Commerical and in Confidence

CRC for Polymers

Melting Chocolate
Research by: Savina Radosavljevic (CRC-P VSR 99/2000-8:Radosavljevic)
Anna Schlunk (CRC-P VSR 99/2000-9:Schlunk)

Supervisors: Professor Roger Tanner

Dr. Simin Nasseri
The University of Sydney

Date due: 25 February 2000

________________________________________________________________________

Abstract
The aim of this study was to investigate the relationship between temperature and viscosity on
samples of chocolate and polyox solution. Technical difficulties with heating the rheometers
above 100°C restricted the temperature range of experimentation to between 0°C and 100°C.
Therefore chocolate, which is solid at 33°C and melts at 34°C is ideal for research into the effects
of crystallization and liquid-solid phase change.
Two types of controlled stress rheometers were used with a cone and plate geometry (40mm, 4°),
the Carri-med CSL and Rheologica Stress Tech. In testing the chocolate, a milk chocolate button,
broken into small pieces was heated in a microwave oven until it become soft and viscous. After
stirring the softened sample, the melted chocolate was mounted on the Rheologica Stress Tech
Rheometer. Three types of test were conducted:
1. Shear Stress Sweep: At temperatures of 25°C, 30°C, 34°C, and 50°C, shear stresses
between 24 Pa and 167 Pa were applied to the sample in an upwards, then downwards
sequence. The resulting shear rates and viscosities were measured.
2. Temperature Sweeps: The temperature was decreased from 47°C to 17°C at a rate of 1°C
per minute and subsequently increased back to the starting temperature. The resulting
shear rates and viscosities for each different temperature were recorded.
3. Constant Shear Stress: The temperature and shear stress were kept constant at 47°C and
51.8 Pa respectively.
It was found that chocolate viscosity is dependent on shear history and temperature. Under
constant shear stress, chocolate viscosity decreases but it also decreases as shear rate is increased.
Decreasing the temperature increases chocolate viscosity, and heating chocolate decreases the
viscosity. Milk chocolate crystallization was found to occur at 23°C and resulted in a rapid rise in
chocolate viscosity.

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1. Introduction
The aim of this study was to investigate the relationship between temperature and
viscosity on samples of chocolate and polyox solution. This was completed to gain a
better understanding of the process of polymer solidification during injection molding
which would contribute to predictive models of the finished properties (e.g. strength) of
molded products. M. Mackley’s 1996 paper “Extrusion Processing Above and Below the
Melting Point” linked the cold extrusion properties of polyethylene and chocolate.

Technical difficulties with heating the rheometers above 100oC restricted the temperature
range of experimentation to between 0oC and 100oC. Therefore chocolate, which is solid
at 33oC and melts at 34oC [7](has a melting range between 35 +/- 15oC[2]) is ideal for
research into the effects of crystallisation and liquid-solid phase change.

Viscosity is a measure of the resistance to flow. It is defined as the shear stress divided
by shear rate. Shear stress is the force per unit area applied to a moving surface. Shear
rate is the speed at which the surface is moving divided by the thickness of the sample
being sheared.

Force, F
Speed, v
x
Moving Plate

y
Liquid

Static Plate

Figure 1.1 Parallel Plate Model

µ = σ/γ (1)
σ = F/A (2)
γ& = v/y (3)
where µ = viscosity (Pa.s)
σ = shear stress (Pa)
F = Force applied to the moving surface (N)
A = Area of moving surface
γ& = shear rate (1/s)
v = velocity (m/s)
y = height of the sample

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To measure viscosity, two rotational viscometers were used, both with cone and
plate geometry. The sample was placed between a cone and a flat plate. The cone was
made to rotate and the viscosity of the sample was measured.

Truncated Cone

Plate

Figure 1.2 Cone and Plate

Cone and plate geometry is good for viscous materials and liquids as the shear rate is
constant over the whole sample when the cone angle is no larger than 4o.

The viscometers used were a Carri-med CSL Controlled Stress Rheometer and a
Reologica StressTech rheometer. Both instruments apply a set stress and the resulting
angular velocity of the cone is measured. The shear rate is calculated from the angular
velocity.

Chocolate
The chocolate tested was Belcolade Milk Drops from Belgium, with the following
ingredients in decreasing order by mass: sugar, milk powder, cocoa butter, cocoa liquor,
emulsifier: lecithin, flavour: vanillin.

Chocolate has more than one crystalline state. Cocoa butter and similar fats can set in
more than one polymorphic form. The form affects the shelf life, setting time, colour and
surface finish of the chocolate.

