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Journal of Food Engineering 145 (2015) 4550

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Journal of Food Engineering

journalhomepage:www.elsevier.com/locate/jfoodeng

Effect of manufacturing process on the microstructural and rheological properties


of milk chocolate
a, a a a,b
Virginia Glicerina , Federica Balestra , Marco Dalla Rosa , Santina Romani
a
Interdepartmental Centre for Agri-Food Industrial Research, Alma Mater Studiorum, University of Bologna, Piazza Goidanich 60, Cesena, FC, Italy
b
Alma Mater Studiorum, University of Bologna, Department of Agro-Food Science, Campus of Food Science & Technologies, Piazza Goidanich 60, 47521 Cesena, Italy
article info abstract

Article history: The effect of different process steps on microstructural, rheological and visual properties of milk choco-late was studied. Each
Received 7 May 2014 process step affects the microstructural characteristics of milk chocolate, involving modifications on its macroscopic
Received in revised form 26 June 2014 properties, such as rheological attributes. Milk chocolate samples were obtained at each phase of the manufacture process:
Accepted 28 June 2014 mixing, pre-refining, refining, conching and temper-ing. Microstructural properties (network structure and particle size) and
Available online 16 July 2014
rheological parameters (yield stress, apparent viscosity, thixotropy, G 0 and G00) were evaluated by using respectively an

environmental scanning electron microscope (ESEM), and a controlled strainstress rheometer. Colorimetric analyses (L , hL
Keywords:
Milk chocolate and C ) were also performed. ESEM analysis revealed important changes in the network structure during process, with a
Manufacture steps reduction in particle size and an increase in the voids between aggregates, from the mixing to the refining step. Moreover, an
Microstructure increase of all rheological analyzed parameters from mixed sample to the refined one was found. Samples obtained from the
Rheology conching and tempering steps were characterized by the lowest statistically significantly values of all rheological parameters.
Appearance This could be related to the changes in the structure aggregation evidenced by ESEM analysis. From colour results, the
samples with the finest particles appeared lighter and more saturated than those with coarse particles.

2014 Elsevier Ltd. All rights reserved.

1. Introduction Schantz and Rohm, 2005). The processing of milk chocolate involves, during
each single step (mixing, pre-refining, refining, conching and tempering),
Milk chocolate is a complex rheological system having solid particles modifications in its final quality and attributes, influencing in a strong way
(cocoa, milk powder and sugar) dispersed in cocoa butter, which represent the the microstructure of the product (aggregation, de-aggregation, reduction of
fat phase (Pajin et al., 2013). Milk powder is one of the main ingredient of particle size, immobilization of cocoa butter, etc.) (Afoakwa et al., 2009a;
milk chocolate (being used at about 20% w/w in the formulation); this Aguilera and Stanley, 1999; Aguilera et al., 2000). In particular, milk powder
ingredient affects the sensory characteristics of the final product, the with its own physical characteristics and inner poros-ity may have a
processing behaviour and the rheological properties of the fluid chocolate significant impact on the chocolate processing con-ditions and on the physical
mass (Franke and Heilzmann, 2008; Taylor et al., 2009). The determination of and organoleptic properties of the final product (Liang and Hartel, 2004).
the rheological properties of chocolate is important during manufac-turing
processes in order to obtain high quality products with well-defined
characteristics (Servais et al., 2002; Gonalves and Lannes, 2010). The To our knowledge no papers are available in literature regarding the
rheological characteristics of milk chocolate (pseudoplastic flow with yield influence of the single process step on microstructural, rheo-logical and
stress, apparent viscosity, thixotropy and viscoelasticity) are in fact influenced appearance properties of milk chocolate.
by formula-tion (amount of fat, amount and type of emulsifiers) as well as by In our opinion, in order to improve the final quality of milk chocolate it
processing steps (mixing, pre-refining, refining, conching and tempering) would be interesting to study in depth the evolution of these important quality
(Tscheuschner and Wunsche, 1979; Vavreck, 2004; characteristics during the different pro-cess phases (mixing, pre-refining,
refining, conching and temper-ing). For this purpose in the present work the
influence of each process phase on microstructural, rheological and
colorimetric properties of milk chocolate were evaluated during the overall
Corresponding author. Tel.: +39 0547/338120; fax: +39 0547/382348. E-mail manufacturing process.
address: virginia.glicerina2@unibo.it (V. Glicerina).

