Journal of Food Engineering 98 (2010) 133–140

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Journal of Food Engineering

journal homepage: www.elsevier.com/locate/jfoodeng

Chocolate demoulding and effects of processing conditions

Esther L. Keijbets a, Jianshe Chen a,*, Joselio Vieira b
a
School of Food Science and Nutrition, University of Leeds, Leeds LS2 9JT, UK
b
Nestlé Product Technology Centre, York YO91 1XY, UK

a r t i c l e i n f o a b s t r a c t

Article history: Traditional chocolate manufacturing relies largely on the experience and skill of the chocolatier. Nowa-
Received 31 March 2009 days, with the replacement of manual processes with automated equipments, it is increasingly important
Received in revised form 7 December 2009 to apply right processing conditions and controlling parameters, such as the time, the temperature, the
Accepted 11 December 2009
moisture content, the relative humidity of the surrounding air, etc. This study investigated the influences
Available online 16 December 2009
of these factors during the moulding and cooling stage of chocolate manufacturing process on the ease of
demoulding. Adhesion of chocolate to the polycarbonate mould surface was used as a measure for the
Keywords:
demoulding properties, and was determined as the force required to separate a flat mould surface from
Chocolate
Adhesion
the solidified chocolate sample. The results demonstrated that processing parameters, like temperature,
Moulding contact time, and the relative humidity of the surrounding environment, have a significant impact on
Demoulding chocolate crystallization and solidification processes and on the adhesion of chocolate to a mould surface.
Crystallization Experimental findings from this work confirmed observations made during commercial chocolate
manufacturing.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction
The knowledge of chocolate manufacturing has evolved hugely
since the introduction of plain chocolate tablets in 1847 by Joseph
Fry, the first solid milk chocolate in 1876 by Daniel Peter, and the
production of smoother and better tasting chocolate in 1880 by
Rodolphe Lindt (Beckett, 2008; Nelson, 1999). Since then, the choc-
olate manufacturing process has undergone various changes for
the purposes of either improved oral experience (flavour and tex-
ture) or increased productivity to meet increasing demands for
chocolate products. With ever increasing product output, it is
essentially important to have a good understanding of the influ-
ences of chocolate manufacturing process, as well as the process-
ing conditions, on the quality of the final product. An important
example in this case is the adhesion of products during processing,
which is a substantial ongoing problem in the food industry in gen-
eral. During chocolate manufacturing the process of demoulding is
particularly prone to adhesion problems, leading to surface defects,
production losses and increased processing costs due to equipment
cleaning.
A basic overview of the main chocolate manufacturing process
has been given by Beckett (2008). The critical stages of the choco-
late manufacturing process are the mixing of the main ingredients
to form a dispersion of cocoa solids (particles) and sugar crystals in
a continuous fat phase, consisting of fat crystals and liquid fat
* Corresponding author. Tel.: +44 113 3432748; fax: +44 113 3432982.
E-mail address: j.chen@food.leeds.ac.uk (J. Chen).
(Walstra, 1996), and the crystallisation of the cocoa butter in the
correct polymorph (Form V). The aim of the tempering process is
to develop the correct polymorphic form, and in order to do so
the chocolate is cooled from 45 °C to approximately 30 °C (depend-
ing on the type of chocolate, e.g. milk or dark chocolate). After the
tempering stage, the liquid chocolate is deposited into polycarbon-
ate moulds and cooled, as is visualized in Fig. 1. Objective of this
cooling phase is the solidification the fat phase of the tempered
chocolate mass with the correct crystallization, as this will lead
to contraction of the chocolate and easy removal of the solidified
chocolate from the mould during the subsequent demoulding
process.
The detrimental effects of moisture on chocolate viscosity and
the ease of processing have been observed. In order to prevent
the chocolate taking up moisture, Beckett (2001) advised to keep
the equilibrium relative humidity (ERH) at around 35–40% during
manufacturing. During moulding, chocolate is deposited at a tem-
perature of approximately 30 °C and is cooled down to below 20 oC
for solidification. Important for the cooling and solidification stage
is to prevent the formation of (moisture) condense on the choco-
late surface, which induces sugar bloom. A general recommenda-
tion is to keep the cooling temperature above the dew point to
prevent against moisture condensation (Beckett, 2008). Another
important reason to avoid too low cooling temperature is the set
of cocoa butter in the wrong crystalline form causing problems
in demoulding. The formation of a larger number of polymorphs
with a lower melting point results in a chocolate with a lower vis-
cosity (softer) at room temperature and less contraction during

