J Am Oil Chem Soc
DOI 10.1007/s11746-017-2973-3
ORIGINAL PAPER
Crystallization Behavior and Kinetics of Chocolate‑Lauric Fat
Blends and Model Systems
Margaret Geary1 · Richard Hartel1 
Received: 8 August 2016 / Revised: 26 February 2017 / Accepted: 11 March 2017
© AOCS 2017
Abstract  Binary mixtures of cocoa butter and lauric fats
have widespread use in chocolates and confections, yet
incompatibilities between these fats can present formula-
tion and processing constraints. This study examined the
phase behavior and crystallization kinetics of cocoa butter-
lauric fat model systems and chocolate-lauric fat blends.
Solid fat content (SFC) profiles and isosolid diagrams
confirmed eutectic and diluent interactions, indicating a
softening of cocoa butter by lauric fat addition. Crystalliza-
tion kinetics of model systems adhered to an exponential
growth model. High lauric fat levels delayed crystal growth
and reduced equilibrium SFC of cocoa butter. Coconut
and palm kernel oils altered the solidification mechanisms
of cocoa butter to a greater extent than fractionated palm
kernel oil. Chocolate systems displayed multi-step crys-
tal growth that contrasted with the exponential growth
observed in the model systems. At high lauric fat levels
(30%), crystallization onset was significantly lengthened.
Blends with high lauric fat contents showed low G′max and
did not achieve final equilibrium after 60 min of cooling,
indicating incomplete crystallization.
Keywords  Chocolate · Lauric fat · Crystallization
Introduction
In the confectionery industry, cocoa butter can be blended
with lauric vegetable fats, such as coconut oil and palm
* Richard Hartel
rwhartel@wisc.edu
1
Department of Food Science, University of Wisconsin-
Madison, 1605 Linden Dr, Madison, WI 53706, USA
kernel oil, to produce a wide array of confectionery prod-
ucts, including chocolate truffle centers, chocolate melta-
ways, and fillings for sandwich-type biscuits. Such products
derive their silky smooth textures and melt-in-your-mouth
sensations from these fat blends. However, cocoa butter
and lauric fat exhibit different melting and crystallization
behaviors, which pose limitations when developing confec-
tions made from these mixtures. Principally, the presence
of lauric fat in a cocoa butter system can result in bloom
or excessive softening (eutectic) in the finished product [1].
The phase behavior of blends of cocoa butter and lau-
ric fat can be studied to understand the compatibility and
equilibrium conditions of a binary system. Eutectic effects
can be visualized through solid fat content (SFC) profiles
or isosolid diagrams, which depict the relationship between
fat composition and temperature with lines of constant
SFC and illustrate fat compatibility. Several authors have
investigated the phase behavior of cocoa butter and lauric
fat using isosolid diagrams [2–4]. In these studies, eutectic
formations were observed at intermediate levels of lauric
fat. Eutectic interactions are said to be due to differences
in thermal properties, triacylglycerol profiles, and polymor-
phic forms of fats [5]. However, these studies were specific
to cocoa butter-palm kernel oil blends and did not com-
pare the phase behaviors of different types of lauric fat in
cocoa butter systems, specifically coconut oil or a lauric fat
fraction.
The crystallization kinetics of cocoa butter has been
a subject of intense focus [6, 7], yet there is a paucity of
research on the effect of lauric fat on cocoa butter crystal-
lization. Ribeiro et al. [8] studied the kinetics of isother-
mal crystallization of cocoa butter-palm kernel oil blends
by analyzing the increase in SFC over cooling time. The
addition of low levels of lauric fat effectively delayed the
onset of cocoa butter crystallization and decreased the
13

