Comparative Evaluation of Rheological Models used

for Evaluating Dark Chocolate Viscosity

Emmanuel Ohene Afoakwa1,2 *, Alistair Paterson1 & Mark Fowler2

1
Center for Food Quality, University of Strathclyde, Glasgow

2
Nestle Product Technology Centre, York
 INTRODUCTION

 Chocolate manufacturing is a complex physical and

chemical process.

 Requires numerous technological operations and the

addition of different ingredients.

 To achieve products of suitable physical and chemical

attributes and an attractive appearance and taste.
Chocolate manufacturing process:

Sugar Agglomeration of ingredients in thick paste,

Cocoa liquor Mixing continuously or with batch mixers
Cocoa butter
Skimmed milk powder (SMP)(a)

Refining Size reduction of mix via 2, 3 or 5

roll refiner

Conching
Final flavour development, final
Addition of the viscosity of the sample with conche
remaining ingredients: 1 Stage: Dry Conching
st
rotations for 4 to 24 hours
surfactants, cocoa butter 2nd Stage: Pasty Phase
3 Stage: Liquid Conching
rd

Most stable form of cocoa butter

Tempering crystals – form V via
heating/cooling systems (maintained
at 35°C)

Enrobing Moulding Panning (b)

Packaging
Chocolate viscosity:

Chocolate behaves as a non-Newtonian liquid exhibiting non-

ideal plastic behaviour, with shear-thinning. Parameters of
interest are yield value and plastic viscosity.

Influential factors:
Particle size distribution (PSD)

 Conching
 Time
 Temperature

 Ingredient variation
 Fat content
 Emulsifiers (Lecithin, PGPR)
Models for evaluating chocolate viscosity:
Model equations for characterizing chocolate viscosity

Models Equation

Herschel-Bulkley τ = τ0 + ηpl . (γ)n

Casson √τ = √ τCA + √ηCA . √γ

Bingham
τ = τ0 + ηpl . γ

(τ: shear stress; τ0: yield stress; ηpl: plastic viscosity; τCA: Casson yield value; ηCA:
Casson plastic viscosity; γ: shear rate; η: viscosity of the suspension; n: flow
viscosity index)
 Casson’s model and ICA Recommendations:
 Since 1973, the flow behaviour of molten chocolate has been
evaluated using Casson’s model by extrapolation techniques.

 In 2000, the ICA (IOCCC) recommended use of interpolation data.

The ICA recommendations:

i. the value of the stress at a shear rate of 5 s-1 be used to represent

yield stress.

ii. the value of the viscosity at a shear rate of either 30 s-1, 40 s-1, or 50
s-1 could be used depending on product characteristics, but
recommended the use of viscosity value at a shear rate of 40 s-1 to
represent apparent viscosity due to it relative reproducibility.
 Limitations on Casson’s model:

i. Mathematical models uses only a small set of parameters, and are

limited in accuracy as chocolate flow properties do not exactly fit
the Casson equation.

ii. At lower shear rates, the rheology data generally do not well fit the
Casson equation.

i. Low degree of repeatability in inter-laboratory analysis of

chocolate viscosity.

 Currently, the National Confectioners Association/Chocolate

Manufacturers Association (NCA/CMA) use the Casson’s model
whilst the ICA uses the new recommendations for evaluating
chocolate viscosity; thus the need for further investigation, for the
appropriate harmonization.
Main research objective:

This work compares the efficiency and relationship

between the two models in defining the rheological
properties of dark chocolate systems.
MATERIALS AND METHODS

Main Ingredients:

 Cocoa liquor of Central West African Origin

 Sucrose (pure cane extra fine granulated sugar)

 Pure prime pressed cocoa butter,

 Soy lecithin
EXPERIMENTAL DESIGN:

A 4 x 3 x 2 factorial experimental design was used

and the principal factors were:

i. Particle size (D90): 18, 25, 35 and 50 µm

ii. Fat content: 25, 30 and 35 %
iii. Lecithin content: 0.3 and 0.5%

All other variables including refiner temperature

and pressure, conching time and temperature, and
cocoa butter (5%) were held constant.
RECIPE FORMULATIONS:
Table 1. Recipes used for the formulation of the dark chocolate