http://dx.doi.org/10.1016/j.jfoodeng.2014.06.039 0260-
8774/ 2014 Elsevier Ltd. All rights reserved.
46 V. Glicerina et al. / Journal of Food Engineering 145 (2015) 4550
parameters were chosen after
2. Materials and methods preliminary trials and according to Dahlenborg et al. (2010), in order to
cause minimal damage on the s0:6 s00:6 gPLy0:6
chocolate surface and in order to 1
2.1. Materials
optimize the images quality. By
using this kind of instrument where s0 is the yield stress and gPL
Milk chocolate samples were
is the so-called plastic viscos-ity.
produced in an Italian confection- ESEM, samples are not coated and
In order to measure the goodness of
ery factory by using an industrial the images are more dependent on fit, the determination coef-ficient
plant (Buhler, Malmo, Sweden) sample rather than coating 2
(R ) was determined. The yield
provided of mixer, pre-refiner, characteristics, in this way the true
stress and the apparent viscosity
refiner, conching and tempering structure can be analyzed were obtained according to ICA
machine, and equipped to produce (Rousseau, 2007). Ten micrographs (2000), Servais et al. (2004) and
6000 kg of chocolate at every for each chocolate sample were Afoakwa et al. (2008), evaluating
production cycle. Milk chocolate taken. The acquired images were the shear stress respectively at 5 and
1
production was made up by dif- subsequently elaborated using the 40 s . In particular, the apparent
ferent steps as shown in Fig. 1. The software Image Pro-plus 6.0 (Media viscosity evaluated at the shear
1
ingredients used in the choco-late Cybernetics Inc., Bethesda, USA). stress of 40 s according to Do et
formulation were: sugar (47%), al. (2007), reflects the
cocoa butter (25%), whole milk microstructure of the sample taking
powder (21%) and cocoa liquor into account the presence of
aggregates.
(18%). The experimental samples
were taken after each production 2.2.2. Fundamental properties
Measurements were carried out The samples thixotropy was
phase: mixing (A), pre-refining (B),
at 40 LC using a controlled strain evaluated according to Servais et al.
refining (C), conching (D) and
stress rheometer (MCR 300, (2004), from the difference between
tempering (E). In particular, the
Physica/Anton Paar, Ostfildern, apparent viscosity mea-sured at 40 s
refining step was realized by using Germany) equipped respectively 1
a five-roll refiner, that consists of a during ramp up and ramp down.
with a bob and cup geometry and The thixotropy values represent in
vertical array of four hollow with a plateplate system to very close way the value of the
cylinders temperature controlled by perform analysis in steady state
hysteresis area between the
internal water flow, held together by Fig. 1. Scheme of chocolate manufacturing conditions and the dynamic tests
apparent viscosity curves during the
hydraulic pres-sure. The process (adapted from Babin, 2005). respectively. In steady state con-
ramp up and the ramp down. The
temperatures of the five cylinders ditions, after a pre-shearing of 500 s
1 loop area designates the energy
used to press particles were: 1st and at 2 s , apparent viscosity was required to break down the structure
2nd cylinder 28 LC; 3th 44 LC, 4th measured as function of increasing not recovered during the
49 LC and 5th 1
shear rate from 2 to 50 s (ramp up) experimentation per-iod (Roopa and
within 180 s, then decreasing from Bhattacharya, 2009) and represents
50 to 2 (ramp down), within each the rate of the internal breakdown
30 LC. ramp 18 measurements were taken of matrix (Dolz et al., 2000).
Samples were stored in plastic (ICA, 2000).
bucket (1 kg capacity) at room In dynamic conditions,
temperature until the analytical oscillatory tests by using a plate
determinations. Before perform-ing Chocolate rheological flow plate geometry were performed in
the analysis the samples were curves are usually fitted (Afoakwa order to investigate the viscoelastic
melted in a microwave (Stortz and et al., 2008, 2009b; Taylor et al., properties of samples and to
Marangoni, 2013) at 150 W for 25 2009) by using the Casson model, evaluate the storage (G0) and the
min. The melting parame-ters were that is a well-known rheological loss (G00)
modulus. In order to
chosen after preliminary model to describe the non-Newto-
experiments in order to avoid
identify the linear
nian flow behaviour of fluids with a
changes in the chocolate properties. yield stress (Joye, 2003). In viscoelastic range (LVR), in
particular, some fluid products, like which the viscoelastic
chocolate, are well described by this properties are independent
model because of their non linear
2.2. Methods
yield-stress-pseudoplas-tic nature. from the stress conditions,
According to Chevalley (1991) strain sweep tests were
2.2.1. Microstructure analysis
Samples microstructure was
curve points represent a case for a applied. Frequency sweep
better fit to chocolate data, if the
observed using an environmental tests were carried out in the
exponent is taken as 0.6 rather than
scanning electron microscope viscoelastic linear region at
0.5.
ESEM (Evo 50 EP, Zeiss,
Germany) equipped with a the constant deformation
For this reason, in this study the
microprobe (EDS Mod. 350, amplitudes of 0.12%,
obtained flow curves were
Oxford Instrument, UK). The
evaluated and fitted according to the previously evalu-ated with
detector used was a backscatter
rheological model of Casson, the strain sweep test, in the
electron detector (QBSE) that
provided good compositional
modified by Chevalley (1991), in range from 1 to 100 Hz.
order to obtain a better fit of the
contrast imaging at 20 kV and in
chocolate samples. The model used
low vacuum mode with 100 Pascal
is represented in the following Eq.
at 500 magnification. These
(1):
V. Glicerina et al. / Journal of Food Engineering 145 (2015) 4550 47
ESEM micrographs showed a In order to better explain the
2.2.3. Colorimetric measurements decrease in the particle size from into account. In particular, the rheological values obtained by the
Colour of chocolate samples sample obtained after mixing (A) to cocoa butter immobilized in large flow curves, the Casson yield value
was measured using a colour spec- the one taken after refining (C) voids can have a significant impact and the Casson plastic viscosity
trophotometer mod. Colorflex (Table 1), parallel to an increase in on the rheological behaviour of the parameters were calculated
(Hunterlab, USA), equipped with a the presence of large voids between milk chocolate system (Windhab, applying the Casson model
sample holder (diameter 64 mm). aggregates (Fig. 2(a)(c)). The 2000). modified by Chevalley (1991),
Colour was measured in the CIE reduction of the particles diameter
The micrographs of Fig. 2(d) moreover yield stress and apparent
L a b scale using the D65 causes an increase in the particles and (e), related to the samples after viscosity values were obtained
illuminant. The instrument was cal- number, parallel to an increase in
conching and tempering steps, show according to Afoakwa et al. (2008)
ibrated with a white tile (L = 98.03, the contact points between them,

