Food Research International 41 (2008) 751757

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Food Research International

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Characterization of melting properties in dark chocolates from varying particle

size distribution and composition using differential scanning calorimetry
Emmanuel Ohene Afoakwa a,*, Alistair Paterson a, Mark Fowler b, Joselio Vieira b
a
b

Centre for Food Quality, SIPBS Royal College Building, University of Strathclyde, 204 George Street, Glasgow G1 1XW, Scotland, UK
Nestle Product Technology Centre York, P.O. Box 204, Haxby Road, York YO91 1XY, United Kingdom

a r t i c l e

i n f o

Article history:
Received 31 January 2008
Accepted 30 May 2008

Keywords:
Chocolate
Fat crystallization
Particle size distribution
Melting properties
DSC

a b s t r a c t
Melting properties in dark chocolates processed from varying particle size distribution (PSD), fat and lecithin content were studied using differential scanning calorimetry (DSC). Compositional parameters were
PSD (D90 (90% ner than this size) of 18, 25, 35 and 50 lm), fat (25%, 30% and 35%) and lecithin (0.3% and
0.5%) contents. Variations in PSD had no inuence on crystallinity of products. Fat and lecithin content
inuenced the degree of crystallinity and melting properties (Tend, Tindex and DHmelt) of the products.
Increasing fat content caused consistent increases in degree of crystallinity and crystal size distribution,
thus effecting signicant changes in Tend, Tindex and DHmelt of their derived products. Increasing lecithin
content however reduced the crystal sizes in products. Particle size (PS) increases had limited effects on
Tonset, Tpeak, and DHmelt independent of fat and lecithin content. Signicant decreases in Tend and Tindex
were noted with PS increases at all fat and lecithin contents. Similar increases in Tend and Tindex were
noted with increases in fat content at all PS and lecithin levels. Contrary, increasing lecithin content in
products resulted in signicant decreases in Tend, Tindex and DHmelt. Thus, variations in fat and lecithin
contents during dark chocolate manufacture inuence the crystallinity of products, and with PSD, they
all inuence the melting index (duration) of their derived products.
2008 Elsevier Ltd. All rights reserved.

1. Introduction
Dark chocolates are suspensions of sucrose and cocoa particles,
coated in phospholipids in a continuous fat phase, generally cocoa
butter, with total solid content of 65% to 75%. The outcome is production of a smooth suspension of particulate solids in cocoa butter (Beckett, 1999; Whiteeld, 2005), solid at ambient temperature
(2025 C) but forms a smooth dense suspension at oral temperatures (37 C). This oral liquefaction is dened by the fat melting
characteristics and inuences the perception of avour and mouthfeel attributes. The intensity of perceived taste and avour changes
over time as the chocolate is melted, manipulated and mixed with
saliva (Afoakwa, Paterson, & Fowler, 2007; Ziegler & Hogg, 1999).
Central to chocolate sensory character is a continuous-phase lipid composition (primarily cocoa butter), which inuences melting
properties and mouthfeel character. Continuous-phase lipids are
primarily triacylglycerides (TAGs) dominated by 1,3-disaturated2-oleoylglycerol type: 1,3-dipalmitoyl-2-oleoylglycerol (POP),
1-palmitoyl-2-oleoyl-3-stearoylglycerol (POS) and 1,3-distearoyl2-oleoylglycerol (SOS) and smaller quantities of mono- and
di-acylglycerides, polar lipids, free fatty acids and fat-soluble compounds (Chaiseri & Dimick, 1987). Cocoa butter can crystallize as a
* Corresponding author. Tel.: +44 (0) 7984288727.
E-mail address: [email protected] (E.O. Afoakwa).
0963-9969/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodres.2008.05.009

function of triglyceride composition (fatty acids; Talbot, 1999) into

six polymorphic forms (IVI), where Form I is the least stable and
V, the most desirable form, which can transform to VI, the most
stable, in storage. Polymorphic triglyceride forms differ in distance
between fatty acid chains, angle of tilt relative to plane of chain
end methyl group and manner in which triglycerides pack in crystallization (Ali, Selamat, CheMan, & Suria, 2001; Talbot, 1999). In
manufacture, a thermal process known as tempering is used to obtain the desirable form V (or 2) in cocoa butter with a melting
temperature of 3234 C, and conferring the desired glossy
appearance, good snap, contraction and enhanced shelf life
(Beckett, 2000; Seguine, 1991; Talbot, 1999; Timms, 2003). Poorly
tempered chocolate develops in storage a white or grey surface
layer, fat bloom, subsequently converting from form V into the
more stable form VI.
Particle size distribution inuences rheology and texture with
specic surface area and mean particle size inuencing yield stress,
plastic viscosity, product spread and hardness (Afoakwa, Paterson,
& Fowler, 2008a; Beckett, 2000; Chevalley, 1999). Smaller particles
improve sensory properties (Ziegler, Mongia, & Hollender, 2001)
but plastic viscosity and yield stress increase due to changes in surface area of particles in contact with fat phase. Particle size optimisations can reduce requirement for viscosity modiers and
improve process control (Afoakwa et al., 2008a). Although PSD
and composition in chocolate inuences on rheology and sensory