final equilibrium SFC. Due to dissimilarities in the tria-
cylglycerol chain lengths and polymorphism, co-crystalli-
zation of lauric fat and cocoa butter is markedly weak [9].
Long-chain triacylglycerols (16–18 carbons) comprise the
majority of cocoa butter whereas short- and medium-chain
triacylglycerols (12–14 carbons) dominate lauric fat. Fur-
thermore, the formation of a β polymorph in cocoa butter
and β′ polymorph in lauric fat has been noted in X-ray dif-
fraction patterns by Quast et al. [4]. While these differences
have recognized inhibitory effects on the crystallization
of cocoa butter, no studies have sought to quantify these
effects by the application of empirical growth models.
The rheological properties of chocolate can be deter-
mined using small amplitude oscillatory rheology, which
does not disrupt the formation of a fat network during crys-
tallization and measures the storage modulus (G′) and loss
modulus (G″) to indicate the relationship between solid-
like and liquid-like properties at a given time [10]. Specifi-
cally, G′ values can be used to compare the effects of cool-
ing conditions on the solidification kinetics of fat systems.
These rheological cooling curves depict an initial lag time,
an increase in G′, and a final plateau region. When melted
cocoa butter is cooled to 15 °C, G′ increases over time as
growing crystals interact and form a matrix, which occurs
rapidly initially but slows toward a state of thermodynamic
equilibrium. A high equilibrium G′ corresponds to a final
crystal network with high hardness. Small amplitude oscil-
latory rheology has been used to evaluate the effect of an
additive on the solidification kinetics of chocolate [11, 12].
However, these studies documented the effects of milk
fat or lecithin on crystallization, and virtually no research
exists for chocolate-lauric fat systems.
In order to optimize the use of lauric fat in chocolate
products in industrial settings, it is important to understand
their effects on the crystallization behavior of cocoa but-
ter. A knowledge of crystallization properties is useful to
maintain efficiency in chocolate manufacture and evade
conditions that might cause inconsistencies or defects in a
product. The objective of this work was to study the crys-
tallization behavior and kinetics of chocolate-lauric fat
blends and cocoa butter-lauric fat model systems.
Experimental Procedures
Materials
Lauric fats coconut oil (CO; Columbus Vegetable Oils, Des
Plaines, IL, USA), palm kernel oil (PKO; AarhusKarlshamn
USA, Port Newark, NJ, USA), and fractionated palm kernel
oil (FPKO; AarhusKarlshamn USA) were used in model
systems with cocoa butter (CB; Archer Daniels Midland
Cocoa, Milwaukee, WI, USA) and chocolate systems with
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J Am Oil Chem Soc
dry-conched chocolate mass and CB. Fats were melted at
65 °C for 1 h and mixed thoroughly. To prepare model sys-
tems, lauric fats were blended with CB at 10% composi-
tion intervals from 0 to 100% wt/wt for SFC profiles and
isosolid diagrams, and from 0 to 30% wt/wt levels for crys-
tallization curves. Chocolate systems were made at 0–30%
wt/wt levels to the same final fat contents of 40.8% to
account for variation in solids. Lauric fat, chocolate mass
(32.5% fat content) and CB comprised 10 and 20% blends,
and 30% blends contained lauric fat and chocolate mass.
SFC Profiles and Isosolid Diagrams of Model Systems
A Bruker nuclear magnetic resonance (NMR) Minispec Mq
instrument (Bruker, The Woodlands, TX, USA) equipped
with Minispec software was used to evaluate equilibrium
SFC. Calibration was performed using oil with 0% sol-
ids and paraffin-based standards of 30 and 70% solids.
Melted fats (2 mL) were filled and capped into NMR tubes
(10-mm diameter) and tempered according to the IUPAC
method 2.150 (IUPAC 1987). Fats were exposed to 80 °C
for 20 min, 0 °C for 90 min, 26 °C for 40 h, and 0 °C for
90 min and stabilized for 60 min at each test temperature
(10, 20, 25, 30, 35, and 40 °C) prior to NMR measurement.
All samples were prepared in triplicate and average SFC
was determined from the three measurements. SFC profiles
were constructed for decrease in SFC over temperature.
Isosolid diagrams were prepared using Matlab R2015A
software and a customized quadratic interpolation code
after a program written by Timms [13]. Isosolid lines were
drawn at constant SFC values of 5, 10, 20, 30, 40, 60, and
80%.
Crystallization Curves of Model Systems
Fats were melted and stirred at 45 °C. A cyclothermic tem-
pering method described by Kleinert [14] was applied to
samples with exact times and temperatures adjusted by trial
and error. After melting at 50 °C, samples were cooled to
24 °C (0 and 10% lauric fat) or 23 °C (20 and 30% lau-
ric fat) and maintained until viscosity reached a maximum.
The temperature was raised to 27 °C until texture appeared
uniformly smooth, lowered again to 26 °C until viscos-
ity reached a maximum, and reheated to 31 °C. To test for
proper tempering, samples were spooned into a temperme-
ter cup set in an ice bath, and a temperature–time cooling
curve was measured at 10-s intervals. Well-tempered sam-
ples displayed cooling curves with a sharp temperature
decrease, a plateau region, and a final temperature drop.
Once a well-tempered profile was obtained in triplicate,
the tempering regimen was adopted as the pre-treatment
for SFC determination. As a second test, a thin layer of
tempered sample was spread onto a strip of wax paper and
J Am Oil Chem Soc