Setting cocoa butter in the most desirable polymorphic form requires a process called
tempering. Chocolate is tempered when partial pre-crystallisation of the cocoa butter is
induced.
The tempering process [1]:
Chocolate at 45oC is cooled gently. This initiates the first stages of crystal growth.
The chocolate is reheated to prevent solidification.
The temperature is held. This promotes crystal maturity.

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During tempering the chocolate is mixed, creating a fine, homogenous structure of small
crystals. The properties of the polymorphic forms of cocoa butter are shown in Table 1.
β-crystals are the most stable and give chocolate the most desirable colour, hardness,
handling, finish and shelf-life characteristics.

Table 1. The polymorphic forms of cocoa butter [1]

Form Crystallizes Melting range Stability
γ Under 16.9oC Up to 16.9oC Unstable
From γ
o
α Up to 23.8 C Unstable
β1
o o
16.9 – 22.5 C 15 – 29.4 C Semi-stable
β 22.5 – 33.6oC 20 – 35oC Stable

Tempering time is important. If chocolate is not tempered for long enough, crystal
growth will be unstable and the chocolate will have bad setting characteristics. The
resulting disorganized crystal growth disorients reflected light and changes the colour of
the chocolate. Bad tempering may also cause ‘fat bloom’, when surface cocoa butter
crystallizes and appears white.

For accurate studying of crystallisation in chocolate, all the fat present was cocoa butter
without the confounding influence of other vegetable fats added as substitutes.

R. B Nelson states that “Chocolate is completely free of crystal growth at 45o

[1]”, hence all tests were started at a temperature 47oC or above.

Polyox
In addition to chocolate, crystallisation in a polymer system, polyox (1% mass) was also
studied. Polyox consists of polyethylene oxide in solution. Polyox resins are completely
water soluble at room temperature. The thickness of the solution increases with
concentration; and aqueous solutions of polyox are shear thinning. Polyox solutions have
low toxicity and can be used for textile-warp sizing, as thickeners in paints, to improve
the flow properties of adhesives, and as a coagulant. They can also be used as a binder,
dispersant and stabiliser for pigment slurries. They do not irritate the skin and find
application in a range of cosmetics and in pharmaceuticals.

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2. Method
2.1 Chocolate
A milk chocolate button, broken into small pieces was heated in a microwave oven, set
on ‘high’ for one minute. After stirring the soft sample (chocolate maintains its shape),
the melted chocolate was mounted on the Rheologica Stress Tech Rheometer using a 40
mm, 4o cone and plate, and the respective test completed.

Shear Stress Sweeps: At constant temperature a series of shear stresses between 24 Pa

and 167 Pa were applied to the sample in an upwards, then downwards sequence. The
resulting shear rates and viscosities were measured. This test was performed at
temperatures of 25oC, 30oC, 34oC, and 50oC.
Temperature Sweeps: Two types of temperature sweep tests were conducted. In the first,
the sample was put under a constant shear stress of 51.8 Pa. The temperature was
decreased from 47oC to 17oC at a rate of 1oC per minute and subsequently increased back
to the starting temperature. The resulting shear rates and viscosities for each different
temperature were recorded. For the second type of temperature sweep the shear rate was
kept constant rather than the shear stress. This test was done with shear rates of 0.054 1/s
and 0.098 1/s. Shearing action tends to change the crystallised state [5]. To minimise the
effect that shearing has on chocolate viscosity, low values of shear rate were chosen.
Constant Shear Stress: This test was conducted to investigate the effect of constant shear
stress on the temperature sweep results. The temperature and shear stress were kept
constant at 47oC and 51.8 Pa respectively.

2.2 Polyox
Polyox solution (1% mass) was mixed using the technique of Keentok et al., [3]. A
sample filled jar was continuously rolled mechanically for 7 days to form a homogenous
solution.

Shear rate sweeps and temperature sweeps were performed using the Rheologica, plate
diameter 40 mm and angle 4o. The shear rate of 0.098 1/s was used between temperatures
of 5oC and 60oC.

2.3 Silicon oil

Silicon oil was tested on the Carri-med viscometer. A sample was placed on the plate
and a shear stress sweep between 0.85 Pa and 50 Pa at 33oC completed.

Each test for each substance was repeated at least three times.