0260-8774/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2009.12.019
134 E.L. Keijbets et al. / Journal of Food Engineering 98 (2010) 133–140
Moulding, cooling and de-
moulding of dark chocolate
Tempered
Deposition of Moulds are pre-
dark
chocolate mass into conditioned
chocolate
polycarbonate moulds Tmould ≈ 28 - 30°C
30-32°C
Vibration,
to release air and
spread chocolate
in moulds
Cooling of
moulds with Tcool ≈ 20°C
dark chocolate tcool ≈ 15 min.
mass
Demoulding of
solidified
chocolate
Dark chocolate
(moulded) product
Fig. 1. A schematic overview of the chocolate moulding, cooling and demoulding
process.
solidification, as a result of which the solidified chocolate does not
easily come away from the mould (Tewkesbury et al., 2000).
Microstructure and composition in relation to processing and
sensory perception have been the predominant topics of chocolate
researches. In their review of ingredient interactions, Awad and
Marangoni (2006) stressed the importance of processing condi-
tions in relation to the texture of chocolate. It is generally acknowl-
edged that the key determining factors for the physical characters
of chocolate, e.g. texture, hardness, smoothness and stability, are
the chemical composition and solid-state structure, which refers
to the 3-dimensional network created as a result of the crystalliza-
tion of cocoa butter.
The chemical composition of chocolate is mainly determined by
the recipe. As described by Afoakwa et al. (2007) the addition of
milk fat to milk chocolate results in a lower melting point, a slow
setting or solidification and a softened texture. Liang and Hartel
(2004) showed that free fat levels present within different milk
powders affected the processing behaviour as well as the physical
and organoleptic properties of the final milk chocolate product.
The addition of emulsifiers to the chocolate recipe is furthermore
known to affect chocolate’s rheological properties, sensitivity to
moisture and temperature, and tempering behaviour. Emulsifiers
are also known to influence the crystallisation behaviour of cocoa
butter, and consequently affect the solidification behaviour. For
example, Schantz et al. (2005) showed that the use of Polyglycerol
Polyricinoleate (PGPR) instead of lecithin as an emulsifier reduced
the seed-forming and crystallisation times in both dark and whole
milk chocolate.
However, the exact microstructure of chocolate is still not ex-
actly understood. Improved knowledge of the microstructure is re-
quired to increase the understanding of oil and fat migration
mechanisms in chocolate and chocolate coatings. Loisel et al.
(1997) used Mercury porosimetry to study the microstructure of
dark chocolate, based on the assumption that chocolate has a por-
ous matrix partly filled with liquid cocoa butter fractions. The
amount of empty spaces depends on the condition of the chocolate,
e.g. well-tempered or over-tempered, as well as on the amount of
cocoa butter present. Aguilera et al. (2004) also assumed the exis-
tence of a porous structure in chocolate and debated whether fat
migrates through its pores due to diffusion or capillary flow.
According to them, chocolate has a microstructure of a particulate
nature. Therefore, interparticle passages and connected pores exist
between the groups of fat-coated particles, in which the liquid co-
coa butter migrates under capillary forces.
Chocolate deposits on a mould surface after demoulding are be-
lieved to be caused by an imbalance between the adhesion force
(between the chocolate and the mould) and the cohesion force
within the chocolate matrix. The authors previously demonstrated
that the surface energy of mould materials had a huge influence on
chocolate–mould interactions, and that a mould material with a
surface energy less than 30 mN m–1 could improve the easiness
of chocolate demoulding (Keijbets et al., 2009). The aim of the cur-
rent study was to investigate the effect of processing conditions on
the level of chocolate adhesion to the mould surface during
demoulding, especially, the processing conditions applied during
the moulding and cooling stages of the chocolate manufacturing
process, e.g. mould and cooling temperature, contact time and rel-
ative humidity (RH). It is hoped that findings from this work will
enhance our understanding of the interactions taking place at the
chocolate–mould interface.
2. Materials and methods
2.1. Materials
Polycarbonate (Barkston Plastics Ltd., Leeds, UK) was chosen as
solid substrate because of its commercial application as a mould
material in chocolate manufacturing. The respective surface finish
of the polycarbonate substrate was obtained by abrasion, using a
P600 (3 M™, MarineWare, Southampton, UK) wet or dry abrasive
paper and an abraded surface plate. The polycarbonate substrates
were cleaned with boiling, distilled water (Millipore, Watford,
UK) and dried using compressed air prior to adhesion force deter-
mination. Dark chocolate samples used for the surface adhesion
determinations were supplied by the Nestlé Product Technology
Centre, York (UK). Samples were tempered using commercial
methods. The final product contained 52% cocoa solids.
2.2. Determination of chocolate-mould adhesion
Experimental determination of chocolate adhesion to the mould
surface was performed on the TA-XTplus Texture Analyser (Stable
Micro Systems, Surrey, UK), using a fixture specifically developed
for this work. The surface adhesion force (or stickiness) was mea-
sured by pulling the flat polycarbonate probe off a solid chocolate
sample, as shown schematically in Fig. 2, imitating the forces in-
volved in the demoulding process of commercial chocolate bars.
A more in-depth description of the experimental determination
of chocolate adhesion has already been given elsewhere (Keijbets
et al., 2009).
pull off at a
mould probe constant speed
liquid (solid surface)
chocolate
60 min.
15 oC
solid chocolate
sample holder
Fig. 2. A schematic diagram of the procedure and conditions of the surface
adhesion measurements.
 E.L. Keijbets et al. / Journal of Food Engineering 98 (2010) 133–140
The experimental adhesion force, Ea, is defined as the force per
surface area,
adhesion force
Ea ¼ ; ð1Þ
surface area
