.,
al p.
p 278
37
Biogenic
g
monolayer:
y Lung
g surfactant
Surface tension is greatly reduced by compression on exhaled breath, regulating capillary
pressure promoting involuntary inhaling
pressure,
inhaling. Premature babies lack lung surfactant.
surfactant The
layers are strong – maximum spreading pressures of 68-72 mN/m compared to stearic
acid of about 40 mN/m. The collapsed films relax slowly on expansion.
Fluorescence microscopy a monolayer of
phospholipids containing Rh-DPPC at different
surface pressures (in units of nMm-1) during
continuous compression at 0.03 nm2 per moleculemin. The non-fluorescent area correspond liquid
condensed domains, fluorescent areas correspond
to liquid expanded domains. Highly fluorescent spots
are collapsed structures.*
*Engelskirchen. Current Contents in Colloid & Interface Sci, 12, 68, 2008.
Lecture 1: Surfactants
Ian Morrison© 2010
40
1. Surfactant Producers
3M Corp.
Air Products
Akzo Nobel Surfactants America
Albemarle Corp.
Arizona Chemical
BASF Corp.
Chemtura
Clariant Corporation
The Cognis Group
Croda Inc.
DeForest Enterprises, Inc.
Dow Corning
DuPont
EAC Chemicals
Ethox Chemicals
Evonik - Degussa
Henkel KGaA (The Henkel Group)
Huntsman Corp.
ICI – Akzo Nobel
Libra Chemicals Ltd
Lonza Inc.
Lubrizol Corporation
MacDermid, Inc.
McIntyre Group Ltd.
Montello Inc.
National Starch and Chemical Company
Nikko Chemicals
Novo Nordisk A/S
Petroferm, Inc.
PILOT Chemical Company
Procter & Gamble Chemicals
Rhodia
Rohm and Haas
Shell Chemical
Stepan Co.
Uniqema
2. Surfactant Distributors
Barton Solvents
Byk Chemie
The M.F. Cachat Company
New Life Chemical & Equipment
Schibley Chemical Company
Spectrum Laboratory Products, Inc.
Surfactants, Inc.
Thornley Company
Univar USA
This information was originally obtained from the
Surfactants Virtual Library by Dr. Paul Huibers but is no
longer active.
Reference material
Ian Morrison© 2010
Lecture 1: Surfactants
42
Bibliography
g p y for surfactants
Becher, P., Ed. Encyclopedia of emulsion technology, Vol. 1 Basic Theory, 1983; Vol. 2
Applications, 1985; Vol. 3 Basic theory, measurement, applications, 1988; Vol. 4,
1996; Marcel Dekker: New York.
Conley R.F.
Conley,
R F Practical dispersion: A guide to understanding and formulating slurries;
VCH Publishers: New York; 1996.
Flick, E. W. Industrial surfactants; Noyes Publications: Park Ridge, NJ; 2nd ed. 1993.
Karsa, D.R., Ed. Industrial applications of surfactants II; Roy. Soc. Chem.: Cambridge;
1990.
Laughlin, R.G. The Aqueous phase behavior ofsSurfactants; Academic Press: New York;
1994.
McCutcheon's: Emulsifiers & Detergents, American Edition, MC Publishing: Glen Rock,
NJ; (An annual publication.)
Mukerjee, P.; Mysels, K.J. Critical micelle concentrations of aqueous surfactant systems;
Nat. Stand. Ref. Data Ser., 36; U.S. Government Printing Office: Washington, DC;
97 .
1971.
Nelson, Jr., RD. Dispersing powders in liquids; Elsevier Publishing: New York; 1988.
Rosen, M.J. Surfactants and interfacial phenomena; John Wiley & Sons: New York; 1st
ed, 1978; 2nd ed., 1989.
Schwuger, M.J., Ed. Detergents in the environment; Marcel Dekker; New York; 1997.
Shinoda, K.; Nakagawa, T.; Tamamushi, B-I; Isemura, T. Colloidal surfactants, Some
physicochemical properties; Academic Press: New York; 1963
1963.
Shinoda, K., Ed. Solvent properties of surfactant solutions; Marcel Dekker: New York;
1967.
Shinoda, K.; Friberg, S. Emulsions and solubilization; John Wiley & Sons: New York;
1986.
Tanford, C. The hydrophobic effect: Formation of micelles and biological membranes;
John Wiley & Sons: New York; 1980.
Ian Morrison© 2010
Lecture 1: Surfactants
43
Typical
yp
entries in Nelson
Ian Morrison© 2010
Lecture 1: Surfactants
45
Dispersants
p
Ian Morrison© 2010
Lecture 1: Surfactants
44
McCutcheon’s Handbook
Ian Morrison© 2010
Lecture 1: Surfactants
46
Typical
yp
entryy in McCutcheon’s
Ian Morrison© 2010
Lecture 1: Surfactants
47
Chemcyclopedia
y p
((ACS annual p
publication))
Ian Morrison© 2010
Lecture 1: Surfactants
48
Typical
yp
page
p g in Chemcyclopedia
y p
Ian Morrison© 2010
Lecture 1: Surfactants
49
Solsperse®
p
Surfactants
Now from Lubrizol Corp.