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3. Results
3.1 Silicon oil

Shear Stress Sweep

60.00
Shear Stress (Pa)

50.00
40.00
30.00
20.00
10.00
0.00
0.00 2.00 4.00 6.00
Shear Rate (1/s)

Figure 3.1 Shear Stress Sweep on 12500 cs silicon oil

Silicon oil is a Newtonian fluid, meaning that the shear rate is directly proportional to the
shear stress. The results of shear stress sweeps performed on Carri-med at 33oC are
shown in Figure 3.1. Silicon oil is shown to be Newtonian, and have a viscosity of about
11 Pa.s. The measured viscosity agrees well with the manufacturers specified viscosity of
12.5 Pa.s

3.2 Polyox

1% Polyox
Shear Rate 0.098 1/s
4.000
Viscosity(Pa.s)

down
3.000
2.000
up
1.000
0.000
0.0 20.0 40.0 60.0 80.0
Temperature(C)

Figure 3.2 Temperature Sweep on polyox solution.

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Figure 3.2 shows the results of a temperature sweep on Reologica whilst shear rate was at
a constant value of 0.098 1/s. The cooling rate was 1°C per minute. The viscosity
increases exponentially as temperature is decreased and decreases along the same path as
the temperature is increased again. This reveals that crystallization happens at a
temperature much lower than the minimum temperature of the operating rheometer.

3.3 Chocolate
Milk chocolate - Shear Rate Vs Viscosity and
Shear Stress at different Temperatures
10 0 0

Viscosity -
Viscosity
25oC
Viscosity -
30oC
Viscosity -
34oC
10 0 Shear Stress
- 25oC
Shear Stress
- 30oC
Shear Stress Shear Stress
- 34oC

10
0 .0 1 0 .1 1 10

Shear rate (1/s)

Figure 3.3 Shear Rate Vs Viscosity and simultaneously Shear Rate Vs Shear Stress.

From Figure 3.3 it can be seen that the logarithms of viscosity and shear stress are
proportional to the logarithm of shear rate. The straight lines are typical of a power law
fluid. It can also be seen that viscosity increases with decreasing temperature.

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Tem p e r a t u r e S weep - Shear Stress 51.8 Pa

600
Viscosity (Pa.s)

500
400
300 C o o lin
200 H e a ting g
100
0
20 30 40 50
T e mperature ( o C )

Figure 3.4 Temperature Sweep at a constant shear stress – 51.8 Pa.

Initially the viscosity decreases as temperature decreases, then begins to increase after the
temperature of 40oC is reached. At approximately 25oC, viscosity exponentially
increases. The shear rate does not remain constant. Starting at 0.15 1/s, it increases to a
value of 0.6 1/s at the temperature 40oC. In the second half of the curve (below 40oC),
shear rate decreases to a value of 0.014 1/s by 24oC.
Upon re-heating the sample, no results were recorded by the rheometer until the heating
curve reached approximately 36oC.

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Constant Temperature (47oC)

Constant Shear Stress (51.8 Pa)
4 experimental runs
400
350
Viscosity (Pa.s)

300
250
200
150
100
Average
50
0
0 100 200 300 400 500 600
Time (s)

Figure 3.5 a. Constant Temperature (47oC)/Constant Shear Stress (51.8Pa)

Four runs completed at a constant temperature of 47oC and shear stress of 51.8 Pa
showed that the effect of shear stress on viscosity at a constant temperature is significant.
The viscosity of the samples decreases rapidly within the first 3 minutes of shear and then
becomes more constant. However, the exact amount that viscosity decreased varied
between samples.
o
Constant Temperature (47 C)
Constant Shear Stress (51.8 Pa)
1000
Viscosity

100
y = 51.793x-1

10
0.1 Shear rate (1/s) 1

Figure 3.5 b. Constant Temperature (47oC)/Constant Shear Stress (51.8Pa)

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The shear rate Vs viscosity of the same tests plotted in Figure 3.5 a. are plotted on a
logarithmic scale in Figure 3.5 b. All data fits the line µ =51.79 γ& -1.

The effect of shear on Temperature Sweep -

Shear Stress 51.8 Pa

600
Viscosity (Pa.s)

500
400
Av. Constant Shear
300
200 Cooling
100
0
0 500 1000 1500
Time (s)

Figure 3.6 Effect of shear on the temperature sweep.

The curve obtained from the average result of the constant temperature (47oC)/constant
shear stress (51.8 Pa) experiments (Figure 3.5a), was superimposed on the graph of
‘cooling’ temperature sweep (Figure 3.4) to show the effect of shear on the temperature
sweep. The x axis variable is time meaning that initially temperature is 47oC. The sharp
increase at 1400 s corresponds to the crystallisation point at 23oC. The curves displayed
similar trends for the first 10 minutes of the temperature sweep, with the average constant
shear curve always below the cooling curve.