Ingredient 25% Fat (% w/w) 30% Fat (% w/w) 35% Fat (% w/w)

Sucrose (%) 58.8 59.0 49.7 49.9 40.7 40.8

Cocoa liquor (%) 35.9 35.5 45.0 44.6 54.0 53.7

Cocoa butter (%) 5.0 5.0 5.0 5.0 5.0 5.0

Lecithin (%) 0.3 0.5 0.3 0.5 0.3 0.5

CHOCOLATE MANUFACTURE:

 Mixing of ingredients (Crypto Peerless Mixer K175)

 Refining (Buhler 3-roll refiner)

 Conching (Lipp Conche) at for 4 h at 60°C

 Storage at ambient temperature (20-22 °C)

Samples were analysed for fat and moisture content to ensure

they within the stipulated level.
ANALYTICAL METHODS:

 Particle size distribution (Malvern MasterSizer® Laser

Diffraction Particle Size Analyzer)

 Fat content (ICA, 1990)

 Moisture content (ICA, 1988)

 Rheological properties
 Casson models
 ICA (2000) Recommendations
RHEOLOGICAL PARAMETERS:

 Casson plastic viscosity - Cason model

 Casson yield value - Cason model
 Yield stress - ICA
 Apparent viscosity - ICA
 Thixotropy - ICA

DATA ANALYSIS:

Statgraphics Plus 4.1 (Graphics Software System, STCC, Inc,

Rockville, USA)
RESULTS
Particle size distribution of (A) 18 & 25 µm D90

10 100 10 100

90 90

80 80

70 70
Volume (%)

60 60

50 50

%
ol

m
e(
V

)
40 40
30 30

20 20
10 10
0 0 0 0
0.1 1.0 10.0 100.0 1000.0 0.1 1.0 10.0 100.0 1000.0
Particle Diameter (µm.) Particle Diameter (µm.)
 Particle size distribution of (C) 35 & (D) 50 µm D90

10 100 10 100

90 90

80 80
Volume (%)

70 70

60 60

50 50

40 40

30 30

20 20

10 10

0 0 0 0
0.1 1.0 10.0 100.0 1000.0 0.1 1.0 10.0 100.0 1000.0

Particle Diameter (µm.) Particle Diameter (µm.)

RESULTS
CASSON PLASTIC VISCOSITY:
25
Legend: Particle size (D90, µm) & Lecithin (%)

Casson plastic viscosity (Pas)

18 25 35 50
0.3% 0.5% 0.3% 0.5% 0.3% 0.5% 0.3% 0.5%
Lec Lec Lec Lec Lec Lec Lec Lec 20

15

10

0
50
35
25 25
30 18 Particle size (D90, µm)
Fat (%) 35
CASSON YIELD VALUE:
Legend: Particle size (D90, µm) & Lecithin (%)
450
18 25 35 50
0.3% 0.5% 0.3% 0.5% 0.3% 0.5%
400
0.5% 0.3%
Lec Lec Lec Lec Lec Lec Lec Lec
350

Casson Yield Value (Pa)

300

250

200

150

100

50

0
50
35
25 25
30
Fat (%) 35 18 Particle size (D90, µm)
APPARENT VISCOSITY:
70
Legend: Particle size (D90, µm) & Lecithin (%)

18 25 35 50 60
0.3% 0.5% 0.3% 0.5% 0.3% 0.5% 0.3% 0.5%
Lec Lec Lec Lec Lec Lec Lec Lec

Apparent Viscosity (Pas)

50

40

30

20

10

0
50
35
25 25
30
18
Fat (%) 35 Particle size (D90, µm)
YIELD STRESS:
Legend: Particle size (D 90, µm) & Lecithin (%) 1000

18 25 35 50 900
0.3% 0.5% 0.3% 0.5% 0.3% 0.5% 0.3% 0.5%
Lec Lec Lec Lec Lec Lec Lec Lec
800

700

Yield Stress (Pa)