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E.O. Afoakwa et al. / Food Research International 41 (2008) 751757

characters have been described (Afoakwa, Paterson, Fowler, &

Vieira, 2008b; Afoakwa et al., 2008a; Mongia & Ziegler, 2000;
Ziegler et al., 2001), their inuence on melting behaviour still
remains unknown.
During chocolate manufacture, the crystalline state and the proportion of solid fat present are important in determining the melting character in nished products. Differential scanning
calorimetry (DSC) has been used to characterize changes in chocolate melting proles and measures the relative amounts of each
crystalline state (Tabouret, 1987; Walter & Cornillon, 2001, 2002;
Ziegleder & Schwingshandl, 1998); and peaks corresponding to latent heat, are observed in temperature ranges related to melting of
specic polymorphs (McFarlane, 1999). Such information is relevant to sensory character and impacts on mechanical and rheological properties of chocolate and confectionery shelf life (Hartel,
2001). In this study DSC was used to characterize the effects of particle size distribution, fat and lecithin content on the crystallinity,
crystal size distribution and melting proles of nished dark
chocolates.

stage tempering unit (Model AMK 10, Aasted Mikroverk A/S, Farum, Denmark). Chocolate was pumped through the multi-stage
units and a worm screw drove the product through the heat
exchangers. Sensors located at specic points in the equipment
measured the temperature of both the chocolate and the coolant
uid at each stage. The temperatures of each of the three stages
were thus set and controlled independently of each other to obtain
a nal chocolate temperature of 27 C to promote crystal growth
of the desired triacylglyceride fractions. Pre-crystallization was
measured using a computerized tempermeter (Exotherm 7400,
Systech Analytics, SA, Switzerland). A built-in algorithm was used
to ensure an optimal temper regime of Slope 0 0.3 (5.0 1 CTU).
The principle of this method has been described by Nelson (1999).
The tempered chocolate was moulded using plastic moulds:
80 mm length; 20 mm breadth; and 8 mm height, allowed to cool
in a refrigerator (5 C) for 2 h before de-moulding onto plastic trays
and conditioned at 20 2 C for 14 days before analysis.

2. Materials and methods

A MasterSizer Laser Diffraction Particle Size Analyzer equipped

with MS 15 Sample Presentation Unit (Refractive index 1.590)
(Malvern Instrument Ltd., Malvern, England) was used. About
0.2 g of rened dark chocolate was dispersed in vegetable oil
(Refractive index 1.450) at ambient temperature (20 2 C) until
an obscuration of 0.2 was obtained. The sample was placed under
ultrasonic dispersion for 2 min to ensure particles were independently dispersed and thereafter maintained by stirring during the
measurement. Size distribution was quantied as the relative volume of particles in size bands presented as size distribution curves
(Malvern MasterSizer Micro Software v 2.19). PSD parameters obtained included specic surface area, largest particle size (D90),
mean particle volume (D50), smallest particle size (D10) and Sauter
mean diameter (D[3, 2]). The four PSD used for the study are as
shown (Table 2).

