Rheology of emulsions

Stefano Guido Dipartimento di Ingegneria chimica Universit degli Studi di Napoli Federico II steguido@unina.it

Background
Emulsions are two-phase mixtures of immiscible fluids containing emulsifier(s)

Rheological (and sensorial) properties are strongly affected by (flow (flow-induced) induced) morphology
Oil/water systems cosmetics and toiletries: sunscreen creams and lotions food products: milk, mayonnaise, margarine agriculture: pesticides pesticides, pharmaceuticals: drug delivery Immiscible polymer blends 2

Examples p

OUTLINE
0

Microstructure

Description Stability y

100

Z [ m]
200

300 400 300 200 400 250 200 150 100

X [ m]

Y [ m]

100

50

Mechanical methods

Preparation i
Phase separation

Drop deformation and breakup

Flow-induced morphology
Drop coalescence Viscosity
25 m

Rheological measurements
Dynamic tests
3

Microstructure - 1
Rheological (and sensorial) properties are strongly affected by microstructure Size (1 (1-100 100 m) Concentration Shape (drops, (d fib fibrils...) il )

D Drops

Fibrils

Co-continuous Co co t uous Lamellae

(Meijer et al., 1988)

S i l cases: multiple-phase Special li l h emulsions, li microemulsions i li (0.01-1 (0 01 1 m), ) microencapsulation i l i

4

Microstructure - 2
Prediction and control of microstructure is a very complex task Effects of flow during processing and usage Emulsions are unstable systems Ostwald ripening
increased solubility with curved interface

rheological properties

Creaming
sedimentation

Aggregation
colloidal interactions (van der Waals attraction)

Coalescence
not well understood

Partial coalescence
Drops containing a network of solid particles
5

Preparation
Mechanical methods: pipe flow (static mixers), stirring, colloid mill, homogenizer
Modelling M d lli is i quite it complex: l it should h ld take t k into i t account t drop d breakup, b k coalescence, l action ti of f emulsifiers, effects of flow field inhomogeneity (e. g., high stretching vs stagnation zones) Monitoring morphology evolution is also a difficult task: optical techniques (turbidity, microscopy, light scattering), rheological methods

Phase separation
Gelatin solution 60C Maltodextrin solution 60C

Example: low-fat margarine

Mixing in stirred vessel 60C P t i ti 72C Pasteurisation

Phase separation and gelation g

Cooling and mixing in scraped surface heat exchangers g

6

Flow-induced morphology - 1
The evolution of morphology during flow is governed by two basic events: drop deformation and breakup drop coalescence

Example: aqueous mixture of gelatin and dextran in shear flow (video)

7

Flow-induced morphology - 2

Flow direction

Example: aqueous mixture of Na-alginate and Na-caseinate in shear flow

No drop breakup!
8

Flow-induced morphology - 3

Flow direction

Same system as in previous slide, but with inverted phases

Here drop breakup takes place

9

Drop

deformation in shear flow - 1

The previous phenomena can be explained by looking at the behavior of an isolated drop in well-defined flow fields

Drop deformation in simple shear flow

The deforming effect of shear flow is opposed by interfacial forces acting to restore spherical shape

Interfacial source of elasticity Finite relaxation time

10

Drop deformation in shear flow - 2

Shear flow can be generated in a parallel plate apparatus
Full characterization of drop shape requires two perpendicular views

View along vorticity (video)

View along velocity gradient

25 m

Example: drop of polydimethylsiloxane in polyisobutilene

11

Drop deformation in shear flow - 3

Analysis of drop shape a, b, view along vorticity
y y

view along g velocity y gradient g

a b

by image analysis techniques (edge finding algorithms)

Drop deformation described by a deformation parameter D

D = a b a +b

0 - spherical shape 1 - in the limit of full elongation

12

Drop p deformation in shear flow - 4

Relevant physical quantities (no emulsifiers, no intertia, Newtonian fluids) : c d viscosity of continuous phase viscosity of drop phase shear rate drop radius at rest interfacial tension R

V
& =
V

&
R

13

Drop deformation in shear flow - 5

Nondimensional parameters governing drop deformation

Ca =

c R&

Capillary p y number (ratio ( of shear stress to interfacial forces) ) Viscosity ratio

= d
y y

a
x

Main theory prediction (under steady state conditions) D = Ca 19 +16 16 +16

D = a b a +b

Good agreement with experimental results - valid up to moderate deformations - holds true even if the components fluids are elastic - provides a method to measure interfacial tension
14

Drop breakup in shear flow - 1

Upon increasing Ca, a critical condition (Cacr) is reached where shape becomes unstable (video)

=1 Ca>Cacr

=1 Ca>>Cacr

15

Drop breakup - 2
Drop breakup in shear flow Breakup k modes d depend d d on and d Ca

<< 1 (tip streaming) 1 1

C just Ca j t above b C cr Ca

C >> Ca Ca C cr

16

Drop breakup - 3

There is a critical value of for breakup in shear flow ( 4)