where the adhesion force is the peak separation force measured by
the probe pulling test and the surface area is the area of contact be-
tween the polycarbonate probe surface and the chocolate surface.
2.2.1. Chocolate processing conditions
In this study effects of different processing conditions on the
adhesion force were investigated under varying conditions of cool-
ing temperature, probe or mould temperature, contact time and
relative humidity. The experimental set-up outlined in Fig. 3 was
developed specifically for this study. A sealed cabinet (9) with a
dimension 145 mm (W)  130 mm (D)  105 mm (H) connected
with a Peltier heating/cooling unit (7) (Stable Micro Systems, Sur-
rey, UK) made it feasible to have a controlled experimental temper-
ature between 0 and 50 °C. The contact between chocolate (11) and
polycarbonate surface (12), i.e. the chocolate–mould interface, was
created at a temperature of approximately 30 °C, after which the
temperature was normally adjusted to 15 °C using a standardized
temperature profile. The set-up was left without disturbance for
60 min, ensuring complete solidification of the chocolate sample.
In order to vary the cooling temperature, the temperature of the
cabinet was decreased to 20, 15, 10, 5 or 0 °C, respectively. Relative
humidity of the air (0% RH) and air flow rate (10 l/min) were kept
constant. Experimental adhesion force was measured after 60 min
of cooling at each specified cooling temperature. For variations in
mould temperature the thermal equilibration step of chocolate
and mould probe of 30 min, before creating contact, was omitted.
The respective mould surface temperatures of 20, 0, 10, 20, 30
and 50 °C were obtained by cooling the polycarbonate mould
probe in a fridge or freezer or heating in an oven, respectively.
The contact time refers to the time that the chocolate–mould inter-
face was in place, i.e. from the moment of contact/interface crea-
tion, until the time of probe separation controlled by the Texture
Analyser (13). A semi-dynamic cooling process was used, with a
flow of cold air (0% RH) being supplied at a rate of 10 l/min. The
1. air supply
2. pressure valve
3. dry column
4. water column
5. valve
6. water bath
7. cooling/heating unit
8. ventilator
9. Peltier chamber
10. sample holder
11. chocolate sample cell
12. adhesion probe
Fig. 3. Experimental set-up to measure the effect of processing conditions on the
surface adhesion force.
135
temperature of the air was decreased from 30 °C, the moment of
interface creation, to 15 °C in 20 min, after which the air tempera-
ture stayed unchanged. During this study the evolution of surface
adhesion with contact time was followed from 0 to 450 min.
The relative humidity was controlled by using compressed air
(1 and 2) that was passed through a dry (0% RH) (3 and 5) and/
or wet column (4), where the air bubbling through distil water to
gain 100% RH. By using different ratios of wet and dry air, the rel-
ative humidity of the air circulation in the Peltier cabinet was con-
trolled. After mixing the air, it was passed through a copper coil
fully merged in a water bath (6) to obtain the designed tempera-
ture, before entering the Peltier cabinet. Using the water bath the
temperature of the air mixture was adjusted according to the cool-
ing profile used to solidify the chocolate. In general, the tempera-
ture profiles used were comparable to those used in industry.
The experimental set-up consisted of a 30 min pre-conditioning
or equilibrium, during which the mould surface was pre-heated
to 30 °C at varying RH conditions (range: 0–100% RH). After that
the pre-conditioned mould was placed on top of the liquid choco-
late surface and the sample was solidified for 60 min using the
standard cooling process with a cooling temperature of 15 °C.
2.2.2. Chocolate and mould parameters
For all measurements the temperature and relative humidity in
the Peltier cabinet were measured at the time of creation of the
chocolate–mould interface and just before determining the exper-
imental adhesion force using a digital thermometer/hygrometer
(Fisherbrand, Loughborough, UK). Additionally, a set of parameters
was measured to determine the effect of different processing con-
ditions on both the chocolate and mould surface:
 Hardness: The solidified chocolate samples were analyzed for
hardness by a method described by (Liang and Hartel (2004))
using the Texture Analyser (TA-XTplus, Stable Micro Systems).
A 2-mm cylindrical stainless steel probe was used to penetrate
the solidified chocolate sample at a constant speed of 0.1 mm/
s to a depth of 5 mm. The maximum force (N) obtained during
this penetration was taken as a measure of the hardness.
 Chocolate residue weight: The chocolate residue weight or the
left-over residues at the probe surface, expressed as the
amount of chocolate per unit surface area (mg m2), refers
to the amount of chocolate left on the mould surface after sep-
aration tests.
 Contact angle: The contact angle of a water drop placed on the
mould surface after the separation tests was assessed using
the sessile drop method. For each mould surface the measure-
ment was done in duplicate. The aim of this test was to estab-
lish the change in surface character of the mould after
contacting with chocolate, e.g. due to the migration or adsorp-
tion of fat from chocolate to the mould surface.
 Gloss: The gloss or light reflection of both chocolate and
mould surfaces was measured at 3 angles, 20, 60 and 85° using
a Tri-GLOSSmaster (Sheen Instruments, Surrey, UK). The gloss-
master measures specular reflection, which is the capacity of a
surface to reflect light. The aim of this test was to determine
the deposition of (fat) residues on the mould surface, as well
as possible changes in chocolate gloss.
2.3. Determination of moisture uptake
Moisture uptake by the polycarbonate mould surface at varying
RH was determined using a Cisorp water sorption analyser (CI Elec-
tronics Ltd., Salisbury, UK). The method of analysis of the Cisorp can
be defined as a gravimetric method at an ambient pressure. Basi-
cally, it consists of three separate chambers: a weighing chamber,
136 E.L. Keijbets et al. / Journal of Food Engineering 98 (2010) 133–140