a further reduction in the par-ticle and ICA (2000). All these data are
a = 0.23, b = 2.05) and the due to chemical and mechanical size coupled to a reduction of the reported in Table 2 for each
calibration was also validated with interactions (Afoakwa et al., 2009a; larger voids between aggre-gates,

chocolate sample.
a green standard tile (L = 53.14, a Servais et al., 2004). The increase that leads to a reduction of the fluid

= 26.23, b = 12.01) before the of particle interactions from sample
immobilization. In the conching All data were well fitted by the
measurements. obtained after mixing (A) to the one
step a destruction of the previous Casson model, providing high
taken after refining (C), due to the 2
obtained agglomerates and a re- determination coefficients (R ) that
Numerical values of a and b raise of their specific surface area,
distribution of cocoa butter between varied from 0.75 to 0.99. A sig-
were converted into hue angle involves a reduction of the particles
particles were noted, according to nificantly increase in both Casson
(hL) and Chroma (C ) that represent mobility, due to their high
Attaie et al. (2003). Cocoa butter in obtained parameters was high-
the hue and the saturation index: C aggregation (Bayod, 2008a; Bayod
2 2 1/2 fact, due to its free-moving lighted from sample (A) obtained
= [(a ) + (b ) ] , hL = et al., 2008b). On the other side, the
lubricating plastic flow, coats after mixing to the one taken after
[arctang(b /a )/2p] * 360 (Mc presence of large voids between
Guire, 1992). particles and reduces forces and refining (C). This could be
aggregates (filled with cocoa butter)
involves an immobi-lization of a aggregation between solid particles attributed to the increase of the
part of cocoa butter that cannot (Beckett, 2000), thus improving contact point between particles, that
2.3. Statistical analyses need of a major amount of stress to
contribute to the con-tinuous fluid their mobility (Aguilera et al.,
2004). initiate the flow, and to the presence
All the analysis were carried out phase flow. According with the
of large void spaces that
in triplicate for each chocolate studies of Windhab (2000), the
immobilized cocoa butter between
sample. effective immobilized fluid fraction
3.2. Fundamental rheological aggregates. In this state the fat
(/eff) in the particle aggregates can cannot contribute to the flow as
properties
Analyses of variance (ANOVA) be considered as an increase of lubricant (Franke and Heinzelmann,
and the test of mean comparison solid volume, as explained in the In Fig. 3 the flow curves of the 2008). Samples after conching (D)
according to Fisher Least following equation: milk chocolate samples, obtained and tempering
Significant Difference (LSD) were increasing the shear rate from 2 to
con-ducted on all obtained data. 1
50 s , are reported. (E) were characterized by the
Level of significance was P 6 0.05. The apparent viscosity (g) lowest and significantly similar val-
/ / / / /
The statistical software used eff s sif vif hifi against shear rate (c) was used to ues of both Casson parameters. In
was STATISTICA, version 8.0. 2
represent the rheological behaviour particular, the obtained values of
(StatSoft, Tulsa, Oklahom). of milk chocolate; it is evident that plastic apparent viscosity are in
where /s = is the volume occupied
the apparent viscosity decreases agreement with the results of
by solid particles, /sif = is the vol-
3. Results and discussion increasing the shear rate, which Wichchukit et al. (2004), that
ume of the fluid immobilized by
proves the pseudoplastic or shear showed that Casson viscosity of
surface, /vif = is the volume of fluid
3.1. Microstructural properties of immobilized in particle cavities and thinning nature of chocolate. milk chocolate with 20% of cocoa
milk chocolate into inner voids in particle butter, ranged from 7 to 48 Pa s and
aggregates and /hifi = is the part of According to Juszczak et al. led to decrease with the adding of