Taylor prediction: Cacr = O(1)

Grace, 1982

No critical value for extensional flow

17

Drop breakup - 4
Breakup can also take place after cessation of flow by Rayleigh instability
1

50 m
2

Growth of perturbation is driven by interfacial tension Relevant in microencapsulation

Flow direction

18

Viscoelastic effects - 1
Liquid-liquid dispersions are always viscoelastic systems, due to interfacial tension Effects of the intrinsic elasticity of the fluid components on flow-induced morphology
Addi i l physical Additional h i l quantities: i i normal l stress differences diff

Drop p orientation is directly y linked to N1

Example (video) outer fluid: non non-Newtonian Newtonian inner fluid: Newtonian =1

Ca = 0 0.4 4

19

Viscoelastic effects - 2
Elastic El i matrix i phase h
Lamellar morphology = 0.1

Elastic drop phase

(Migler, 2001)

Vorticity alignment

Breakup modes (video)

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Coalescence - 1
The evolution of morphology during flow is governed by two basic events: drop deformation and breakup drop coalescence Collision between two drops in shear flow (video)

The resulting Th lti drop d is i broken b k up and d the th daughter d ht drops d are made d to t collide llid again (video)

Examples: p polyisobutilene p y in polydimethylsiloxane p y y ( 1) )

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Coalescence - 2
h

External flow
Collision frequency q y Contact force Contact time

Internal flow
Flattening g (film radius, a) Film drainage (film thickness, h)

Confluence

Film rupture (h = hc)

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Coalescence - 3
Film drainage: effect of interface mobility

Film rupture: the actual mechanism of is unknown

Formation of a hole by chance (Brownian motion) Development p of varicose capillary p y wave (instability) ( y)
Film

Drop 1 Drop 2

Predictions for deformable, partially-mobile drops in shear flow: y low C Ca and low-dispersed p p phase viscosity y coalescence is favored by
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Coalescence - 4
Action of emulsifiers Surfactants amphiphilic nature lower interfacial tension emulsion preparation stabilize emulsions by preventing coalescence
Interface behaves like a viscoelastic membrane

Interfacial tension Low High Low Flow of continuous phase induced by interfacial tension gradients (Marangoni effects) hinders film drainage and coalescence The continuous phase of an emulsion is commonly the one in which surfactant is soluble (Bancrofts (Bancroft s rule)

Polymers
Slow (even irreversible) adsorption kinetics Stabilize emulsions by steric interaction
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Coalescence - 5
Fl Flow-induced i d d coalescence l

d n vs. strain - 5% PIB, step-down from 3 to 0.3 s

-1

dn (m)

10

10 1

10 2

10 3 strain

10 4

10 5

25

Drop size can be measured by automated image analysis l i techniques

Dextran in Gelatin Mix 8 - 8; Blend 3%wt

Relative refractive index (n1,2)= 0.993

26

Rheological measurements - 1
Emulsion rheology is strongly affected by morphology
Importance of deformation history (e. g., preshear to eliminate loading effects)

Effect of volume fraction on viscosity

Phase inversion Effect of surfactants Positive deviations from the log additivity rule: log = c log c + d log d

27

Rheological measurements - 2
Effect of shear rate and drop size
Oil in water (with ( i h 20 wt% % anionic i i surfactant f and d 2.3 23 wt% polyacrylic acid) = 8.19 d = 6.54 x10-2 Pas

c = 7.99 7 99 x 10-3 Pa Pas s = 3.2 mN/m

Sauter mean diameter (m) 8.9 15.4 26 3 26.3

Sample E1 E2 E3

(Otsubo and Proudhomme, 1994)

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Rheological measurements - 3
Master curve at = 0.8 Viscosity curves do not scale with Ca
Viscosity dissipation due to deformation of continuous thin films and internal circulation inside the drops

Dynamic viscoelasticity

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Rheological measurements - 4
Vi Viscoelastic l ti behavior: b h i G
Polydimethylsiloxane (PDMS) Polyisoprene (PI) y weight g PI:PDMS = 1:9 by d = 60.9 Pas = 0.826 c = 73.7 Pas

= 3.2 mN/m

The shoulder in G vs is related to the presence of drops Drop size can be estimated from Palierne model: G = f(/R) Ch Characteristic i i emulsion l i time: i

c R ( 2 3 )( 19 16 ) + + 0 f ( ) = 40 ( + 1 ) &
(Kitade et a., 1997) 30

Conclusions

The behavior of isolated drops in well-defined well defined flow fields provides some insight and guidelines for the preparation and processing of emulsions predictions of breakup (provided that the emulsion viscosity is used in place of c (Janssen et al al., 2001))

Smaller attainable drop size and emulsion stability is limited by coalescence Rheological tests can be used to estimate average drop size (up to moderate concentrations) The presence of an interface is a source of elasticity

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