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Determination of chocolate melting properties by capacitance based thermal

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DOI: 10.1007/s11694-017-9677-0

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Food Measure
DOI 10.1007/s11694-017-9677-0
ORIGINAL PAPER
Determination of chocolate melting properties by capacitance
based thermal analysis (CTA)
Juzhong Tan1 · William L. Kerr1   
Received: 22 March 2017 / Accepted: 31 October 2017
© Springer Science+Business Media, LLC 2017
Abstract  In this study, a capacitance thermal analyzer
(CTA) was designed and tested for measuring the melting
properties of chocolates, and compared with those measured
by DSC and dynamic rheology. Chocolates with different
fat content and particle size distribution (PSD) were placed
between stainless steel plates, while capacitance and temper-
ature were monitored between 20 and 60 °C. The PSD did
not influence the ­Tonset (~ 25 °C) and ­Tpeak (33 °C) measured
by DSC. However, samples with finer particles had lower
­Tend than those with coarser particles (36.59–37.28 °C). Var-
ying fat content did not result in differences in the DSC melt-
ing curves. Samples with smaller particle sizes had lower
temperatures at peak capacitance than those with larger par-
ticles, with peak temperatures ranging from 30.8 to 39.3 °C,
while higher peak capacitance values (2.61–2.84 ­10− 11 F)
were measured by CTA. Samples with higher fat content had
lower peak temperatures (range 34.7–39.71 °C) but higher
peak capacitance values (range 3.29–4.3 1­ 0− 11F). Values
from the CTA were best correlated with results determined
by dynamic thermal rheometry.
Keywords  Chocolate · Melting properties · Capacitance ·
Thermal analysis
Introduction
Chocolate is a complex semi-solid suspension of fine
particles containing cocoa, sugar, and sometimes dairy
* William L. Kerr
wlkerr@uga.edu
1
Department of Food Science and Technology, University
of Georgia, Athens, GA 30602, USA
ingredients in a continuous fat phase [1]. Chocolates are
categorized as dark, white, or milk chocolate based on the
content of cocoa mass, dairy ingredients and cocoa butter.
The production of chocolate starts from raw cocoa beans,
which are then subjected to fermentation, roasting, milling,
winnowing, refining, and tempering. The melting properties
of chocolates are critical to their quality because they greatly
influence consumer acceptability, appearance and storage
stability of the product. Improper processing can lead to
undesirable melting temperatures and crystal states, along
with loss of glossy appearance or formation of fat bloom
during storage [2–4].
One important factor that influences melting properties
is the crystal form of the fat phase in chocolate. The fat
crystals may exhibit polymorphism, that is they may have
more than two distinct crystalline forms in the same sam-
ple [2]. At least six polymorphic forms have been identi-
fied, designated Forms I through VI in the Roman numeral
system [5]. The forms have different melting temperatures:
16–18 °C for Form I (γ), 22–24 °C for Form II (α), 24–26 °C
for Form III (β′), 26–28 °C for Form IV(β1′), 32–34 °C for
Form V (β1), and 34–36 °C for form VI (β2). The Greek
letter designations refer to the way in which triglycerides are
packed into a unit cell in the crystal structure. The preferred
polymorph is Form V in most cases. Thus, most chocolate
undergoes tempering to ensure that mostly Form V exists in
the finished product. Typically, the chocolate is heated just
enough (~ 50 °C) to melt and remove all crystal structures
from the cocoa butter. The chocolate is cooled to ~  27 °C
allowing Form V, and some Form IV, crystals to grow. The
product temperature is then raised (~  29–31 °C) to melt off
Form IV crystals, and Form V seed crystals may be added
to encourage the process.
Particle size distribution and fat content of the chocolate
are also important factors influencing appearance, consumer
13
Vol.:(0123456789)