a balance chamber and a humidifier. The humidifier is responsible

A
for the temperature conditioning and for supplying a wet air flow,
by passing dry gas (nitrogen or air) at reduced pressure through a
cavity filled with distilled water. This wet flow is mixed with a
dry flow, after which it is fed to the weighing chamber. A calibrated
humidity probe present in the weighing chamber is used to monitor 1800

chocolate residue / mould surface [g m ]

-2
the RH. Two microbalances are placed in the balance chamber, with 500 1600

Surface adhesion (x 1000) [N m ]

-2
a thin rod being suspended into the weighing chamber, to which a
sample holder is connected. A counterweight is used to mechani- 1400
400
cally balance the weighing arm. A microprocessor is responsible 1200
for the conversion of the forces required to hold the balance arms
horizontal into weight readings (Mangel, 2007). 300 1000
In order to determine the moisture sorption by a polycarbonate 800
surface during the pre-moulding stage, a polycarbonate mould
200
piece was placed in the Cisorp weighing chamber for 30 min at a 600
specific RH and a temperature of 30 °C, and the change in weight 400
per minute was recorded. The moisture uptake by the polycarbon- 100
Chocolate residue weight 200
ate mould surface was calculated as a percentage compared to the
surface adhesion
moisture uptake responsible for saturation, e.g. 100%, 0 0
mRH 0 100 200 300 400 500
Moisture uptake ½% ¼  100; ð2Þ Contact time [min]
msat
where mRH is the amount of moisture uptake after 30 min at a spe- B
cific RH, and msat is the amount of moisture uptake at saturation. 550 50
-2
Surface adhesion (x 1000) [N m ] 500 45
3. Results and discussion 450 40
400
3.1. Contact time 35
350