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Milk chocolate - Increasing shear-rate

choc34_2
1000 choc36_2
y = 59.028x-0.7839
choc40_1
y = 64.728x-0.6591 choc30_2
choc50_4
Viscosity (Pa.s)

Pow er (choc30_2)
Pow er (choc40_1)
Pow er (choc50_4)
100
y = 66.683x-0.4255

10
1.00E-02 1.00E-01 1.00E+00 1.00E+01
Shear rate (1/s)
Figure 3.7 Modelling viscosity as a function of shear rate and temperature.

The viscosity model µ = K (T )γ& ( n −1) , was fitted to the experimental data and plotted with
a power law trendline. The fit is close between the experimental and modelled results.

µ = viscosity (Pa.s)
K(T) = A exp (B/T) where A and B are constants
γ& = shear rate (1/s)
n = f(T)
T =Temperature

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Temperature Sweeps at constant shear rates

2000

1600
Viscosity (Pa.s)

1200 0.054 (1/s)

800

400
0.098 (1/s)
0
20 25 30 35 40 45 50

Temperature (o C)

Figure 3.8 Temperature sweeps at constant shear rates.

Two temperature sweeps at shear rates 0.054 1/s and 0.098 1/s follow the same patterns
when cooled and heated. The viscosity at the lower shear rate 0.054 1/s remained
consistently lower than that at 0.098 1/s. The viscosity increased rapidly at 23oC on the
cooling curve, and decreased rapidly at 23oC when the chocolate was heated.

Milk Chocolate - Shear Stress sweep

Shear rate Vs Viscosity / Shear Stress at 50oC

Viscosity 1000
Viscosity
Viscosity (Pa.s)

100
Shear stress

10

1
1.00E-02 1.00E-01 1.00E+00 1.00E+01 1.00E+02
Shear rate (1/s)

Figure 3.9 Shear Stress Sweep at 50oC

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The viscosity of chocolate is shown to depend on the shear history. As the shear stress is
increased, viscosity decreases. When the shear stress is decreased again the viscosity
increases at the same rate, but at lower values.

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4. Discussion

Before using chocolate samples, Silicon oil and a polyox solution were tested to establish
the reliability of the rheometers. A shear stress sweep on Carri-med (Figure 3.1) gave a
Newtonian shear stress vs shear rate curve with a slope of approximately 10. The slope is
equal to the measured viscosity of the oil. As the test results were good for Silicon oil the
equipment was expected to give reliable results for chocolate.

The results of a temperature sweep on a 1% polyox solution at a constant shear stress

(Figure 3.2) showed that Reologica also gave reasonable measurements. Viscosity was an
exponential function of temperature, and there was no hysteresis at the temperature of the
operating device.

As the viscosity of Silicon oil and polyox could be successfully measured it was assumed
that the rheometers would give good readings when chocolate was tested.

When temperature is decreased, the viscosity of chocolate is commonly observed to

increase. However, this was not the trend observed in Figure 3.4. The results of a
temperature sweep are shown in thus figure. The shear stress is kept constant at 51.8 Pa,
however shear rate varies. Thus both shear rate and temperature affect the viscosity
values. The higher the shear rate, the less viscous one expects a substance to be.
Conversely, the lower the temperature, the more viscous one expects chocolate to
become.

The results obtained in Figure 3.4 can be explained by Figures 3.5a and 3.6. Constant
shear stress at constant temperature has a significant effect on viscosity (as seen in Figure
3.5a). However, from Figure 3.6 it can be seen that decreasing the temperature does
increase the viscosity. Initially, the effect of constant shear stress is larger than that of
decreasing temperature, eventually the effect of decreasing temperature dominates.

The results of both types of temperature sweeps conducted (Figures 3.4: constant shear
stress, and 3.8:constant shear rate), displayed a sharp exponential increase in viscosity at
23oC. The very low rate of cooling (1oC per minute) affects the rate of crystallisation.
The lumps of polymer have more chance to form ordered structures when cooling is
slow. These result in an increased resistance to flow and hence higher viscosity values
than if cooling was faster [6]. Cocoa butter crystallises in the stable β form between
22.5oC – 33.6 oC in the melting range 20 – 35 oC (Table 1). Thus one concludes that the
chocolate sample solidifies between 23oC, forming β crystals.

Shear Stress Sweeps completed at different temperatures (Figure 3.3) verified that the
higher the temperature, the lower the viscosity of chocolate. Both shear stress Vs Shear
rate and Viscosity Vs Shear rate were linear on a logarithmic scale. This is typical of a
power law fluid which follow the relationship σ ∝ γ& n , where n varies with temperature.