acceptance, and processing properties. The influence of
these factors on the rheological properties, texture and
consumer evaluation of chocolates have been well studied.
Afoakwa et al. [6] found that higher fat content and smaller
particle size decreased the plastic viscosity of molten dark
chocolate. Some researchers have noted that large particle
size of the cocoa mass can lead to sensations of grittiness
or coarseness in the mouth [7]. Do et al. [8] studied how fat
content and particle distribution of chocolate liquor influ-
ence the hardness and heat resistance of solid chocolates.
They also found that chocolates with higher fat content need
longer heating times to be completely melted. In addition,
chocolates with finer particles exhibited longer melting
times than those with larger particles. However, the influ-
ence of fat content and particle size distribution on melting
temperatures has been barely studied.
Differential scanning calorimetry (DSC) is one of the
most commonly used methods to determine the melting
properties of chocolates. The DSC compares the flow of
heat between a sample and empty reference pan during a
constantly changing temperature. Large changes in heat flow
are indicative of increases in specific heat related to phase
transitions. Often the heat flow change during a phase transi-
tion is not a specific point, but associated with a temperature
range. Therefore, there are several ways to characterize melt-
ing properties. That is, starch gelatinization, fat melting and
other first-order transitions can be characterized by an onset
temperature ­(Tonset), peak temperature (­ Tpeak), ending tem-
perature ­(Tend) and enthalpy of melting (∆Hmelt) [9].
The melting properties of chocolates have also been stud-
ied by dynamic thermal rheology [10]. These instruments
measure the storage modulus (G′) or loss modulus (G″). As
cocoa butter melts, the firm chocolate becomes softer and
may begin to flow. Thus, G′ is a good indicator to show the
beginning and the end of chocolate melting. Generally, G′
is on the order of 1­ 03–104 Pa for the solid and diminishes to
­100–101 Pa once melted.
Dielectric thermal analysis (DETA) is another method to
study phase transitions of food materials. DETA is carried
out by a dielectric analyzer, which measures the change of
dielectric constant ε′ and dielectric loss ε″ of a food mate-
rial as a function of temperature or AC frequency. The ε′
is the ability of a material to store energy in response to an
applied electric field. In contrast, ε″ describes the ability of
one material to dissipate energy in response to an applied
electric field, and that typically results in heat generation
[11]. The dielectric loss of a food material reaches a peak
value when it reaches the second-order transition tempera-
ture, as with a glass transition. On the other hand, when
a food material undergoes a first-order transition such as
melting, the dielectric constant will increase greatly [12].
Capacitance is an electrical property dependent upon the
dielectric properties of the medium. However, it is an easier
13
J. Tan, W. L. Kerr
property to measure as it does not require determination of
both the real and imaginary components of ε*. In addition,
many capacitance measuring instruments determine values
at discrete frequencies. Thus, they are much simpler to build
and less expensive than full-scale network analyzers. In this
study, a capacitance based thermal analysis (CTA) system was
proposed to study the melting properties of chocolate. The
apparatus was constructed at the University of Georgia using
metal plates and an inexpensive capacitance meter. Capaci-
tance is the ability of a subject to store electrical charge, and
the capacitance of a parallel-plate capacitor can be determined
as:
A
C = ε� ε0 (1)
d
where ε′ is dielectric constant or permittivity of the medium
between the parallel-plates, ε0 is the dielectric constant when
the medium is air, Ais the overlap area (completely and
exclusively filled with medium) of the two parallel plates,
and d is the distant between the two plates. The value of
ε0 varies only by 0.005% as temperature increases from 0
to 50 °C [13]. A medium such as food, particularly when
undergoing a phase transition, will have an ε′ and capaci-
tance that changes with temperature.
A few studies have used capacitance sensors similar to the
CTA to study the glass transition and melting temperatures of
frozen carbohydrate and NaCl solutions [14]. They found tran-
sition temperatures similar to those measured by differential
scanning calorimetry. A similar system has been successful
for measuring glass transitions in soft and hard sugar candies
[15]. In this study, a system is described to study the melt-
ing properties of chocolates with different fat content, particle
size distribution and cocoa mass content. DSC and viscoelastic
properties were also measured for comparison.
Frozen or glassy aqueous systems containing salts or
low molecular weight compounds such as sugars and acids