In industry, liquid tempered chocolate (28–32 °C) is deposited
into pre-heated polycarbonate moulds (25 °C), which are subse-
quently placed in a cooling tunnel. These cooling tunnels can be di-
vided into different sections, enabling the use of temperature
profiles. The first section uses gentle cooling conditions, to quickly
set the chocolate. Whilst the chocolate matrix is still liquid, there is
the possibility of cocoa butter migrating to the surface, resulting in
the presence of fat bloom on the surface of the chocolate bar. Sec-
tion 2 applies the coldest air flow (12–13 °C), resulting in the larg-
est amount of latent heat being removed. The 3rd and final section
applies again a relatively gentle cooling, to limit the temperature
difference between the chocolate sample and the air in the packag-
ing area. A cold chocolate surface may otherwise result in the con-
densation of water vapour, causing the formation of blemishes
and/or sugar bloom. On average, it takes 40 min for a chocolate
sample to set, if a cooler with a constant air flow and a temperature
of 10–15 °C is used.
Fig. 4A indicates that, at t0 (zero contact time), the surface adhe-
sion is zero, but the chocolate residue weight is high. Due to the li-
quid character of the chocolate at this time, the chocolate should
be in close contact with the probe or mould surface and may form
a bridge during separation. With time the liquid character of the
chocolate declines, as crystallization and solidification processes
continue, resulting in a clean separation after approximately
60 min. The adhesion force, meanwhile, increases linearly with
time until a contact time of about 90 min, after which the adhesion
force appears to become stabilised at around 430 kPa (kN m2).
In Fig. 4B a plot is shown of the probe separation force together
with the hardness of chocolate samples at respective contact times.
It is obvious that both parameters follow the same trend. The crys-
tallisation taking place during cooling is basically a transformation
of a significant part of the liquid fat into solid fat crystals. Depend-
ing on the stage of crystallisation, there are different quantities of
solid and liquid fat present, which are responsible for the differ-
ences in hardness observed during this study. The results indicate
that with the cooling conditions used during this study a contact
time of 60 min is required to form a relatively strong crystal net-
Hardness [N]
30
300
25
250
20
200
15
150
10
100
50 surface adhesion hardness 5
0 0
0 100 200 300 400 500
Contact time [min]
Fig. 4. (A). Surface adhesion of dark chocolate (j) and the amount of residues after
probe separation (s) as a function of contact time. (B) Surface adhesion of dark
chocolate (j) and the hardness of the solidified chocolate samples (s) as a function
of contact time.
work so that the chocolate will be cohesive enough to withstand
the separation force of demoulding. In general, crystallization
and solidification are very important factors in the surface adhe-
sion and demoulding. However, one may conclude that there is
probably no need to wait for a complete solidification at the time
of demoulding.
In addition to tempering and the type and thickness of the choc-
olate coating in the case of enrobing, several other parameters are
known to affect the cooling time (Nelson, 1999). If a chocolate
sample is properly tempered, the cooling time will depend purely
on the type of chocolate. Tscheuschner and Markov (1989) ob-
served significant texture changes of chocolates within the first
six weeks of storage, which they described as after-crystallization.
According to Liang and Hartel (2004) the packing arrangement of
the dispersed phases in chocolate influences the mechanical prop-
erties, such as hardness, of the solidified chocolate. As described by
Afoakwa et al. (2007) the Form IV polymorph crystallizes in a dou-
ble chain, whereas the Form V polymorph crystallizes in a triple-
chain, consequently enabling closer packing and probably a denser
and harder end product. During the early stages of the cooling pro-
cess a limited number of crystals are formed, resulting in a low
 E.L. Keijbets et al. / Journal of Food Engineering 98 (2010) 133–140 137