In Fig. 2(a)(e) micrographs of fluid immobilized when particles or (2004) this behaviour can be lubricant. In the samples studied in
milk chocolate samples obtained by aggregates move within the attributed to the breakdown of the this research work the highest value
continuous phase such as in inner structure dispersions, in fact
ESEM analysis are shown. rotation. of Casson apparent viscosity was
ESEM was employed in order the increase of shear rate causes the lower (25.7 Pa s), than the one
For this reason in order to know
to evaluate the main microstruc- drop in the apparent viscosity of the obtained in the study of Wichchukit
the effective solid content in a
tural modifications occurred on molecules orientating along the et al. (2004), probably due to a
dispersion, all the parameters
chocolate samples during the dif- flow lines. higher amount of cocoa butter used
presents in Eq. (2) must be taken
ferent process steps, concerning As illustrated in Fig. 3, sample in formulation (25%), that caused a
sugar crystalline networks, particle C achieved after the refining step, greater lubricating effect and a
particle interactions, presence of had the highest apparent viscosity reduction of particleparticle
voids and particle-fat behaviour with initial values ranging around interactions (Vernier, 1998).
(Afoakwa et al., 2009a). In Table 1 60 Pa s, followed by sample B,
are reported the size diameters of taken after the pre-refining step
the largest particles measured on with initial apparent viscosity The yield stress and apparent
chocolate samples, being those that values between 20 and 30 Pa s and viscosity parameters, exhibited the
underwent the main modifications sample A obtained from the first same trends of the Casson yield
during pro-cess. Microstructure step, with values between 10 and 20 value and of the Casson Plastic
examination, highlighted different Pa s. D and E samples, obtained
structures between samples from the last two steps of the
obtained from the manufacturing manufacture process, had the lowest
steps. apparent vis-cosity values, ranging
from 0 to 10 Pa s.
48 V. Glicerina et al. / Journal of Food Engineering 145 (2015) 4550

Fig. 2. Micrographs of milk chocolate after different processing steps: (a) mixing, (b) pre-refining, (c) refining, (d) conching and (e) tempering.
Table 1
Sample Particle Size (Feret
Microstructural analysis of the milk
chocolate. s Diameter)
A 103.002.57
Samples Particle size (Feret
B diameter) 67.003.54
A a
mixing 103.00 2.57 C 29.002.37
B b
pre-refining 67.00 3.54 D 22.002.56
C c
refining 29.00 2.37 E 17.013.73
D c
conching 22.00 2.56
case indicates an higher degree of
E c
tempering 17.91 3.73 particles aggregation, while a
ac
Values in the same column followed by decrease of this parameter, as for
different letters differ significantly at p < samples after conching (D) and
0.05 level.
after tempering (E), underlines a
lower degree of interactions, as
confirmed by microstructural
Viscosity in milk chocolate analysis results.
samples. According to the studies of Thixotropy results are shown in
Do et al. (2007) in fact an increase Fig. 4. It is possible to notice how C
in the apparent viscosity, as from and B samples obtained
sample after mixing (A) to the one respectively after the refining and
after refining (C), also in this pre-refining steps, that had the most
aggregate structure, presented also
the significantly highest thixotropy
values, related to a more damaged
structure. This result according to
be
Afoakwa et al. (2008) could
attributed to the high
aggregation of the par-
ticulate system and to an
elevate number of
interactions between
particles. Sample A taken
after the mixing was
characterized by an
intermediate thixotropic
value, between BC and DE
ones, strictly related with
the results obtained from
microstructural
V. Glicerina et al. / Journal of Food Engineering 145 (2015) 4550 49
Fig. 4. Changes of thixotropy of milk chocolate samples during mixing (A), pre-refining (B),
refining (C), conching (D) and tempering (E) steps.