undergo a large change in ε′ when transitioning from solid to
liquid. In contrast, high fat systems have comparatively smaller
differences in ε′ between solid and liquid states. Thus, the cell
was modified from previous versions to enhance the measured
differences between states. The modified CTA consists of one
smaller upper plate and one larger base plate. During a tem-
perature scan, the chocolate sample (with larger area than the
upper plate but smaller than the base plate) melts and collapses
when the temperature reaches its melting point. The composi-
tion of the medium between the parallel plates changes from
chocolate only to layers of chocolate and air. If the layers are
separate, the capacitance of the medium is given by:
A
C = (𝜃(T)ε� + (1 − 𝜃(T))ε0 )ε0 (2)
d
where 𝜃(T) is the volume fraction of chocolate in the
medium at a specific temperature.
Determination of chocolate melting properties by capacitance based thermal analysis (CTA)
The objective of this research was to evaluate the use of
a modified CTA system to measure melting transitions in
chocolate. These were compared to results measured by DSC
and rheometry. In addition, samples with differing cocoa
mass particle size and fat content were tested to determine
if these had an influence on the measured properties.
Materials and methods
Materials
Cocoa mass containing 70.4% cocoa solids was purchased
from Callebaut (Wieze, Belgium). Raw organic cocoa butter
was purchased from Saaqin (Hicksville, New York). Raw
cocoa nibs were provided by Cocoatown (Roswell, Atlanta).
Commercial chocolates were purchased from a Kroger gro-
cery in Athens, Georgia.
Preparation of chocolate samples
Chocolate samples with different fat content were produced
by mixing raw cocoa butter with cocoa mass in percentages
of 10, 20, 30, 40, and 50% by weight. Each mix was treated
in a tempering machine (Model Revolution 2, ChocoVision
Corp., Poughkeepsie, NY). The program heating schedule
included an increase to 46 °C (over 10 min) followed by
a decrease to 27 °C (over 12 min). At that point Form V
chocolate seed crystals were added followed by an increase
in temperature to 31 °C with a hold for 5 min. The well-
tempered chocolate was poured into to 5 cm × 5 cm × 1.5 cm
chocolate molds (Wilton INC. Woodridge, IL) and held
overnight at 4 °C .
Particle size of the chocolate samples was controlled by
varying the grinding time. Raw cocoa butter was mixed with
cocoa nibs in a percentage of 10% and processed by a dou-
ble-conical stone grinding concher (Model ECGC05, Cocoa-
town, Roswell, Atlanta). About 5 ml cocoa liquid was taken
from the mix for particle size analysis every 15 min for the
first 2 h, and every 1 h thereafter. Five different batches of
cocoa butter and mass were processed in the concher for 15,
30 min, 1 h, 2, 4, and 12 h, respectively. The final chocolate
liquor from each batch was used to make chocolate samples
using the tempering method described above.
Particle size distribution
The particle size distribution was determined by laser dif-
fraction using a Malvern Mastersizer (Model MSS, Mal-
vern Instruments Ltd., Malvern, England). The presenta-
tion was selected as “Custom” with refractive indices of
n(CH3 )2 CHOHn = 1.378 and ­nparticle = 1.590 [16]. About 2 g
of chocolate sample was melted and dispersed with 30 ml
isopropanol in a 50 ml centrifuge tube, then mixed with a
vortex mixer for 2 min. The samples were then introduced
into the Mastersizer dispersion mixer until an obscuration of
20% was reached. Between samples, the detector and laser
were aligned and backgrounds were calibrated. The size dis-
tribution was expressed as the relative volume of particles
in each size range (Malvern MasterSizer Micro Software
v 2.19). Several particle size distribution parameters were
determined including d­ 10, ­d50 and d­ 90, that is the particle size
below which 10, 50 or 90% of the sample lies. In addition,
the Sauter mean diameter ­(d3,2) and volume mean diameter
­(d4,3) were determined.
Capacitance based thermal analysis (CTA)
The parallel-plate capacitor cell (Fig. 1) was built at the Uni-
versity of Georgia Instrument Design and Fabrication Shop
(Athens, GA). It consisted of a 100 mm diameter stainless
base plate, a 60 mm diameter stainless upper plate, a cylin-
drical Teflon side wall, and a threaded Teflon cap through
which a 12.5 mm diameter stainless screw could turn, and
which was welded to the upper plate. This allowed the upper
plate to be spaced a specified distance from the base plate.
The base plate and upper knob had 4 mm holes drilled to
provide connection with a banana or needle plug. A cylinder
spacer was made from Teflon with outer diameter 100 mm,
inner diameter 80 and 100 mm in height. The lower side was
fixed to the base plate by a groove on the base plate.
Plug jack
Knurled knob
Teflon
Adjustable
screw
Stainless
plates Upper plate
Plug jack Base plate
Thermocouple
Heating plate
Fig. 1  Capacitance-based thermal analysis (CTA) cell showing stain-
less conducting plates, Teflon container and hating plate
13