adhesion force and soft, liquid-like, product. Increasing the contact the cooling air at a low cooling temperature, e.g. 0 °C, a much faster
time at a cooling condition will enable further crystallization, and heat transfer occurs between the chocolate and the air or a much
the formation of an enhanced fat crystal network. The packing faster heat removal. Consequently, a larger amount of crystals is
arrangement of this network will depend on the cooling tempera- formed within the same length of time. This indicates that a large
ture, temper of the chocolate and the presence of Form V seeding amount of small fat crystals with a dense packing could be formed
crystals. These factors, in combination with the amount of liquid at low cooling temperatures. On the other hand, higher cooling
cocoa butter fat present, are expected to determine the porosity temperatures promote the formation of significantly larger crystals
of the final chocolate product. because of the faster growth of crystals in relation to the rate of
crystal nucleation. Due to the dense and more compact packing
arrangement of the crystals at low air temperatures, the chocolate
3.2. Cooling temperature
sample becomes harder (see Fig. 5). The penetration force was al-
most four times higher for the chocolate solidified at below 5 oC
As described in Section 3.1, the air temperature used in commer-
than that formed at 20 oC.
cial cooling tunnels during chocolate manufacturing is usually
Tewkesbury et al. (2000) developed a model to predict the tem-
10–15 °C. The provision of cold air flow is to remove both sensible
perature distribution within a cooling chocolate and applied the
and latent heat from the liquid chocolate sample, so that a solid
model to compare the cooling curve of tempered chocolate versus
product could be formed for easy handling during packaging. On
that of untempered chocolate. They demonstrated that different
average, a temperature decrease of 10 °C is required. Assuming
polymorphic forms formed during the chocolate solidification
the specific heat capacity of chocolate to be about 1.6 kJ kg–1 °C1,
and crystallization process were a result of different cooling paths.
and the latent heat to be 45 kJ kg–1 (Beckett, 2008), a total of 60 J
As can be seen from the hardness curve in Fig. 5, the chocolate is
needs to be removed to cool and solidify each gram of chocolate.
relatively less hard when cooled at a temperature of 20 °C. These
The time required for cooling and solidification depends on the rate
results indicate that solidification may take a much longer time
of heat transfer from the chocolate product to the air, which in turn
at higher cooling temperatures. Therefore, the use of appropriate
depends on the temperature and flow rate of the cooling air. As
cooling times and temperatures is essential to ensure that the cor-
described by Nelson (1999), the cooling process should not be too
rect crystallization and solidification process are pursued.
short in order to prevent against poor chocolate quality. At a low
air temperature, there is an increased risk of sugar bloom and a dull
3.3. Probe (mould) temperature
finish on the chocolate surface, due to moisture condensation on
chocolate surface. A low air temperature may also affect the crystal-
The manufacturing of tablets of chocolate requires the liquid,
lization of the cocoa butter into the correct polymorphic form, con-
tempered chocolate (28–32 °C) to be deposited into pre-condi-
sequently decreasing the volume-reduction or contraction desired
tioned moulds, which are subsequently passed over a vibrator, to
for easy demoulding (Beckett, 2008).
spread the chocolate evenly throughout the mould without air
Fig. 5 shows the relationship between the cooling temperature
bubble incorporation. The main controlling point is the pre-condi-
and the surface adhesion force. It should be stated that, at all cool-
tioning of the polycarbonate moulds. The pre-conditioning basi-
ing temperatures, a clean surface separation was observed, indicat-
cally consists of a pre-heating of the mould to a temperature of
ing that the cohesive force of the chocolate sample exceeded
28–30 °C, in a low RH environment. The tempered chocolate is sen-
surface adhesion force and no fracture was observed at the surface
sitive to large temperature variations and as a result the tempera-
region. The surface adhesion decreases almost linearly with
ture of the mould should be as close to the temper temperature as
increasing cooling temperature until 15 °C, after which a sharp
possible when the chocolate is deposited in the moulds. A too high
drop in surface adhesion was observed for a cooling temperature
mould temperature will cause the chocolate tablets to stick to the
of 20 °C (room temperature). Similar to the adhesion force, the
mould upon demoulding. Due to the temperature of the mould
hardness of the chocolate samples also decreases with increasing
being higher than that of the chocolate, seed crystals present with-
cooling temperature. The temperature difference between the tem-
in especially the surface or interfacial layer will be melted out. This
pered chocolate (30 °C) and the cold air is expected to be responsi-
will generally lead to the formation of less form V crystals during
ble for the different surface adhesion forces. Due to the relatively
cooling, as the seed crystals are not present, and consequently
large difference in temperature between the liquid chocolate and
hinder chocolate setting. On the other hand, a too low mould tem-
perature causes a flash shock of the chocolate. The sudden temper-
600 ature drop will cause the chocolate to release excessive heat or
50
energy to the mould surface, resulting in immediate crystallization
Surface adhesion (x 1000) [N m ]

of the fat present in the interfacial layer. Unfortunately, this crys-

-2

500
tallization often results in the formation of unstable polymorphic
40 forms, rather than the stable form V. Unlike form V crystal, poly-
400
morphic forms are much less closely packed and lead to little vol-
Hardness [N]

30 ume contraction, a common reason causing demoulding defects.

300 In Fig. 6A the surface adhesion of chocolate is plotted against
the mould temperature, to investigate the effect of different mould
20 temperatures at the time of moulding on the final demoulding
200
properties as measured by the surface adhesion force. Notable dif-
100 10 ferences are clearly observable. The adhesion force increases al-
hardness most linearly with the decrease of mould or probe temperature,
surface adhesion except for a mould temperature of 20 °C, where the adhesion
0 0
0 5 10 15 20 force drops to a lowest level. The low surface adhesion at 20 °C
is assumed to be caused by the formation of a hydrophilic layer
Cool temperature [°C]
at the interface between the mould and chocolate surface. At such
Fig. 5. Surface adhesion of dark chocolate (j) and the hardness of the solidified a low temperature, there is an increased risk of moisture vapour
chocolate samples (s) as a function of cooling temperature. condensation, as well as the formation of ice crystals during the
138 E.L. Keijbets et al. / Journal of Food Engineering 98 (2010) 133–140

30 °C. A significant reduction in hardness and cohesive strength of

A surface adhesion
500 chocolate weight the chocolate, together with a reduction in the surface adhesion

chocolate residue / mould surface [g m ]

force causes an increase in cohesiveadhesive failure and the

-2
Surface adhesion (x 1000) [N m ]