2.1. Materials
Cocoa liquor of Central West African Origin was obtained from
Cargill Cocoa Processing Company (York, UK); sucrose (pure beet
extra ne granulated) from British Sugar Company (Peterborough,
UK); pure prime pressed cocoa butter and soy lecithin from ADM
Cocoa Limited (Koog aan de Zaan, Netherlands) and Unitechem
Company Ltd. (Tianjin, China), respectively.
The recipe (Table 1) and formulations used for the production of
samples have been described previously (Afoakwa et al., 2008a).
Chocolates were formulated with total fat of 2535% (w/w) from cocoa liquor and cocoa butter with >34% total cocoa: composition as
specied for dark chocolate by relevant directives (Codex Revised
Standard, 2003; European Commission Directive, 2000). Experimental samples (5 kg batch for each formulation) were produced
by mixing sucrose and cocoa liquor in a Crypto Peerless Mixer (Model K175, Crypto Peerless Ltd., Birmingham, UK) at low speed for
2 min and then at high for 3 min, then using a 3-roll rener (Model
SDX 600, Buhler Ltd., CH-9240 Uzwil, Switzerland) to a specied
particle size (D90:18 1 lm, 25 1lm, 35 1 lm & 50 1 lm) conducting particle size analysis, during rening, to ensure D90 values.
Rened chocolates were placed in plastic containers and conditioned at 5055 C for 24 h to ensure melting of fat within chocolate
mass prior to conching in a Lipp Conche (Model IMC-E10, Boveristr
40-42, D-68309, Mannhein, Germany) at low speed for 3.5 h at
60 C. Lecithin and cocoa butter were added and mixtures then conched at high speed for 30 min to effect adequate mixing and liquefaction. Samples were kept in sealed plastic containers at ambient
(2022 C) and moisture and fat contents determined using Karl
Fischer and Soxhlet methods (ICA, 1988) and (ICA, 1990).
2.1.1. Tempering procedure
Samples were incubated at 50 C for 4 h for melting and tempered using an Aasted Mikrovert laboratory continuous three-

Table 1
Recipes used for the formulation of the dark chocolate
Ingredient

25% Fat (w/w)

30% Fat (w/w)

35% Fat (w/w)

Sucrose (%)
Cocoa liquor (%)
Cocoa butter (%)
Lecithin (%)

58.80
35.90
5.0
0.3

49.70
45.00
5.0
0.3

40.70
54.00
5.0
0.3

59.00
35.50
5.0
0.5

49.90
44.60
5.0
0.5

40.80
53.70
5.0
0.5

2.2. Determination of particle size distribution

2.3. Determination of melting properties of dark chocolates

Differential scanning calorimeter (DSC Series 7, Perkin Elmer
Pyris, Norwalk, CT, USA) equipped with a thermal analysis data station was calibrated using indium and octadecane at a scan rate of
5 C/min using an aluminium pan as reference. Samples (5 mg)
were loaded into 40 ll capacity pans with holes and sealed with
lids using a sample press. Pans were heated at 5 C/min from 15
55 C in a N2 stream. Onset temperature (Tonset), peak temperature
(Tpeak), end temperature (Tend) and enthalpy of melting (DHmelt)
were calculated automatically by the software. Melting index
(Tindex) was computed as (Tend Tonset), as described by Vasanthan
and Bhatty (1996). Each sample was analyzed in triplicate and
mean values and standard deviations reported.
2.4. Experimental design and statistical analysis
Three experimental variables comprising PSD, fat and lecithin
contents were used. Other variables including rener temperature
and pressure, conching time and temperature were held constant.
A 4  3  2 factorial experimental design was used with: PSD
(D90): 18, 25, 35 and 50 lm; fat: 25%, 30% and 35% (w/w); lecithin:
0.3% and 0.5% (w/w). Statgraphics Plus 4.1 (Graphics Software System, STCC, Inc, Rockville, USA) examined melting properties (Tonset,
Tend, Tindex, Tpeak and DHmelt) using two-way analysis of variance
(ANOVA) and multiple range tests to determine the effects of factors and their interactions. Tukey multiple comparisons (95% signicance level) was employed to determine the differences
between levels. All process treatments and analysis were conducted in three replicates and the mean values reported.

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E.O. Afoakwa et al. / Food Research International 41 (2008) 751757

Table 2
Particle size distribution of the dark chocolates
Particle size (PS) d(0.9)a (lm)

18 1.0

Fat content (%)

25
30
35

25 1.0

25
30
35

35 1.0

25
30
35

50 1.0

25
30
35

Lecithin (%)

Particle size distribution

Specic surface area (m2/g)

D(v, 0.1)a (lm)

D(v, 0.5)a(lm)

D[3, 2]a (lm)

D(v, 0.9)a (lm)

