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INTERFACIAL

PHENOMENA and

MICRO-NANOPARTICLES

Shlomo Magdassi
Casali 204
magdassi@mail.huji.ac.il

A. Interfacial phenomena and


colloid chemistry

1. Basic concepts; surface energy;


systems characterization.
2. Adsorption at interfaces.

3. Electrical charges at interfaces


4. Colloidal systems.
5. Wetting, foaming, detergency.

PEPPER

B. Particles
6. Fundamental processes for the
achievement of particles
Precipitation and chemical reduction
in solutions.
Evaporation from emulsion.
Reaction in a gas phase.
Grinding.

Polymerization in emulsion.
Syntheses in ordered systems
Sol-gel.
Reactions at the interface.
Coacervation.

7. Representative processes for


preparation of particles;
Organic microspheres

Microcapsules
Metallic nanoparticles
Latex

Bibliography
1. Principles of Colloid and Surface
Chemistry, P.C. Hiemenez, Marcel Dekker,
N.Y., 1977.
2. Physical Chemistry of Surfaces, A.
Adamson, John Wiley & Sons, N.Y., 1990.
3. Surfactants and Interfacial Phenomena,
M.J. Rosen, 1991.
4. Specific references indicated during class.
Additional books related to this course can be
found in the library.
Key words: Interfaces, surfactants, colloid
chemistry, adsorption, emulsions, dispersions,
nanoparticles, microparticles, etc.
Attending Classes
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Change in general energy as a result of


a change in surface area.

Surface layer

At the surface, attractive forces act


asymmetrically.
7

Water-Air Interface

C18H38

H2O

Interface Increased Energy


9

A change in general energy as a result of a


change in surface area.
dG = dA
= ( dG
dA

)T,V,n

GS = Surface Free Energy, erg/cm2


GS min
A min

Coalescence of
of droplet

Curvature of
liquid surface

Formally, the surface tension is defined as the


partial derivative of the free energy G with
respect to area A.
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Division of bulk into particles:


Increased Surface Area

11

1 cm3 , A = 6 cm2

1 m3 cubes,

0.1 m3 cubes,

A = 6 104 cm2

A = 6 105cm2

Dispersion Systems: Examples

Aerosols
Paints
Cement
Cosmetic Creams

Particle/Droplet Size
Surface Energy
Interactions/Stabilization

13

Two-Phase Colloidal Systems: Definitions

Acceptable name

Dispersion phase

Medium

Aerosol

Aerosol

Foam

Emulsion

Suspension,
colloidal solution

Solid foam

Gel, solid emulsion

Alloy

Colloid = Glue (Greek)

14

Dispersion Systems Examples

Examples

Name

Medium

Dispersed
phase

Fog

Liquid aerosol

Dust

Solid aerosol

Soap bubbles

Foam

Milk,
cosmetic cream

Emulsion

Paint, ink

Sol, suspension
Dispersion

Tooth paste

Paste

Insulating foam

Solid foam

Margarine

Solid emulsion

Dry paint

Solid
dispersion

15

Typical Colloidal Dispersions

Micelles

Dispersions

Emulsions
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Particles in Nature

Virus

Clay
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E Ink ( Kindel )

Surfactants

RCOO Na+

R8-18c

cmc

log C

wetting
micelles
emulsion
flocculation
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SDS Micelle
Micellar Solutions (Shampoo)

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Self Organized Structures

A) A cylindrical micelle
B) A bilayer
21

Application of Colloid-Surface
Phenomena
Detergency
Enhanced oil recovery

Emulsification
Adhesion
Ore floatation
Lubrication
Water repellency
Protein adsorption
Latex formation

Precipitation
Filtration
22

Colloid Chemistry in Israel


Paints
Inks and printing
Resins

Cosmetics
Pharmaceutics
Agriculture

Food
Detergents
23

Surface / bulk molecules


Cube: Total number of molecules
in a cube:
(molecule length = h) = d3/h3
d: edge of a cube
Number of molecules at the
surface = 6d2/h2

Ratio of surface molecules:


total number: 6h/d

24

25

Percentage of molecules
in the surface
Percentage of molecules in the surface

25

20

15

10

-2

-1

log d/m
Variation of the percentage of molecules in the
surface as a function of particle size for a
substance with a molar volume of 30 cm3 mol-1

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Fluid Interfaces
air

liquid

Molecules will leave the interface for the


interior of the liquid.

Surface curvature
Surface

Interface

27

Surface Tension
A

D
d

l
B

F
C

Surface area of a film (two sides) : l d 2


W = F d
If is defined as the force acting along DC (dyne/cm)
F = l 2
W = l 2 d = S
= W/S
is the work in ergs necessary to generate 1cm2
of a new surface
28

The surface energy may be defined as the


excess energy at the surface of a material
29
compared to the bulk.