Each chocolate sample was placed on the base plate and
the upper plate lowered until it contacted the sample. The
base plate was then heated by a Thermolyne Nuova hot-
plate at constant temperature (80 °C). The measurement of
capacitance was done with an LCR meter (NI PXI 4072,
National Instrument Corporation, Austin, TX) attached to
a PXI chassis (NI PXI 1042, National Instrument Corpo-
ration, Austin, TX). A T-type thermocouple (Probe 1/16′′
diameter, OMEGA Engineering, Stamford, CT) penetrated
the base plate to just make contact with the sample on one
side. Temperature data was collected with a data acqui-
sition board (NI 9219, National Instrument Corporation,
Austin, TX). The virtual instrument interface and data col-
lection were accomplished with LabVIEW software (Ver-
sion 2015, National Instrument Corporation, Austin, TX).
DSC
The melting temperature of each sample was determined
by differential scanning calorimetery (Model DSC 1, Met-
tler-Toledo International Inc., Greifensee, Switzerland).
Approximately 12 mg of each sample was sealed into a
40 μl aluminum pan. An empty pan was used as a refer-
ence sample. Dry nitrogen gas was used to minimize water
condensation in the measuring cell. The temperature was
scanned from 0 to 60  °C at a heating rate of 5  °C per
minute. The onset temperature ­(Tonset), peak temperature
­( T peak), end temperature ­( Tend) and enthalpy of melting
(∆Hmelt) were calculated using the STARe Thermal Analy-
sis Software. The melting index ­(Tindex) was computed as
­(Tend − Tonset). Each sample was analyzed in triplicate and
mean values and standard deviations reported.
Dynamic rheological analyses
The viscoelastic properties of the samples as a function
of temperature were measured with a dynamic rheometer
(Model Discovery HR-2, TA Instrument Inc., New Cas-
tle DE). Before the tests were initiated, the samples were
melted and tempered in the rheometer. Approximately 4 g
of each chocolate sample was placed on the temperature-
controlled stage below a 40  mm cone and plate probe
(1.997°), then raised to 48 °C at a rate of 5 °C/min. The
sample was then cooled to 26.7 °C at a rate of 2 °C/min.
After a 5 min rest period, the temperature was raised to
31.6 °C at a rate of 2 °C/min. After the solid chocolate
was formed, the sample was then cooled to 10 °C at a rate
of 15 °C/min. The instrument was run in the small-strain
oscillatory mode, with dynamic strains set to 1%. The tem-
perature ramp was set at 10–60 °C at a rate of 5 °C/min.
13
J. Tan, W. L. Kerr
Statistical methods
All tests were repeated at least three times and results pre-
sented as the mean and standard deviation. The results were
compared by one-way ANOVA using SAS 9.3 (SAS Institute
Inc., Cary NC) to determine the effects of the fat content
and the particle size distribution of the chocolate sample on
the melting properties measured by DSC and CTA. Tukey′s
HSD was used to determine significant differences amongst
treatments at the 95% level of confidence.
Results and discussion
Particle size reduction and particle size distribution
The largest particle size ­(d90) for a typical cocoa mix (fat and
nibs) is shown in Fig. 2 as a function of grinding time. A
compilation of the size and distribution measurements (­ d10,
­d50, ­d90, ­d32, ­d4,3) is shown in Table 1. Most of the particle
size reduction was achieved within the first 2 h of grind-
ing. The initial ­d90 was 77 ± 22 µm, which was reduced to
15.5 ± 5.3 µm within 4 h, to 11.7 ± 4.1 µm within 8 h, and
finally reached a constant value of ~  8 µm (Fig. 2). As shown
in Table 1, the ­d90 and ­d4,3 were significantly smaller after
15 min, 30 min, 4 h and 8 h. The smallest diameter particle
­(d10), however, did not decrease after 15 min. This indicates
that the stone grinding is most effective at reducing the size
of large particles, but a point is reached at which no further
reduction in particle size is achieved.
A few researchers have studied the effects of particle size
on the properties of chocolate products. Bolenz and Man-
ske [17] researched the impact of fat content during grind-
ing on particle size distribution in chocolate milk. Afoakwa
et al. [18] reviewed the role that particle size distribution
100
80
Particle Size d90 (µm)
60
40
20
0
0 5 10 15 20 25
Time (h)
Fig. 2  Change in average particle size (­d90) of chocolate over time
during refining
Determination of chocolate melting properties by capacitance based thermal analysis (CTA)