0.3
0.5
0.3
0.5
0.3
0.5

1.98 0.02
1.95 0.05
1.84 0.03
1.93 0.01
1.53 0.03
1.55 0.05

1.12 0.02
1.06 0.04
1.07 0.03
1.01 0.03
1.40 0.05
1.37 0.03

4.81 0.05
4.62 0.09
4.93 0.05
4.85 0.04
6.04 0.06
6.01 0.05

2.66 0.04
2.56 0.02
2.70 0.04
2.56 0.02
3.12 0.05
3.22 0.03

18.53 0.19
18.88 0.70
18.76 0.46
18.67 0.50
18.70 0.24
18.50 0.25

0.3
0.5
0.3
0.5
0.3
0.5

1.68 0.08
1.61 0.02
1.57 0.02
1.58 0.02
1.46 0.02
1.44 0.03

1.19 0.04
1.25 0.02
1.31 0.02
1.17 0.03
1.44 0.05
1.46 0.03

5.45 0.04
5.79 0.07
5.92 0.06
5.65 0.04
6.60 0.06
6.65 0.03

2.83 0.04
3.01 0.04
3.06 0.03
2.98 0.02
3.40 0.06
3.46 0.04

25.47 0.04
25.73 0.57
25.30 0.65
25.76 0.40
25.10 0.32
25.01 0.13

0.3
0.5
0.3
0.5
0.3
0.5

1.43 0.04
1.48 0.09
1.39 0.02
1.46 0.04
1.28 0.05
1.28 0.01

1.43 0.04
1.37 0.03
1.51 0.03
1.41 0.04
1.67 0.06
1.68 0.04

6.73 0.07
6.44 0.06
6.72 0.02
6.66 0.05
7.49 0.06
7.59 0.05

3.31 0.03
3.41 0.04
3.50 0.02
3.47 0.06
3.84 0.05
3.86 0.03

35.98 0.14
35.06 0.26
35.73 0.27
35.45 0.58
35.55 1.14
35.23 0.75

0.3
0.5
0.3
0.5
0.3
0.5

1.29 0.01
1.31 0.02
1.34 0.04
1.18 0.05
1.12 0.04
1.07 0.03

1.62 0.03
1.56 0.05
1.56 0.03
1.79 0.05
2.02 0.04
2.05 0.04

7.70 0.03
7.67 0.06
7.69 0.05
8.25 0.05
8.95 0.09
9.21 0.03

3.76 0.05
3.73 0.04
3.70 0.06
3.92 0.04
4.42 0.06
4.54 0.04

50.29 0.65
50.12 0.48
50.40 0.79
50.41 0.90
50.01 0.48
50.15 0.46

Mean values standard deviations from triplicate analysis.

a
D(v, 0.1), D(v, 0.5), D[3, 2] and D(v, 0.9) respectively represent 10%, 50%, Sauter mean diameter and 90% of all particles ner than this size.

3. Results and discussion

3.1. Particle size distribution of dark chocolates
Wide variations in PSD (Table 2) were observed for 18, 25, 35
and 50 lm (Fig. 1) using D90 values (>90% ner) that correlate with
chocolate character and micrometer measurements of largest particles (Beckett, 2000). The volume histograms showed narrow
(18 lm PS) and wide (25 lm PS) bimodal and narrow (35 lm
PS), and wide (50 lm PS) multimodal size distributions (Fig. 1).
These PSD range 1850 lm covers the optimum minimum and
maximum sizes with direct effects on texture and sensory character in nished chocolate (Beckett, 2000; Ziegler & Hogg, 1999).
Data on PSD (Table 2) gave specic surface area, mean particle
volume D(v, 50) and Sauter mean (D[3, 2]) with increasing D90 par-

ticle sizes. An inverse relationship in D90 from 1850 lm and specic surface area was signicant with direct relationships with
Sauter mean and mean particle diameters (Table 2). Largest PS
(D90) was directly proportional to D10, D50 and Sauter mean
(D[3, 2]), and inversely proportional to specic surface area of particles. Increasing fat from 25% to 35% of samples gave signicant
reductions in specic surface area with increases in all other PSD
parameters (Table 3), explaining that the fat content of samples
during rening had a direct inuence on PSD. Beckett (1999) concluded largest particle size and solids specic surface area were the
two key parameters for chocolate manufacture. The former determines chocolate coarseness and textural character, the latter is
associated with requirement of fat for desirable ow properties.
Specic surface area has been inversely correlated with component
PSD previously (Beckett, 1999; Sokmen & Gunes, 2006; Ziegler &

10

100
90
80

Volume (%)

70
60
50
40

d
c

30

20

0
0.1

10
0

1.0

10.0

100.0

1000.0

Particle Diameter (m)

Fig. 1. Particle size distribution of dark chocolate with D90 of (a) 18 lm (b) 25 lm (c) 35 lm (d) 50 lm.