450 200
-2

amount of chocolate residue present on the mould surface. A closer

400
look at the mould surface after the adhesion tests reveals signifi-
350 cant changes in the contact angle of water, whereas the gloss of
150
300 the different mould surfaces is fairly constant, as can be observed
from Fig. 6B. At intermediate mould temperatures, e.g. 10, 20
250
100 and 30 °C, an increase in contact angle can be ascribed to the depo-
200 sition of a thin film of fat on the mould surface, leading to an in-
150 creased surface hydrophobicity. Wettability experiments by
100 50 Luengo et al. (1997) on mica surfaces used for thin film tribology
of chocolate also confirmed the presence of a hydrophobic mono-
50
layer on the solid (mould) surface after contact with chocolate.
0 0 At a temperature of 50 °C, the chocolate residue at mould surface
-20 -10 0 10 20 30 40 50 was so high that contact angle measurements became less relevant
Probe temperature [°C] to mould surface but more to chocolate. The low contact angles at
0 and 20 °C may indicate the existence of a thin film (monolayer)
B 20 of water molecules at the interface, due to condensation and/or the
45
formation of ice crystals. This monolayer prevents fat from migra-
40 tion to the mould surface.
35 A frozen cone/plunger method has been used to investigate
15
adhesion and crystal formation (Beckett, 1999), where a frozen
Δ Contact angle [°]

30
plunger (temperature range 5 to 21 °C) is inserted into a liquid
[-]

25 chocolate sample for a short time (2–5 s) to solidify a thin shell of

Δ Gloss

10
chocolate. A better release of the plunger from the chocolate is ob-
20
served, according to the manufacturer, if the plunger is coated with
15 a very thin film of ice crystals. Under such a circumstance, the fat is
5 expected to set in the unstable crystalline form, due to the shock
10
cooling. Whether this observation is true or not requires further
5
investigation, but results from our investigation have at least con-
0 0 firmed a strong correlation between mould temperature and crys-
-20 -10 0 10 20 30 40 50 tallization behaviour. A mould temperature of 50 °C causes melting
Probe temperature [°C] contact angle of seed crystals, limiting form V crystallization, whereas a temper-
gloss ature of 0 °C or lower leads to the formation of more unstable poly-
Fig. 6. (A) Surface adhesion of dark chocolate (j) and the hardness of the solidified
morphic forms rather than form V. One may conclude that the
chocolate samples (column bar, ) as a function of probe temperature. (B) mould temperature affects surface crystallization of chocolate
Differences of contact angle (column bar, ) and surface glossiness (j) of the deposits, which in turn determines the ease of demoulding, as
polycarbonate mould surface before and after chocolate contact as a function of measured by the force required to pull a mould probe off the solid-
probe temperature.
ified chocolate.

pre-conditioning stage. The decrease in surface adhesion with 3.4. Relative humidity
increasing mould temperature is expected to be related to the crys-
tallization and solidification processes taking place at the interface, The effect of moisture at the chocolate–mould interface on the
especially the formation of unstable polymorphs and the melting demoulding has also been investigated by exposing the mould
out of seed crystals, as described previously. probe to varying relative humidity before in contact with the choc-
Fig. 6A also shows the amount of chocolate residue present on olate. Results shown in Fig. 7 indicate that the surface adhesion in-
the mould surface after demoulding. Nearly all surfaces show some creases initially with increasing RH. At approximately 25% RH the
degree of cohesiveadhesive failure, indicating that the cohesive adhesion force stabilizes forming a constant plateau till ca. 50%
strength of the chocolate sample is approximately the same as RH. The surface adhesion starts to decrease sharply once the RH
the interfacial adhesive bonding strength between mould material is higher than 50%. A similar observation has also been made in
and chocolate, resulting in a break within the chocolate sample and industry, where the adhesion of chocolate to roll-refiners increased
chocolate residues adhering to the mould surface. This behaviour significantly if the air in the factory was 20–25% RH. The assump-
can be expected, due to the formation of different polymorphic tion is made that these changes observed in surface adhesion are
forms at the chocolatemould interface as a result of the variation related to the change of surface hydrophilicity due to the adsorp-
in mould temperature. A mould temperature of 50 °C results in the tion of water vapour on the polycarbonate surface. The initial in-
melting out of seed crystals, consequently reducing the crystalliza- crease in surface adhesion coincided with an increase in
tion and solidification of the chocolate sample. The amount of cohesiveadhesive failure, i.e. the amount of chocolate sticking
chocolate residues adhering to this mould surface was large, and to the mould surface. A high RH resulted in a smaller surface adhe-
is thought to be caused by the fact that there was no extensive sion, but caused a detrimental effect on the chocolate surface gloss
crystal network present to give the chocolate the required cohesive (not shown). The moisture present at the mould surface could dis-
strength and hardness. solve some of the sugar molecules present at the chocolate inter-
The hardness of the chocolate samples (not shown) followed face, an effect known as sugar bloom. Therefore, an optimal
the same trend as the adhesion force indicating that solidification relative humidity that gives minimum surface adhesion and max-
might not be complete when mould temperature was set at above imum chocolate quality is at an as low as possible RH. However,