Table 1  Particle size d10 (μm) d50 (μm) d90 (μm) d(3,2) (μm) d(4,3) (μm)
distribution of samples as a
function of refining time 15 min b
1.13  ± 0.14 c
11.63  ± 2.1 d
46.41  ± 19 b
2.94  ± 0.27 39.46d ± 5.4
30 min 0.84a ± 0.11 7.64b ± 1.3 30.67c ± 7.9 2.73b ± 0.18 15.98c ± 3.3
4 h 0.71a ± 0.07 5.93a ± 1.6 15.50b ± 5.3 2.06a ± 0.22 7.25b ± 1.2
8 h 0.68a ± 0.07 5.16a ± 1.1 11.75a ± 4.1 1.95a ± 0.25 5.85a ± 0.71

Mean values  ± 95% confidence intervals

Values in a column not followed by the same superscript letter are significantly different (p < 0.05)

10 Table 2  DSC melting temperatures as a function of refining time

15min Tonset (°C) Tend (°C) Tpeak (°C) Tindex (°C)

8 30min
15 min 24.60a ± 0.24 37.28b ± 0.31 32.97a ± 0.11 12.68b ± 0.19
4h 30 min 25.04ab ± 0.18 37.05b ± 0.13 32.86a ± 0.08 12.01b ± 0.23
Volume (%)

6 8h 4 h 25.50b ± 0.14 36.62ab ± 0.22 32.94a ± 0.21 11.12a ± 0.26

8 h 25.46b ± 0.27 36.59a ± 0.17 32.83a ± 0.14 11.13a ± 0.22
4 Mean values  ± 95% confidence intervals
Values in a column not followed by the same superscript letter are
significantly different (p < 0.05)
2

0 affect the melting temperature as measured be either ­Tonset

0.01 0.1 1 10 100
Particle size (um)
Fig. 3  Particle size distribution in chocolate at different times during
refining
and ingredients have in determining rheological and sensory
properties of dark chocolate. In these cases, the researchers
used a three-roller refiner followed by sifting to control par-
ticle size distribution, thus quickly creating fairly uniform
particle size distributions with one peak. In our case, particle
properties were determined solely by the grinding time. This
is more reflective of industry practices, where stone grinding
is often used to create small and uniform particle sizes after
long grinding times.
Figure 3 shows how the particle size distribution changed
during refining. Initially, there is a trimodal distribution with
sizes centered around 1, 8 and 190 µm. During grinding,
the peak with largest particles diminished, and disappeared
within 4 h. In conjunction, the middle peak shifted to smaller
sizes, with the peak value going from 9 to 5 µm. The volume
fraction of the medium size particles also increased with
time, suggesting that this fraction grew at the expense of
the larger particles.
DSC measurements of chocolate melting
The melting temperatures of chocolate samples measured by
DSC are shown as a function of the refining time (Table 2) or
fat content (Table 3). In general, particle size did not greatly
1000
and ­Tpeak. Samples with smaller particles had slightly higher
­Tonset and slightly lower ­Tend (and therefore smaller ­Tindex).
The differences were small, however, with ­Tend rang-
ing from 36.59 ± 0.17 to 37.28 ± 0.31 °C and T ­ index from
11.13 ± 0.22 to 12.68 ± 0.19 °C. Other researchers have seen
similar trends [2, 19], suggesting that in chocolate, particle
size distribution (PSD) has only a small influence on melting
properties. They concluded that chocolates with finer parti-
cles would take longer time to melt than their corresponding
products with larger particles. There is no particular reason
that the lipid phase would have differing properties due to
the cocoa mass particles. Thus, any measured differences
in melting behavior might be attributed to different crystal
sizes or polymorphs, or more likely due to differences in
heat transfer rates in samples with different size particles.
Differences in fat content (10–50%) resulted in slightly
different ­Tonset, ­Tpeak and T
­ end values. ­Tonset varied from
25.70 ± 0.14 to 26.11 ± 0.23 °C with increasing fat content,
while ­Tend varied from 36.33 ± 0.25 to 37.47 ± 0.31 °C. Thus,
­Tindex (reflective of peak width) increased from 10.22 ± 0.07
to 11.77 ± 0.16 °C. Again, this may reflect differences of
heat transfer rates in the samples. In addition, samples with
more fat will take longer to melt, and this plays out even as
the calorimeter temperature is constantly increasing. Previ-
ous studies have shown that the melting properties can be
influence by PSD, crystallization form [20, 21], lipid types,
additives, and composition [22] of chocolates. Others have
suggested that the amount of fat in dark chocolates influ-
ences the degree of crystallinity and crystal size distribution
(CSD) of the samples [23].