600

500

400

300

200

100

0
50
35
25 25
30 18
Fat (%) 35 Particle size (D90, µm)
THIXOTROPY:
Legend: Particle size (D 90, µm) & Lecithin (%)
700
18 25 35 50
0.3% 0.5% 0.3% 0.5% 0.3% 0.5% 0.3% 0.5%
Lec Lec Lec Lec Lec Lec Lec Lec
600

500
Thixotropy (Pa)

400

300

200

100

0
25 30 35

Fat (%)
RELATIONSHIP BETWEEN CASSON MODELS AND ICA RECOMMENDATIONS:
Table 6. Regression and correlation analyses

Parameter Analysis Casson Casson yield Apparent Yield Thixotropy

plastic value viscosity stress
viscosity
Casson plastic Regression - 0.8368* 0.9053* 0.8919* 0.9021*
viscosity
Correlation - 0.8903* 0.9467* 0.9349* 0.9447*
Casson yield Regression - - 0.9582* 0.9694* 0.9665*
value
Correlation - - 0.9786* 0.9844* 0.9823*
Apparent Regression - - - 0.9898* 0.9955*
viscosity
Correlation - - - 0.9941* 0.9977*
Yield stress Regression - - - - 0.9939*
Correlation - - - - 0.9957*
Thixotropy Regression - - - - -
Correlation - - - - -

* Significant at P< 0.05

CASSON YIELD VALUE AND CASSON PLASTIC VISCOSITY:

500
Casson yield value (Pa)

400 R2 = 0.84

300

200

100

0
0 4 8 12 16 20 24

Casson plastic viscosity (Pa.s)

CASSON PLASTIC VISCOSITY AND APPARENT VISCOSITY:

Casson plastic viscosity (Pa.s)

24

20
R2 = 0.91
16

12

0
0 20 40 60 80

Apparent viscosity (Pa.s)

CASSON YIELD VALUE AND YIELD STRESS:

500
Casson yield value (Pa)

400 R2 = 0.91
R2 = 0.97

300

200

100

0
0 200 400 600 800 1000

Yield stress (Pa)

YIELD STRESS AND APPARENT VISCOSITY:

1000
R2 =0.99
800
Yield stress (Pa)

600

400

200

0
0 20 40 60 80

Apparent viscosity (Pa.s)

YIELD STRESS AND THIXITROPY:

1000

R2 =0.99
800
Yield stress (Pa)

600

400

200

0
0 20 40 60 80

Thixotropy (Pa)
APPARENT VISCOSITY AND THIXITROPY:

80
Apparent viscosity (Pa.s)

R2 =0.99
60

40

20

0
0 20 40 60 80

Thixotropy (Pa)
 PRINCIPAL COMPONENT ANALYSIS:

Biplot
5.1
Component 2

3.1 Casson plastic viscosity D(v,90)

Apparent viscosity D[4,3]
Yield stress D(v,50)
Thixotropy D[3,2]
1.1
Casson yield value

-0.9
Lecithin content Fat content
Specific surface area
-2.9
-9 -6 -3 0 3 6
Component 1

PC1, PC2 and PC3 respectively account for 74.2%, 13.7% and 7.3% of the variability. PSD,
fat content and lecithin content, together accounting for ~ 95% of the variability in the
rheological data.
 CONCLUSIONS:
 The Casson reference parameters (Casson yield value and Casson
plastic viscosity) and the new recommendations by ICA
recommendations (yield stress and apparent viscosity) for evaluating
chocolate rheology are very closely related, and could be effectively
used independently.

 The ICA method is relatively more efficient than the Casson’s model
but has some limitations as well.

 Both rheological models are dependent on PSD, fat and lecithin, as key

factors influencing chocolate rheology under controlled processing

conditions.

 For purposes of global harmonization, the use of Casson reference

parameters could be maintained for routine (industrial) quality control

purposes, while the new recommendations by ICA are used for

research purposes where wide variations in component viscosity occur.
 ACKNOWLEDGEMENT

Government of Ghana

Nestle PTC (York)

THANK YOU