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E.O. Afoakwa et al. / Food Research International 41 (2008) 751757

PSD inuences chocolate rheological and microstructural properties as well as texture in derived molten and tempered products
(Afoakwa, Paterson, Fowler, & Vieira, in press; Afoakwa et al.,

2008a). The thermogram (Fig. 3) showed similar peak shapes and

sizes for dark chocolates manufactured with varying PSD, suggesting no characteristics differences in crystallinity and degree of
crystallization between the products. Table 4 shows values for
key DSC parameters (Tonset, Tend, Tpeak, DHmelt and Tindex). Increasing
PS from 18 lm to 50 lm caused no signicant (P = 0.675) changes
in Tonset, at all fat and lecithin levels (Table 5). Values for Tonset were
in the range of 26.526.6 C in products containing 25% fat and
0.3% lecithin at 18 lm and 50 lm PS respectively. Similar insignificant differences (P > 0.05) in Tonset were noted with varying PS at
all fat and lecithin levels (Table 5). Likewise, Tpeak in products with
varying PSD, fat and lecithin contents showed only marginal differences. The results (Table 4) showed that Tpeak of products with
increasing PS from 18 lm to 50 lm ranged between 32.3 C and
32.5 C respectively in products containing 25% fat and 0.3% lecithin, and this trend was similar at all fat and lecithin concentrations. These showed that the initiation and maximum
temperatures in dark chocolate melting are independent of PSD,
with mean values for Tonset and Tpeak of 26.5 C and 32.4 C,
respectively (Table 4). Similar non-signicant differences
(P > 0.05) in DHmelt were found between products with varying
PS at all fat and lecithin contents (Table 5). Values of DHmelt in
products with increasing PS from 18 lm to 50 lm ranged from
30.07 J/g to 30.62 J/g in products containing 25% fat and 0.3% lecithin, and this marginal and insignicant differences (P > 0.05) in
trends were similar at all fat and lecithin levels. The non-signicant
relationship between PSD and DHmelt, implies that enthalpy of
melting was similar for chocolates at all PS at specied fat and lecithin levels. This indicates that irrespective of the ingredient (fat or
lecithin content) used for the formulation, dark chocolates produced with varying PS would require similar energy to complete
melting.
In contrast, varying PSD had signicant effects on Tend and Tindex
of products. Generally, there were inverse relationships between
particle size and Tend and Tindex, at all fat and lecithin contents (Table 4). Products with smaller PS (18 lm) at 25% fat and 0.3% leci-

Fig. 2. Illustration of DSC thermogram used to characterize the melting properties.

Fig. 3. Typical DSC thermograms for dark chocolate at 30% fat and 0.5% lecithin
content varying PSD: (a) 18 lm, (b) 25 lm, (c) 35 lm and (d) 50 lm.

Table 3
ANOVA Summary of F-ratios from particle size distribution
Process variables
A: Particle size (D90)
B: Fat
AB
*

Specic surface area

*

302.77
115.88*
4.37*

D(v, 0.1)
*

455.54
312.87*
6.63*

D(v, 0.5)
*

1007.84
311.17*
2.59*

D[3, 2]
546.01*
228.10*
3.52*

Signicant F-ratios at P 6 0.05.

Hogg, 1999). Fat content analyses showed values of 25 1, 30 1

and 35 1 respectively. Moisture contents were also within the
range 0.800.98%.
3.2. Melting properties of dark chocolate
Peak onset corresponds to the temperature at which a specic
crystal form starts to melt; peak maximum, that at which melting
rate is greatest; and end of melting, completion of liquefaction all
these information are related to the crystal type. Peak height, position and resolution are dependent on sample composition and
crystalline state distribution (McFarlane, 1999). All the samples
exhibited similar distinct single endothermic transitions between
15 and 55 C, the range expected for chocolate melting proles.
Fig. 2 shows a typical DSC thermogram used for evaluating the
melting properties of dark chocolates manufactured from varying
PSD, fat and lecithin content. It recorded that heat capacity cp gradually and consistently increased to onset temperature (Tonset), and
then progressively increased more rapidly until peak temperature
(Tpeak), after which it decreased to the end temperature (Tend) indicating the chocolate was completely melted.
3.3. Effects of particle size distribution

E.O. Afoakwa et al. / Food Research International 41 (2008) 751757

Table 4
Melting properties of dark chocolate from varying PSD, fat and lecithin content
Particle size
(Dv, 0.9) (lm)

Fat Lecithin Melting properties

(%) (%)
Tend
Tonset
(C)
(C)

18 1.0

25
30
35

25 1.0

25
30
35

35 1.0

25
30
35

50 1.0

25
30
35

Tindex
(C)

Tpeak
(C)

DHmelt
(J/g)