13
 J. Tan, W. L. Kerr

Table 3  DSC melting Fat content (%) Tonset (°C) Tend (°C) Tpeak (°C) Tindex (°C)
temperatures of chocolate with
different fat content 10 b
26.11  ± 0.23 a
36.33  ± 0.25 a
33.19  ± 0.25 10.22a ± 0.07
20 25.90ab ± 0.37 37.02b ± 0.17 33.40a ± 0.34 11.12b ± 0.11
30 25.68a ± 0.18 37.19b ± 0.36 33.80a ± 0.27 11.51c ± 0.06
40 25.61a ± 0.21 37.23b ± 0.41 33.57a ± 0.22 11.62cd ±
0.09
50 25.70a ± 0.14 37.47b ± 0.31 34.28a ± 0.40 11.77d ± 0.16

Mean values  ± 95% confidence intervals

Values in a column not followed by the same superscript letter are significantly different (p < 0.05)

Table 4  Rheometric melting temperatures as a function of refining Table 5  Rheometric melting temperatures of chocolate with different
time fat content
Tonset (°C) Tend (°C) Tindex (°C) Fat content Tonset (°C) Tend (°C) Tindex (°C)
(%)
15 min 28.4d ± 0.3 37.1a ± 0.2 9.08a ± 0.1
30 min 26.2c ± 0.4 37.9ab ± 0.3 11.7b ± 0.1 10 28.1d ± 0.3 37.2a ± 0.4 9.08a ± 0.2
4 h 25.6ab ± 0.3 38.3b ± 0.2 12.7c ± 0.03 20 27.2c ± 0.3 37.7ab ± 0.5 10.5b ± 0.2
8 h 25.1a ± 0.4 38.9c ± 0.2 13.8d ± 0.1 30 26.2bc ± 0.3 37.9b ± 0.3 11.7c ± 0.2
40 26.1b ± 0.2 38.2c ± 0.4 12.1d ± 0.1
Mean values  ± 95% confidence intervals 50 25.3a ± 0.4 38.9d ± 0.2 13.6e ± 0.1
Values in a column not followed by the same superscript letter are
significantly different (p < 0.05) Mean values  ± 95% confidence intervals
Values in a column not followed by the same superscript letter are
significantly different (p < 0.05)
Dynamic rheological analyses of chocolate melting
29
Changes in the dynamic rheological properties during tem-
perature scans of chocolate were best characterized by the 28.5
storage modulus (G′) (Table 4). In general, G′ in the solid
Capacitance (pF)

state was ~ 103–104 Pa and decreased over a short tempera-

ture range corresponding to melting, to values near 1­ 01 Pa 28

in the molten state. The beginning of melting was character-

ized as ­Tonset, where the gradient of this temperature point is
at least 3 times greater than the previous three data points.
The end of melting was characterized as T ­ end, where the
gradient after T ­ end was less than 10% less than its previous
three data points. The T ­ index of each sample was calculated
as ­Tend − ­Tonset.
As found with the DSC results, increasing fat content
resulted in larger ­Tindex values, indicating samples with
higher fat content had a broader temperature range over
which they melted (Table 5). In addition, the T ­ onset and ­Tendset
measured by the rheometer were similar to DSC measure-
ments, but did have slightly greater ­Tonset values. The differ-
ence may be attributed to the differing sample sizes (~ 3 g
vs. ~ 10 mg) required by the rheometer and DSC, respec-
tively, and that different physical phenomena are being
measured by the two instruments.
However, rheometric measurements did show a greater
range in ­Tonset (25.3 ± 0.4 to 28.1 ± 0.3 °C) than measured
by DSC, and greater statistical significance amongst values
measured for samples with differing fat levels.
27.5
27
20 30 40 50 60
Temperature (°C)
Fig. 4  Capacitance as a function of temperature during chocolate
melting. (circle) raw data, (-) processed through low-pass Butterworth
filter
CTA measurements of chocolate melting
Figure 4 shows a representative figure of how capacitance
changes with temperature for chocolate samples in the CTA
device. In general, capacitance values were in the picofarad
range for samples in the solid state. As the temperature
increased there was a slight increase in the capacitance,
followed by a decrease after melting had commenced. The
initial increase is likely due to an increase in the dielec-
tric constant ε′ as temperature increased, stemming from