maintained at room temperature. A well-tempered sample
hardened after 1–2 min, easily peeled away from the wax
paper, and had a glossy surface. Tempered fats were filled
into NMR tubes, equilibrated to 31 °C, then quickly cooled
to the crystallization temperature. The increase in SFC
over crystallization time at 10, 15, and 20 °C was moni-
tored at 2-min intervals for 60 min or until SFC reached a
maximum. Average cooling rates were recorded and ranged
from 0.05 to 0.1 °C/min. All samples were prepared in trip-
licate and the average SFC was determined from the three
NMR measurements. Crystallization curves were plotted
and fit to an empirical model using Origin 9.1 software.
The model equation was selected based on the exponential
growth shape of data and quality of fit (Eq. 1):
SFC = A1 − A2 e−kt , (1)
where SFC = solid fat content (%), A1 = equilibrium solid
fat content (%), A2 = pre-exponential factor (%), t = time
(min), and k = rate parameter (min−1). The fit of the model
was analyzed using linear regression to compare the SFC
predicted by the model to the SFC determined experimen-
tally. Standard error was used to evaluate the fit of each
constant within individual experiments. Constants were
compared across different experiments using the standard
error and evaluating the z-score for multiple comparisons
(α < 0.05).
Rheology of Chocolate Systems
A Discovery Hybrid Rheometer 2 (TA Instruments, Wood
Dale, IL, USA) equipped with parallel-plate geometry
and TRIOS software was used to evaluate the rheological
properties of chocolate systems. The distance between the
upper and lower plates was calibrated prior to each sample
loading. Each sample was subjected to cyclothermic tem-
pering according to Kleinert’s method and proper temper-
ing was confirmed using the two tests described previously.
Approximately 0.8 g of sample were loaded and slightly
compressed between parallel plates set to a 1000-µm gap
and temperature of 31 °C. Small amplitude oscillatory rhe-
ology was analyzed using a temperature sweep program
from 31 to 12 °C at a cooling rate of 0.3 °C/min. Dynamic
oscillatory test parameters storage modulus (G′) and loss
modulus (G″) were calculated using TRIOS software.
Experiments were performed on three different samples,
and average moduli were determined from the three meas-
urements. Crystallization curves of G′ and G″ over time
were plotted. To compare data, G′ curves were sectioned
and assigned parameters: time of initial crystallization
onset (t1), slope of initial crystallization phase (Δ1), time
of secondary crystallization onset (t2), slope of secondary
crystallization phase (Δ2), and maximum G′ (G′max). Time
values were determined from inflection points on the curves
using Matlab R2015A software and slopes were calculated
using an Excel spreadsheet. Statistical analyses were based
on analysis of variance (ANOVA) and Tukey’s test to deter-
mine significant differences of the means (p < 0.05).
Results and Discussion
SFC Profiles and Isosolid Diagrams of Model Systems
SFC profiles were used to compare the melting properties
of the fat blends. Figure 1 shows the SFC profile for CB
and blends of CB with (a) 10%, (b) 20%, and (c) 30% lau-
ric fat. Blends with 10% lauric fat (Fig. 1a) had lower SFC
than CB at a given temperature, and the three blends exhib-
ited similar SFC profiles across the melting range. Below
25 °C, FPKO had a slightly higher SFC than PKO and CO,
which were not different at any temperature. However, the
SFC of the three blends were nearly identical above 25 °C.
The SFC profiles of blends with 20% lauric fat (Fig. 1b)
showed greater deviation from the SFC profile of CB than
10% blends and displayed wider melting curves. At 20 °C,
distinctions were observable between types of fat, with
FPKO having the highest SFC followed by PKO and sub-
sequently CO. Compared to CB, which had a slow decrease
followed by a rapid decline in SFC at 25 °C, blends of 30%
lauric fat (Fig. 1c) exhibited significant decreases in SFC
at 10 °C with more gradual melting at higher temperatures.
Whereas the SFC profile of CB displayed a more convex,
outwardly inflected shape due to sharp melting properties,
the SFC profiles of the 30% blends appeared concave or
inward-facing. The differences in solid fat profiles can be
explained by the triacylglycerol compositions of each fat.
Lauric fats are rich in short- and medium-chain triacylglyc-
erols, which have lower melting points than the long-chain
triacylglycerols of CB, resulting in faster melting behavior
[15]. The exception to the trend of lower SFC with high
lauric fat addition was found in FPKO at 10 °C. While
going from 0 to 10% reduced SFC at first, increasing FPKO
beyond 10% increased the SFC of the blend. It is likely that
the fractionation process yielded a palm kernel stearin with
a melting point virtually the same as that of CB. When CB
was blended with another fat of the same melting point, a
depression in SFC corresponding to a lower melting point
of the mixture was observed when going from 0 to 10% but
not from 20 to 30%.
Figure 2 shows the isosolid diagram for the addition of
(a) CO, (b) PKO, and (c) FPKO to CB. In both CO and
PKO systems (Fig. 2a, b), eutectic and dilution interactions
were evident across the composition range with the most
pronounced eutectics occurring at the 60% lauric fat addi-
tion levels. At high PKO levels (Fig. 2b), the isosolid lines
were farther separated from each other, indicating broad
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 J Am Oil Chem Soc