0.3
0.5
0.3
0.5
0.3
0.5

26.2 0.2
26.0 0.1
26.5 0.3
26.3 0.2
26.4 0.1
26.5 0.2

34.6 0.3
34.2 0.4
34.4 0.4
33.9 0.2
33.8 0.2
33.7 0.3

8.4 0.2
8.2 0.4
7.9 0.2
7.5 0.3
7.4 0.1
7.2 0.3

32.5 0.2
32.0 0.3
32.5 0.4
32.4 0.3
32.4 0.2
32.5 0.2

30.07 0.38
28.20 0.12
36.52 1.05
30.02 0.42
44.59 0.62
43.10 1.23

0.3
0.5
0.3
0.5
0.3
0.5

26.3 0.1
26.3 0.2
26.6 0.2
26.5 0.1
26.6 0.3
26.5 0.2

34.4 0.2
34.1 0.2
33.9 0.3
33.5 0.2
33.7 0.2
33.5 0.3

8.1 0.2
7.8 0.3
7.3 0.4
7.0 0.3
7.1 0.3
7.0 0.1

32.4 0.3
32.4 0.3
32.2 0.1
32.5 0.3
32.2 0.1
32.2 0.1

30.52 0.73
29.08 0.46
37.09 1.24
32.46 0.66
45.01 1.42
43.41 1.28

0.3
0.5
0.3
0.5
0.3
0.5

26.3 0.1
26.4 0.1
26.6 0.3
26.7 0.3
26.8 0.4
26.9 0.4

34.2 0.5
34.0 0.4
33.8 0.2
33.7 0.1
33.6 0.3
33.4 0.2

7.9 0.2
7.6 0.3
7.2 0.2
7.0 0.1
6.8 0.3
6.5 0.1

32.6 0.3
32.4 0.3
32.4 0.2
32.6 0.2
32.8 0.3
32.2 0.3

30.68 0.28
28.60 0.34
37.19 0.94
34.01 0.63
45.15 1.05
42.79 0.84

0.3
0.5
0.3
0.5
0.3
0.5

26.6 0.2
26.7 0.1
26.8 0.3
26.7 0.3
26.8 0.4
26.8 0.3

34.0 0.4
33.9 0.2
33.5 0.3
33.3 0.3
33.2 0.1
33.0 0.4

7.4 0.5
7.2 0.3
6.7 0.3
6.6 0.2
6.4 0.1
6.2 0.4

32.3 0.2
32.4 0.2
32.9 0.4
32.2 0.2
32.7 0.3
32.4 0.1

30.62 0.53
28.62 0.23
37.29 0.15
33.25 1.05
45.40 0.87
43.43 0.46

Mean values from triplicate analysis standard deviation.

Table 5
ANOVA Summary of F-values of the melting properties
Process variables
A: Particle size
B: Fat
C: Lecithin
AB
AC
BC
ABC
*

Tonset (C)
1.53
12.54
2.43
0.89
2.16
2.45
1.73

Tend (C)
*

11.00
32.32*
18.18*
2.89*
2.39
0.53
1.01

Tindex (C)
*

199.84
2330.26*
148.84*
99.22*
31.69*
198.58*
19.76*

Tpeak (C)

DHmelt (J/g)

0.84
0.23
3.13
0.49
0.91
0.66
2.17

121.52
3535.29*
376.74*
4.22
1.46
401.87*
3.73

755

kwa et al., in press; Do, Hargreaves, Wolf, Hort, & Mitchell, 2007;
Afoakwa, Paterson, Fowler, & Vieira, 2008d). Do et al. (2007) also
noted that decreases in the amount of particle aggregation and
structure build up in ow affect chocolate melt down, suggesting
that in its crystallized state, the particle skeleton of chocolates with
larger PS is less interconnected, providing less resistance to breakage and melt down. This knowledge is important as it provides
information on likely oral melting behaviour with an impact on
temporal components of avour release and also oral epithelial
sensation. Beckett (1999) and Ziegler et al. (2001) noted that variations in PS might inuence melt, avour, colour and gloss of
chocolates.
3.4. Effects of fat content
Data from the DSC (Fig. 4) indicated that varying fat content produced changes in crystallinity and melting properties observed in
the differences in their peak widths. This suggests that the fat content in dark chocolates during manufacture inuences the degree of
crystallinity and crystal size distribution (CSD) of their corresponding tempered products. Lonchampt and Hartel (2004) also noted
that amount and composition of fat in chocolate production had
unpredictable effects on crystal size, and polymorphism and crystallization rate in products. Hartel (2001) concluded distribution
of crystal sizes in foods play key roles in nal product quality, dened by total and specic characteristics of the crystalline material.
Number of crystals and range of sizes, shapes, and polymorphic stability, as well as arrangements in network structures dictates
mechanical and rheological properties. Knowledge and control of
CSD can be important for optimising processing conditions.
Results from the DSC data on Tonset. Tend, Tpeak, DHmelt and Tindex
with varying fat content are as shown on Table 4. ANOVA and multiple mean comparisons showed no signicant difference (P > 0.05)
for Tonset and Tpeak in chocolates with different fat contents (Table
5), implying limited inuence on temperatures for onset and peak
melting. There were signicant differences (P < 0.05) among Tend,
Tindex and DHmelt (Table 5). Increasing fat content from 25% to
35% caused consistent reductions in Tend from 34.6 C to 33.8 C