Fig. 3. Changes of apparent viscosity (Pa s) of milk chocolate samples, during mixing (A), pre-
refining (B), refining (C), conching (D) and tempering (E) steps, evaluated at 40 LC. Table 3
Storage and loss modulus of milk chocolate samples evaluated at 1 Hz and at 40 LC.
0 00
Samples G (Pa) G (Pa)
examination, that reflects the presence of coarse particles and a weak solid A b b
mixing 8416 125 1281 32
structure compared to B and C samples obtained from the pre-refining and B c c
pre-refining 13673 644 2357 24
refining phase. The lowest significantly values of thixotropy were showed by C
refining 72746 890
d
16873 298
d
D a a
chocolate samples D, after conching and E, after tempering. According with conching 3983 112 807 34
literature (Afoakwa et al., 2008) in fact, a well conched and tempered E a a
tempering 2873 97 798 84
chocolate should not be thixotropic and hence should not have a very ad
Values in the same column followed by different letters differ significantly (p < 0.05).
aggregate struc-ture. Anyway, it is very unusual to have not any thixotropy.

The results of frequency sweep test in terms of storage and loss modulus,
evaluated respectively at a frequency of 1 Hz, are reported in Table 3. The
response of all samples to the imposed deformation is the stored potential
energy, characterized by the predominance of the elastic modulus (G 0) over
the viscous one (G00) (Ahmed and Ramaswamy, 2006; Bayod and Tornberg,
2011).
B and C samples, obtained from pre-refining and refining steps, were
characterized by a relative more elastic structure compared to that of the other
samples (A, D and E, taken after mixing, con-ching and tempering). As
reported in previous studies (Johansson and Bergensthal, 1992; Glicerina et
al., 2013) high values of G0 are related to a high level of interactive forces
between particles; this confirms the high amount of stress necessary to pre-
refining
(B) and refining (C) samples to start flow.
The significantly lowest values of G 0 and G00 were found for the samples
after conching (D) and after tempering (E), constituted by a weakly structure.

3.3. Colorimetric measurements



Fig. 5. Lightness (L ) and hue angle (hL) colorimetric parameters of milk chocolate samples
during mixing (A), pre-refining (B), refining (C), conching (D) and tempering (E) steps.
The lightness (L ) and hue angle (hL) values of AE milk choco-late
samples are shown in Fig. 5.
A similar trend of lightness and hue angle values was observed in all
samples. A and B samples, taken from the first two steps and characterized by Afoakwa et al., 2008), the human eye detects colour according to how the
coarser particles, had the lowest significantly val-ues of both colour light is reflected from the surface, thus the size of the both non-fat solid and
parameters. As known (Voltz and Beckett, 1997; crystalline fat particles affects the colour of

Table 2
Casson yield values, Casson plastic viscosity, yield stress and apparent viscosity of milk chocolate samples.

Samples Casson yield value (Pa) Casson plastic viscosity (Pa s) Yield stress (Pa) Apparent viscosity (Pa s)
A b b b b
mixing 6.82 0.63 4.38 0.30 37.10 3.14 3.84 0.11
B c c c c
pre-refining 11.97 0.58 7.82 0.83 91.10 5.95 10.84 1.39
C d d d d
refining 35.70 4.70 15.36 2.30 209.33 8.14 23.23 2.15
D a a a a
conching 2.75 0.23 1.55 0.35 16.93 2.17 1.53 0.13
E a a a a
tempering 1.95 0.04 0.21 0.00 14.56 1.45 1.32 0.12
ad
Values in the same column followed by different letters differ significantly at p < 0.05 level.
50 V. Glicerina et al. / Journal of Food Engineering 145 (2015) 4550
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