10% PKO 20% PKO 30% PKO

80 10% CO 80 80 30% CO
20% CO
10% FPKO 30% FPKO
20% FPKO
CB CB
CB

Solid Fat Content (%)

Solid Fat Content (%)
60

Solid Fat Content (%)

60 60

40 40 40

20 20 20

0 0 0
10 30 10 30 10 30
Temperature (oC) Temperature (o C) Temperature (oC)
(a) (b) (c)

Fig. 1  Solid fat profiles for blends of 10% (a), 20% (b), and 30% (c) coconut oil (CO), palm kernel oil (PKO), and fractionated palm kernel oil
(FPKO) with cocoa butter (CB). Data represent means of measurements of three different mixtures with error bars indicating standard deviation

Fig. 2  Isosolid diagrams for the addition of (a) coconut oil (CO), (b) palm kernel oil (PKO), and (c) fractionated palm kernel oil (FPKO) to
cocoa butter (CB). Each line represents a constant solid fat content (SFC) given by the number above the line

melting ranges for these fat blends. It can be reasoned that
CO and PKO are both incompatible with CB, and the great-
est extent of incompatibility occurs at the 60% addition
level. The eutectic interaction and incompatibility of CB
and lauric fat has been extensively reported in the literature
[1–3] and can be attributed to the weak co-crystallization
of shorter-chain PKO triacylglycerols and longer-chain CB
triacylglycerols in addition to differences in polymorphic
forms of the two fats. The isosolid diagram for the blends
of CB with FPKO (Fig. 2c) showed a clear eutectic at the
70% addition level, which was a slightly higher value than
that observed in CO and PKO blends. Unlike CO and PKO,
FPKO and CB had about the same melting points across
the range of temperatures. As explained previously, these
findings may be due to the fractionation process yielding
a palm kernel stearin with high melting properties similar