In small dimensions, surface


tension dominates over other forces

30

Film: 0:30-2:05

31

= Surface free energy per


unit area
Dyne
cm
cm cm

erg
= cm2

Surface tensions of pure liquid


(dynes/cm)
Water

72.8

Mercury

485.0

Nitrobenzene

43.38

Oleic acid

32.5

Benzene

28.86

Toluene

28.4

n-Octane

21.77

n-Hexane

18.43

Olive oil

35.8

Molten metals
Ethanol

350-1800
22.5

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Surface Tension - Solution


Isooctane/Benzene

Molten Nitrates

Water/
ethanol

NaCl/
water

surfactants

33

Surfactants

RCOO Na+

R8-18c

Soap

cmc

log C

wetting
micelles
emulsion
flocculation
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OF SOLUTIONS
Changes at High Concentrations

35

Temperature Effect
T

= o (1- T/TC)n
Guggenheim-Katayama
o - constant for each liquid
n - empirical factor, ~1.3 organic liquid
TC - critical temperature

Pressure Effect
P
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Surface Tension of Water as a


Function of Temperature

37

Dynamic Surface Tension


72

68

15

t (msec)
0.1N adipic acid
HOOC - (CH2)4 - COOH

50

0.1 mg/ml

40

1 mg/ml
2

BSA

t (hrs)
38

Water Calming Film

39

demonstration - wetting with


heating

/ : -
12

Hexane

51.0

18.4

CCl4

48

26.9

Benzene

35

28.9

n-Octanol

8.5

27.5

n-Hexanol

6.8

n-Pentanol

4.4

n-Butanol

1.6

Ethanol

Mercury

375

485

Hexane

Butanol

Water

Water

41

Estimation of Interfacial Tension

1. Antonoffs Rule
12 = 1 - 2
(1,2 at saturation)

2. Girifalco & Good


12 = 1 + 2 - 2(12)1/2

4V11/3 V2 1/3
=
(V1 1/3 + V2 1/3)2

V - molar vol.

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Estimation of Interfacial Tension


3. Owens & Wendt
Surface tension value is composed of
polar (P) and non-polar (d) parts

12 = 1 + 2 - 21d 2d - 21p 2p
w =h + d = p + d
http://www.firsttenangstroms.com/pdfdocs/
OwensWendtSurfaceEnergyCalculation.pdf
43

oil

(dwater oil)1/2
Oil phase

(d

water

oil

)1/2

water

Water phase

Schematic representation of the contributions to an


oil-water interfacial tension.

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An Example for Calculating d p


Data:
12 hexane water : 51.1 dyne/cm
hexane = 18.4 dyne/cm
H2O = 72.8 dyne/cm
phexane = 0
51.1 = 18.4 + 72.8 - 2wd 18.4
wd = 21.8 dyne/cm

wh = 72.8 - 21.8 =51 dyne/cm


Adhesion p,d

45

46

47

Surface Curvature
gas

G1 = 4R2, G2 = 4(R2 - 2Rdr + dr2)

G 8 Rdr
P 4R2dr = 8 Rdr
Work against pressure difference.

P = 2 (/R)
( P = 4 (/R) for two surfaces )
Young & Laplace : P = (1/r1 +1/r2 )
Sphere: r1 = r2
Flat surface: r1 = r2 =

48

p for water drops of different radii at

Droplet
radius

1 mm

0.1 mm

1 m

10 nm

p (atm)

0.0014

0.0144

1.436

143.6

49

Liquids in Capillaries
r

Wetting
h
P=0

Capillary rise

non-Wetting

Capillary depression

P = 2/r
P = gh
= (rhg )/2

hydrostatic pressure
( = 0o, 180o)

50

Up to 200 lit/hr!

Filling channels,
membranes
51

Surface Tension Measurement


by a Capillary
= (rhg )/2
Chloroform:

d = 1.476 g/cm3
h = 3.67 cm
r = 0.01 cm
=?

= 0.50.013.671.476981 = 26.6
(gcm/sec2cm)

= 26.6 dynes/cm
Water:

= 72 dynes/cm
h = 9.9 cm

Water,

r = 0.1 cm

h = 0.99 cm
52

Capillary demo

Surface Tension Measurements Methods


Ring Method (Du Nouy)

R >> r
f = 22R ( =0 )

= f/4 R
For i, ring must be wetted (=0 ) by the lower
Liquid. If CCL4/H2O, ring must be hydrophobic54

From:http://www.kruss.de/en/theory/measur
ements/surface-tension/ring-method.html
55

56

57

58

Interfacial Tensic

Interfacial Tension of
Clean and Dirty Engine Oils

Time(s)

Synth-C
Synth-D
Nat-C
Nat-D
SunOil
59

Wilhelmy Plate Method

platinum, glass, mica

Wtotal = Wplate + 2( w + t )
(for complete wetting (=0)

=0
w : width
t : thickness
W : weight

Wtotal = Wplate + 2( w + t ) cos


60

61

O
C12

O-

Na+

O
62

Drop Weight Method

Drop weight method (drop and tip enlarged)

2r = mg

= (mg/ 2r)
mg: max. weight which can be supported
by surface forces.
: empirical tables.
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64

65

Pendant Drop Method


The shape of the drop is determined by
its radii of curvature.

Sw

H=SE

SE

66

* Maximum bubble pressure:


P + P1 = gh +2/R

67

Contact Angle

68

Wetting demo

Sessile Drop

70

Oscillating Jets

71

Droplet Ejection Process


HP Printer
viewing

From : C. Shih, http://www.eng.fsu.edu

72

Formation of Particles by Jetting

73

Controlling Surface
Tension by Surfactants

RCOO Na+

R8-18c

cmc

log C

wetting
micelles
emulsion
flocculation
74

Surfactants Classification

1. Anionic

R C OO() Na(+)

2. Cationic

R (+)N(CH3)3 Cl()

3. Zwitterionic

R (+)NH2CHCH2 COO()

4. Nonionic

C OH O
COCR
C O C R
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Module :Amphiphilic structure :


1-7

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Usage of Surface Active Agents

Micellization solubilization
Production and stabilization of emulsions
Production and stabilization of dispersions
Foaming

Fluctulation
Floatation
Wetting

Products: Detergents, medical and cosmetic


emulsifiers, inks and paints.
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Demo Foaming,
Wetting With Surfactant

78

Film :
0-2:57
4:46-13:35

18:30-20:20

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