13
Determination of chocolate melting properties by capacitance based thermal analysis (CTA)
increased molecular mobility. However, changes would only
be slight for molecules in the solid phase. There are different
lipid fractions in cocoa butter, and some may begin to melt at
lower temperatures. For example, Torbica et al. [24] showed
that cocoa butter had a solid fat content of 82, 76, 51 and 8%
at temperatures of 20, 25, 30 and 35 °C, respectively.
At a critical temperature, the capacitance began to drop.
This coincided with melting of the chocolate, and its flow
into the outer chamber, which began to reduce the volume
of chocolate between the plates. The receding chocolate was
replaced by air, which has a much lower dielectric constant
(1.00059 at 20 °C), and thus the measured capacitance began
to decrease.
The particle size distribution (PSD) of the samples sig-
nificantly influenced the temperature at peak capacitance,
which ranged from 30.8 ± 0.6 to 39.3 ± 0.4 °C (Table 6),
while peak capacitance values ranged from 26.1 ± 0.4 to
28.4 ± 0.3 pF. That is, finer PSD resulted in lower peak
capacitance temperature and greater peak capacitance
value. As previously noted, larger cocoa mass particle size
can produce chocolate that is more difficult to melt. This
likely resulted in higher peak temperatures for the CTA. In
addition, and by design, the heating rate in the CTA was not
carefully regulated, and this also resulted in slower melting.
It has also been observed that PSD influences the rheo-
logical properties of chocolate. Samples with larger PSD
yielded lower apparent viscosity and lower yield stress [25].
Changes in such properties may influence how the melted
chocolate spreads away from the capacitance plates, and
thus affects the measured transition temperature. However,
this would be expected to give lower measured transition
temperatures. Thus, the influence of particle size on heat
transfer and the resulting rate of melting are likely to be the
predominant factors.
Table 7 shows how the peak capacitance temperature var-
ied with fat content in the chocolate. Samples with greater
fat content resulted in lower peak capacitance temperature
(range 34.7 ± 0.3 to 39.7 ± 0.5 °C). This may be attributed to
the fact that chocolates with greater fat content have lower
apparent viscosity and yield stress, again making them easier
Table 6  CTA transitions as a function refining time
Capacitance peak tem- Peak capacitance (pF)
perature (°C)
15 min 39.3d ± 0.4 28.4d ± 0.3
30 min 36.1c ± 0.4 27.5c ± 1.1
4 h 32.4b ± 0.4 26.6b ± 0.8
8 h 30.8a ± 0.6 26.1a ± 0.4
Mean values  ± 95% confidence intervals
Values in a column not followed by the same superscript letter are
significantly different (p < 0.05)
Table 7  CTA transitions for samples with different fat content
Fat content (%) Capacitance peak tem- Peak capacitance (pF)
perature (°C)
10 39.7c ± 0.5 3.29a ± 0.15
20 37.5b ± 0.4 3.70b ± 0.02
30 36.4b ± 0.5 4.11c ± 0.05
40 35.5ab ± 0.3 4.16c ± 0.02
50 34.7a ± 0.3 4.30d ± 0.07
Mean values  ± 95% confidence intervals
Values in a column not followed by the same superscript letter are
significantly different (p < 0.05)
to flow [26, 27]. These observations concurred with results
from the dynamic rheology, which also indicated that higher
fat content in chocolate samples produced lower ­Tonset.
Overall, samples with finer particles or lower fat content
had lower peak capacitance values than those with larger
particles and more fat. One of the critical factors that influ-
ences capacitance is the dielectric constant ε′ of the medium.
The ε′ of cocoa butter (ε′ ~ 2.5) is higher than cocoa mass
(ε′ ~ 1.5), so that higher fat content in chocolate samples will
lead to higher absolute capacitance values. The way in which
particles influence the dielectric properties of inhomogene-
ous media is complex. Several models have attempted to
predict the complex permittivity of such media [28]. These
models typically incorporate the ε′ and ε” values for each
phase, the volume fraction (α), and in some cases the shape
or size factors of suspended media. In general, increasing
the volume fraction would tend to emphasize the properties
of the suspended phase. Experimental studies suggest that
these models perform better at lower α, and fail at some criti-
cal value at which percolation behavior becomes dominant.
This critical value is thought to be dependent on particle
size and shape.
Comparison of CTA, DSC and rheological data
The fat content and particles size had only a limited influ-
ence on melting temperatures as measured by DSC. In con-
trast, CTA measurements were more sensitive to variations
in fat content and PSD. Rheological assessments of melting
behavior were also more dependent on fat content and PSD.
These observations reflect that melting has a thermodynamic
component as well as a time-dependent element depend-
ent on rates of heat transfer. Thus, the rheometer and CTA
both require samples of greater mass as compared to that for
DSC. Thus, DSC might be expected to give transition tem-
peratures with greater precision, but may not totally reflect
melting behavior as experienced by real world users of a
product.
13