Signicant F-ratios at P 6 0.05.

thin content had Tend value of 34.6 C, whilst those with 50 lm had
34.0 C, representing a difference of 0.6 C. Similar marginal but
signicant (P < 0.05) decreasing trends in Tend were observed at
all fat and lecithin levels (Table 5), suggesting that dark chocolates
with larger PS (50 lm) require slightly lower temperatures to complete melting than their corresponding smaller PS (18 lm) products. However, Tend values in all the products were in the range
33.0 to 34.6 C indicating all samples had similar Form V (2) polymorphic stability. A similar inverse relationship was observed between Tindex and PSD. The data (Table 4) showed that increasing
PS for 18 lm to 50 lm in chocolates containing 25% fat and 0.3%
lecithin caused signicant (P < 0.05) reductions in Tindex from
8.4 C to 7.4 C, respectively. ANOVA showed signicant (P < 0.05)
inuence of PSD on Tend and Tindex with signicant interactions
for fat and lecithin contents (Table 5). Multiple range test revealed
signicant differences (P = 0.001) between Tend of products containing 18 lm, 35 lm and 50 lm, indicating that chocolates with
ner particles would take relatively longer time to melt than their
corresponding products with larger particles, suggesting their possible relationships with the relative strengths of the inter-particle
aggregations and occulation in the different products. Chocolates
with smaller PSD (D90, 18lm) have been found to contain higher
particle-to-particle strengths with resultant increases in hardness
(texture) than their corresponding larger PSD (D90, 50 lm) (Afoa-

Fig. 4. Typical DSC thermograms for dark chocolate at 18 lm PS and 0.5% lecithin
content with varying fat content: (a) 25%, (b) 30%, (c) 35%.

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E.O. Afoakwa et al. / Food Research International 41 (2008) 751757

in products containing 18lm PS and 0.3% lecithin level. Similar

marginal but signicant (P < 0.05) decreasing trends in Tend with
increasing fat content were noted at all PS and lecithin concentrations (Table 5). These suggest that low fat (25%) chocolates completed melting at higher temperatures than those with more fat
(3035%). Likewise, increasing fat content caused consistent decreases in Tindex of products, suggesting an inverse relationship of
Tindex with fat content (Table 4). Products with lower (25%) fat content, 18 lm PS and 0.3% lecithin had Tindex of 8.4 C and this reduced consistently with from 7.9 C and 7.4 C, respectively with
increasing fat content to 30% and 35%. Similar reducing trends in
Tindex were noted at all PS and lecithin levels. These explain that
lower fat chocolates required longer time to melt than similar
products with higher fat contents, again with a likely impact on
behaviour during consumption. Lower melting duration in high
fat chocolates can be attributed to reductions in inter-particle
interactions and increased free-moving plastic ow, possibly related to yield value of products (Afoakwa et al., in press; Beckett,
2000; Do et al., 2007). Fat lls voids between particles in molten
chocolate and reduces resistance to ow, with a direct relationship
between fat content and DHmelt, independent of particle size. This
implies that enthalpy is reduced in products of lower fat contents.
From ANOVA and multiple comparison tests, fat content had the
greatest inuence on melting characteristics in these chocolates
(Table 5).
3.5. Effects of lecithin
The amphiphilic nature of lecithin promotes deagglomeration
with effects on physical properties ( Beckett, 2000; Dhonsi &
Stapley, 2006; Lonchampt & Hartel, 2004; Talbot, 1999). Fig. 5
shows typical DSC thermograms for dark chocolate manufactured
from varying lecithin content (0.3% and 0.5%) at 18 lm PS and
30% fat content. The thermograms (Fig. 5) revealed the effect of lecithin concentration on crystallinity of products. The differences observed in peak widths suggest a moderate reducing effect of
lecithin addition on degree of crystallinity, with consequential ef-