The viscosity model in Equation 1 was fitted to the data obtained from the shear stress
sweeps at varying temperatures by Dr Simin Nasseri. This is shown in Figure 3.7. Close

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experimental and theoretical results verified that the behaviour of chocolate can be
modelled as below:
µ = K (T )γ& ( n −1) (4)
µ = viscosity (Pa.s)
K(T) =Α exp (BT) where A and B are constants
γ& = shear rate (1/s)
n = f(T)= CT+D, where C and D are constants.

Figure 3.9 indicates that the viscosity depends on the shear history. This confirms the
results shown in Figures 3.4 and 3.6.

Results obtained from a temperature sweep at constant shear rates, indicates that
increasing the shear rate decreases the viscosity of chocolate. The sharp increase in
viscosity at 23oC verifies that crystallisation occurs at 23oC.

Further areas for future and improvements

The viscosity of the chocolate noticibly decreased when the sample was stirred before
being loaded. Stirring was done manually introducing inconsistencies. As chocolate is
dependent on its shear history (Figures 3.8 and 3.9) the amount of mixing will affect
rheological properties. Samples could be prepared mechanically at a set shear rate for a
predetermined amount of time to reduce this uncertainty, and the results compared with
the existing (manually) obtained results.

The location of the thermocouple in Reologica is situated at the bottom of the water bath.
The temperature of the sample was assumed to be that of the water bath, meaning that the
temperature of the sample was never accurately measured. If the temperature of the
sample itself was measured, then the exact point of crystallisation could be found. The
Bohlin (constant strain) rheometer has a thermocouple located within the cone tip and it
is recommended that the experiment be repeated upon it. (Unfortunately the temperature
unit at The University of Sydney was not in working condition)

The use of a strain controlled rheometer (Bohlin) at Mechanical Engineering Department,

Sydney University, would also be beneficial to further research into the polymer
crystallisation process. The temperature unit when working has an operational range up
to 350oC.

The rate of heating and cooling in the temperature sweeps conducted was 1oC per minute,
which is very slow. A further area of investigation would be to increase this rate (up to
4oC per minute) and to observe if the slope of the viscosity curve varies and if the
temperature of crystallisation remains the same.

The next logical progression in understanding crystallisation is to determine and check

the actual point at which it occurs. X-ray diffraction or electron microscopy could be
investigated to monitor crystal structure formation.
5. Conclusions

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Commerical and in Confidence

From this investigation if can be seen that chocolate viscosity is dependant on shear
history and temperature. Under constant shear stress, chocolate viscosity decreases but it
also decreases as shear rate is increased.

Decreasing the temperature increases chocolate viscosity, and heating chocolate

decreases the viscosity.

Milk chocolate crystallisation was found to occur at 23oC, and resulted in a rapid rise in
chocolate viscosity.

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6. References

1. Beckett, S. T., ‘Industrial Chocolate Manufacture and Use’, 1988, Blackie, Glasgow

2. M. R. Mackley, ‘Extrusion Processing Above and Below the Melting Point’,

Proc.XIIth International Congress on Rheology, Quebec, Canada, 1996.

3. Keentok, M., Georgescu, A.G., Sherwood, A.A., Tanner, R.I, “The Measurement of
the Second Normal Stress Difference for some Polymer Solutions”, Journal of Non
Newtonian Fluid Mechanics, 6 (1980) pg 303-324.

4. Kennedy, Peter., “Flow Analysis of Injection Molds”, 1995, Hanswer Publishers,

Munich.

5. Han, S and Wang, K. K, ‘Shrinkage Prediction for Slowly-Crystallizing

Thermoplastic Polymers in Injection Molding’, International Polymer Processing XII
(1997) volume 3.

6. Kamal, Frydrychowicz, Ansari.,'High-Temperature Properties and Applications of

Polymeric Materials', 1994, 207th National Meeting of the American Chemical
Society.

7. Kerry, Cath., “The Haigh’s Book of Chocolate”, 1998, Wakefield Press, Kent Town.
South Australia

8. Davidson, Robert L., Sittig, Marshall, ‘Water-Soluble Resins’, 1962, Reinhold

Publishing Corporation, New York.

9. Woodward, Arthur E., ‘Understanding Polymer Morphology’, 1995, Hanser

Publishers, Munich.

10. Jenkins, A.. D., ‘Polymer Science’, 1972, North-Holland Publishing Company,
Amsterdam.

11. Powell, Peter C., ‘Engineering with Polymers’, 1983, Chapman and Hall, London.

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