The transition temperatures measured by CTA were gen-
erally greater than those measured by DSC or rheometric
techniques. However, a correlation between CTA values and
the other methods was achieved. Several regression models
were tested but the best fit, without overfitting, between T
­m
measured rheological and CTA methods was achieved with
a quadratic model:
)2
( ( )
Tm,rhe = a Tm,CTA + b Tm,CTA + c
where a, b and c are fitted constants; ­Tm,CTA the melting
temperature determined by the CTA device; and T ­ m,rhe the
melting temperature determined by rheological methods.
Equation 3 was used to model all data, that is, where particle
size was varied or where fat content was varied. In addition,
the model was applied using both the rheological onset and
endset transition temperatures.
Figure 5 shows the results of the regression analyses.
Both onset and endset temperatures were correlated to the
CTA measured values. In the case of the onset temperature,
the relationship was negative (­ r2 = 0.952) while for the end-
set temperature it was positive (­ r2 = 0.950). This does show
that, if desired, the CTA method could be correlated with
another technique.
This does raise the issue as to which approach provides
the truest measure of melting point. For a pure substance, the
­Tm is more easily determined as melting occurs over a very
sharp range. Chemists have often placed crystalline materi-
als in capillary tubes and denoted where a sample visually
melts as the temperature is increased slowly. In theory, a
pure substance melts at one temperature, however there is
always the need to impose a higher external temperature
to allow heat transfer. Mixed crystalline systems, such as
40
35
Tm,on = -0.0169 (Tm,CTA)2 + 0.998 (Tm,CTA) + 24.14
r2 = 0.952
Rheo Tm (°C)
30
25
Tm,en = 0.0468 (Tm,CTA)2 - 2.937 (Tm,CTA) + 71.34
r2 = 0.950
20
30 32 34 36
CTA Tm (°C)
Fig. 5  Comparison of T­ m values determined by change in storage
modulus (G′) during temperature scanning, and by CTA
13
J. Tan, W. L. Kerr
cocoa butter, melt over a broader range of temperature. This
occurs as various distributions of fatty acids create fats with
different melting fractions. In addition, fats may exist in one
or more polymorphic forms that have different melting tem-
peratures. These materials are best analyzed by scanning
the temperature. The change in signal with time/temperature
depends on the device. Thus the way that heat flux changes
(in DSC) with solid fat ratio (as different fractions melt) is
not identical to the way that molecular relaxations respond
(3)
during thermal rheology.
Sample size and heating rate are other factors that skew
the results. Samples with more mass take longer to melt,
thus spread the melting process over a wider temperature
range. However, overly small samples may hamper sensitiv-
ity. In general, lower heating rates should give truer results,
but may compromise sensitivity and cause unacceptably
long measurement times. All of the methods discussed are
only as good as the temperature measurement. Thus, DSC,
rheological or dielectric thermal devices need to be cali-
brated with materials of known melting properties.
The above factors also influence the various transition
temperatures that are recorded. For example, the peak tem-
perature often reported for DSC depends on both the sample
size and heating rate. The CTA device was more sensitive
to measuring the onset melting temperature than the other
techniques studied, thus we expect it to be most beneficial
to determine where melting begins.
Conclusions
The CTA device introduced in this study measured melt-
ing temperatures in chocolate with good repeatability.
The device also showed some sensitivity to the effects of
cocoa particle size and fat content on melting behavior. The
instrument was inexpensive as it was built from metal plates
connected to a capacitance meter, and did not require pre-
cise control of temperature ramping as used with DSC or
dynamic thermal rheometers. While the measured tempera-
tures were not identical to those from DSC or rheometric
techniques, they could be easily correlated with those values
if required.
Acknowledgements  We would like to thank Dr. M. Balu and the
CocoaTown Company in Atlanta, Georgia for their help with funding
and acquisition of supplies.
38 40
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