fect on some melting properties of products. Earlier studies reported that lecithin content had signicant (P < 0.001) effect on
the rheological and textural properties of dark chocolates with signicance among the interactions with PS and fat content (Afoakwa
et al., 2008a, 2008b). Table 4 shows the results from the DSC data
on Tonset. Tend, Tpeak, DHmelt and Tindex with varying lecithin. Analysis
of the values deduced from ANOVA and multiple mean comparisons showed no signicant difference (P > 0.05) between Tonset
and Tpeak for the different lecithin concentrations, but signicant
differences (P < 0.05) among Tend, Tindex and DHmelt (Table 5). Both
Johansson and Bergenstahl (1992), and Lonchampt and Hartel
(2004) reported lecithin inuences sugar coating, fat crystallization, crystal growth, polymorphism and oil migration, but has limited effect on solid fat content.
Generally, there were inverse relationships between Tend and
Tindex, independent of particle size and fat content (Table 4). Thermograms (Fig. 5) showed increasing lecithin content inuenced
crystal dimensions and melting character in products. Increasing
lecithin content of products from 0.3% to 0.5% caused marginal
but signicant differences in Tend of products, noticeable at all PS
and fat concentrations (Table 4). The Tend values were between
33 and 34 C, an indication that the crystallizations were in V
polymorph, imply limited inuence under normal tempering conditions. On the other hand, Tindex decreased consistently with
increasing lecithin content, suggesting that products containing
lower lecithin levels (0.3%) might require relatively longer residence time to melt than those of their corresponding products with
higher lecithin levels (0.5%), with likely impact on the melting residence time of products during consumption. The lower melting index (duration) observed with products containing higher lecithin
levels might be attributed to sugar coating ability of lecithin during
processing, and thus reducing their inter-particle interaction to induce chocolate melting properties. Dhonsi and Stapley (2006) reported lecithin migrates to sugar/fat interfaces and coats sugar
crystals, inuencing rheology and aiding dispersion of sugar crystals in the continuous phases. Chevalley (1999) suggested lecithin
forms a monolayer on sugar particle surfaces allowing greater
mobility in suspensions while increasing fat spreadability. Increasing lecithin content caused signicant and consistent decreases in
DHmelt, trends noted at all PS and fat content (Table 4). This implies
that products with relatively higher lecithin content would require
lower enthalpies to melt than those of their corresponding products with lower lecithin levels. Signicant (P < 0.05) interactions
were observed among all the processing parameters. Multiple
comparison test revealed that fat content had the greatest effect
on Tindex and DHmelt of dark chocolates followed by lecithin content
and then PSD (Table 5).

4. Conclusion

Fig. 5. Typical DSC thermograms for dark chocolate with varying lecithin content
showing (a) 0.3%, (b) 0.5% at 18 lm PS and 30% fat content.

Variations in PSD, fat and lecithin content during dark chocolate

manufacture inuence to varying levels, the degree of crystallinity
and melting properties (Tend, Tindex and DHmelt) of their derived
products. Changes in PSD had no effect on the crystallinity of products. Increasing fat content resulted in consistent increases in crystallinity of products formed during tempering. Products containing
25% fat had the smallest crystal size, followed by those with 30%,
with the 35% fat having the largest crystal size, causing signicant
changes in Tend, Tindex and DHmelt of products. Similarly, increasing
lecithin content from 0.3% to 0.5% moderately reduced the crystallinity of products with signicant variations in Tend, Tindex and
DHmelt of products. Neither PSD, fat nor lecithin content inuenced
initiation (Tonset) or maximum (Tpeak) melting temperatures. Chocolates with ner particles, higher fat and lower lecithin contents,
took longer and higher temperatures to complete melting than

E.O. Afoakwa et al. / Food Research International 41 (2008) 751757

their corresponding products with larger PS, lower fat and higher
lecithin content. This suggest that for chocolate of the same composition, processed under identical conditions, the PSD of the suspended non-fat solid, fat and lecithin contents play important roles
in determining their melting behaviour. These ndings would have
application in dening chocolate quality as the nature of crystalline material, dimensions of crystals and polymorphic stability dictate the mechanical and rheological properties of chocolate
products.
Acknowledgements
This study was co-funded by the Government of Ghana and
Nestl Product Technology Centre (York, UK). The sponsors are
gratefully acknowledged for the Research Support. We also wish
to thank Drs. Steve Beckett, John Rasburn Jeremy Hargreaves and
Angel Manez (Nestl PTC, York) for useful discussions.
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