500
Surface adhesion (x 1000) [N m ]
-2
400
300
200
100
0 0
0 20
Relative humidity [%RH]
Fig. 7. Surface adhesion of dark chocolate (j) and the amount of residues after
probe separation (column bar, ) as a function of relative humidity.
such a condition is practically difficult to achieve in an industrial
environment.
The hypothesis proposed to explain the relationship between
relative humidity and chocolate adhesion is based on the adsorp-
tion of water vapour onto the mould surface, consequently forming
a wet film of water molecules at high RH, which prevents interac-
tions between the chocolate and mould surface. In order to test this
hypothesis, the moisture adsorption by the polycarbonate mould
surface at varying RH was measured using CISORP (CI Electronics)
as described in Section 2.3. A simple linear relationship was ob-
served between the average moisture uptake (%) of the mould sur-
face and the RH of the air (see Fig. 8). What is interesting is that at
low RH (<40%) actually desorption of moisture takes place. Water
vapour deposited on the mould surface during the cleaning process
was removed from the mould surface at a low RH, resulting in a
negative moisture uptake. Deposited surface water could be those
molecules existing in multi-layer absorption or even in surface mi-
cro-roughness. One important experimental observation worth of
noting is that the point of changing from desorption to adsorption
almost coincides with that of the sharp decrease of surface adhe-
sion as shown in Fig. 7.
Contact time, cooling and mould temperature all affect the crys-
tallization and solidification of the cocoa fat, and consequently the
15
10
Moisture Uptake [%]
5
0
-5
-10
-15
0 20
Relative Humidity [%RH]
Fig. 8. Moisture uptake by the polycarbonate surface as a function of environmen-
tal relative humidity.
E.L. Keijbets et al. / Journal of Food Engineering 98 (2010) 133–140 139
chocolate weight ease of demoulding, as measured by the surface adhesion force.
500
surface adhesion During crystallization a three-dimensional amorphous crystal net-
chocolate residue / mould surface [g m ]
-2
work is formed (Awad and Marangoni, 2006). The network forma-
400 tion is, however, dependent on the presence of nuclei formed
either in the bulk phase, i.e. homogeneous nucleation, or at the sur-
face of existing (foreign) particles, i.e. heterogeneous nucleation
300 (Mullin, 2001). The polycarbonate mould surface is expected to
act as a foreign body, inducing nucleation and affecting crystal
growth. Varying the temperature of the mould surface will change
200 its characteristics, consequently affecting the crystal formation of
the fat phase at the chocolate–mould interface. Fluctuations in
mould temperature may cause crystal nuclei at the surface of the
100
chocolate sample to either melt or crystallize and solidify in an-
other polymorphic form. Using a specifically developed STEPSCAN
DSC, Baicoo et al. (2006) demonstrated that the cooling conditions
40 60 80 100 affect the kinetics of crystal growth. Within a tempered chocolate
the formation of low-melting polymorphs is enhanced when using
a fast cooling rate, whereas the formation of higher-melting poly-
morphs was favoured on slow cooling. The formation of different
polymorphic forms furthermore influences the crystal packing at
the chocolate–mould interface. Schenk and Peschar (2004) discuss
0
the differences in crystal packing of the b structure, where the lay-
ers are packed loosely due to the fatty acid chains being organized
perpendicular, compared to that of the b structure, where the
chains are organised parallel, consequently forming a much more
dense and closely packed structure. The varying crystal packing
of different polymorphs is responsible for differences in the degree
of contraction obtained on solidification, which in turn affects the
demoulding of the solidified chocolate bar (Beckett, 2001).
4. Conclusions
The processing conditions used especially during the moulding
and cooling stages of the chocolate manufacturing have been
shown to significantly influence the mechanism of adhesion be-
tween chocolate and mould surface, consequently affecting the
demoulding process. Different processing conditions mainly affect
crystallization and solidification of the fat phase of the chocolate.
The melting out of crystal nuclei and the formation of polymorphic
forms other than Form V as a result of processing conditions affects
the crystal arrangement of the cocoa butter fat. Consequently, lim-
ited contraction is acquired, causing difficulties in demoulding.
With respect to the effect of relative humidity, the presence of
water vapour leads to the formation of a hydrophilic mould sur-
face, which lowers the surface adhesion, due to limited choco-
late–mould interactions. The ease of demoulding can be
optimised by pre-heating the (polycarbonate) mould under con-
trolled environmental conditions, i.e. an extremely low RH (0%)
and 25–30 °C, and using a cooling temperature of approximately
10–15 °C.
Acknowledgements
We acknowledge the award of an Industrial CASE Studentship
to EK from BBSRC (UK) in collaboration with Nestlé (York) PTC.
Special thanks go to Prof. E. Dickinson, Drs. M. Fowler and M. Lead-
beater for constructive comments and suggestions.
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