Ian Morrison© 2010
Lecture 1: Surfactants
750
From Byk
y Chemie – Low MWs
Ian Morrison© 2010
Lecture 1: Surfactants
51
From Byk
y Chemie – High
g MWs
Ian Morrison© 2010
Lecture 1: Surfactants
52
From Byk
y Chemie – Media p
properties
p
Ian Morrison© 2010
Lecture 1: Surfactants
53
Acid/Base scale: Drago
g E and C p
parameters
Bases
Pyridine
Ammonia
Methylamine
Dimethylamine
Trimethylamine
Ethylamine
Di th l i
Diethylamine
Triethylamine
Acetonitrile
p-Dioxane
Tetrahydrofuran
Dimethyl sulfoxide
E h l acetate
Ethyl
Methyl acetate
Acetone
Diethyl ether
Isopropyl ether
Benzene
p-Xylene
Cb
13.09
13
09
7.08
11.41
17.85
23.6
12.31
18 06
18.06
22.7
2.74
4.87
8.73
5.83
3 56
3.56
3.29
4.76
6.65
6.52
1.452
3.64
Ian Morrison© 2010
Eb
2.39
2
39
2.78
2.66
2.33
1.652
2.80
1 771
1.771
2.03
1.812
2.23
2.00
2.74
1 994
1.994
1.847
2.018
1.969
2.27
1.002
0.851
Acids
Iodine
Iodine monochloride
Thiophenol
p-tert-Butylphenol
p-Methylphenol
Phenol
p-Chlorophenol
tert-Butyl alcohol
Trifluoroethanol
Pyrrole
Isocyanic acid
Sulfur dioxide
Antimony pentachloride
Chloroform
Water
Methylene chloride
Carbon tetrachloride
Lecture 1: Surfactants
Ca
2 05
2.05
1.697
0.405
0.791
0.826
0.904
0.978
0.614
0.922
0.603
0.528
1 652
1.652
10.49
0.325
0.675
0.02
0.00
Ea
22.05
05
10.43
2.02
8.30
8.55
8.85
8.88
4.17
7.93
5.19
6.58
1 88
1.88
15.09
6.18
5.01
3.40
0.00
54
Acid/Base scale: Gutmann Acceptor-Donor
p
Numbers
Acidic Solvents
AN
Basic Solvents
kcal mol-1
Hexane (reference solvent)
Diethyl ether
Tetrahydrofuran
B
Benzene
Carbon tetrachloride
Diglyme
Glyme
HMPA
Dioxane
Acetone
N-Methyl-2-pyrrolidinone
DMA
Pyridine
Nitrobenzene
Benzonitrile
DMF
Dichloroethane carbonate
PDC
CH3CN
DMSO
Methylene chloride
Nitromethane
Chloroform
Isopropyl alcohol
Ethyl alcohol
Formamide
Methyl alcohol
Acetic acid
Water
CF3COOH
CH3SO3H
SbCl5 as ref. in DCE
0
3.9
8.0
82
8.2
8.6
9.9
10.2
10.6
10.8
12.5
13.3
13.6
3.6
14.2
14.8
15.5
16.0
16.7
18.3
18.9
19.3
20 4
20.4
20.5
23.1
33.5
37.1
39.8
41.3
52.9
54.8
105.3
126.3
100
DN
Basic Solvents
kcal mol-1
1,2-Dichloroethane
Benzene
Sulfuryl chloride
Thi l chloride
Thionyl
hl id
Acetyl chloride
Tetrachloroethylene carbonate
Benzoyl fluoride
Benzoyl chloride
Nitromethane
Dichloroethylene carbonate
Nitrobenzene
Acetic
ce c anhydride
a yd de
Phosphorous oxychloride
Benzonitrile
Selenium oxychloride
Acetonitrile
Sulfolane (tetramethylene sulfone)
Dioxane
Propanediol 1,2-carbonate
Benzyl cyanide
Ethylene sulfite
Isobutyronitrile
Propionitrile
Ethylene carbonate
Phenylphosphonic difluoride
Methyl acetate
n-Butyronitrile
Acetone
Ethyl acetate
Water
Phenylphosphonic dichloride
Diethyl ether
0.1
0.1
04
0.4
0.7
0.8
2.3
2.3
2.7
3.2
4.4
10.5
0.5
11.7
11.9
12.2
14.1
14.8
14.8
15.1
15.1
15 3
15.3
15.4
16.1
16.4
16.4
16.5
16.6
17.0
17.1
18.0
18.5
19.2
DN
kcal mol-1
Tetrahydrofuran
Diphenylphosphonic chloride
Trimethyl phosphate
T ib l phosphate
Tributyl
h h
Dimethoxyethane
Dimethylformamide
N-Methyl-2-caprolactam
N-Methyl-2-pyrrilidinone
N,N-Dimethylacetamide
Dimethyl sulfoxide
N,N-Diethylformamide
N,N-Diethylacetamide
N,N
e y ace a de
Pyridine
Hexamethylphosphoramide
Hydrazine
Ethylenediamine
Ethylamine
Isopropylamine
tert-Butylamine
Ammonia
Triethylamine
20.0
22.4
23.0
23 7
23.7
∼24
26.6
27.1
27.3
27.8
29.8
30.9
32.2
3
.
33.1
38.8
44.0
55.0
55.5
57.5
57.5
59.0
61 0
61.0
W.B. Jensen
The Lewis Acid-Base Concepts:
An Overview
Wiley-Interscience: NY; 1980
Ian Morrison© 2010
Lecture 1: Surfactants
55