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J Am Oil Chem Soc
to CB. According to Calliauw et al. [16], unhydrogenated
palm kernel stearin has exceptionally sharp melting and
crystallization behavior that make it ideal for use as a CB
substitute. However, it still shows eutectic phase behavior
when mixed with CB due to differences in triacylglycerol
profile and polymorphism.
Crystallization Curves of Model Systems
An empirical model was applied to the crystallization
curves in order to describe the isothermal crystallization
kinetics of fat mixtures. By fitting data to a model, the crys-
tallization properties of the blends could be compared. The
model equation (Eq. 1) was chosen based on the exponen-
tial growth shape of data:
SFC = A1 − A2 e−kt ,
where SFC = solid fat content (%), A1 = equilibrium solid
fat content (%), A2 = pre-exponential factor (%), t = time
(min), and k  = rate parameter (min−1). Once the model
equation was verified, its overall quality of fit was assessed
by linear regression analysis. Figure 3 depicts the compari-
son between the SFC predicted by the model to the SFC
measured experimentally. The relationship between pre-
dicted versus measured SFC was linear with an R2 value
of 0.99657, indicating that the model equation provided
a good fit and could accurately predict SFC for the data.
The fit of the exponential model to the experimental SFC
data can be seen in Fig. 4 using the crystallization of CB
and blends at 15 °C for illustration. All crystallization
curves displayed an initial exponential increase in SFC
followed by an asymptote at equilibrium SFC. For all fat
blends, crystallization slowed down after approximately
30 min, with most blends having reached equilibrium SFC
100
Measured Solid Fat Content (%)
80 y = 0.9976x + 0.0843
R² = 0.9966
60
40
20
0
0 20 40 60 80
Solid Fat Content Predicted by Model (%)
Fig. 3  Relationship between the measured solid fat content (SFC) for
all experiments in triplicate and the SFC predicted by the exponential
model (Eq. 1)
(1)
Fig. 4  Representative solid fat content (SFC) cooling curves for the
crystallization at 15 °C of cocoa butter (CB) and blends with 20%
coconut oil (CO) palm kernel oil (PKO), and fractionated palm kernel
oil (FPKO). The continuous lines represent the fit of the experimental
data using the model equation (Eq. 1). Data points represent means
of measurements of three different mixtures with error bars indicat-
ing standard deviation
after 60 min. Although the Avrami model has been widely
used to quantify the solidification kinetics of confectionery
fats [17, 18], this theory is based on isothermal crystalli-
zation without any pre-crystallization (tempering or seed-
ing). As the fats used in this study were tempered prior to
SFC measurement, a lag or nucleation phase was absent,
and crystallization was underway before the hold tempera-
ture was reached. Average cooling rates ranged from 0.05
to 0.1 °C/min, which varied based on the crystallization
temperature, with crystallization starting immediately upon
cooling. Thus, the crystallization curves in this study did
not conform to the Avrami model. Further, a simpler model
with a single A value also did not fit the data very well.
Ultimately, the model in Eq. (1) was selected as the best for
data analysis.
Kinetic parameters of crystallization are compared in
Table 1. At all three cooling temperatures, pure CB reached
the highest equilibrium SFC (A1) compared to blends with
lauric fats. For blends containing CO or PKO, increasing the
concentration of lauric fat (10–30%) decreased equilibrium
SFC, which is in agreement with previous research [4, 8].
Triacylglycerols that contain long-chain saturated fatty acids
tend to crystallize more quickly and have higher melting
100 points than those with shorter chains. Thus, fats with higher
proportions of long-chain triacylglycerols (CB and FPKO)
have higher SFC and crystallize earlier during cooling. Simi-
lar studies on fat blend crystallization showed that the most
pronounced effects on kinetics were observed when the chain
length of the additive was markedly dissimilar from that of
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Table 1  Equilibrium SFC (A1), pre-exponential factor (A2), and rate parameter (k) for crystallization of cocoa butter (CB) and blends with coco-
nut oil (CO), palm kernel oil (PKO), or fractionated palm kernel oil (FPKO)
10 °C % in blend Fat A1 (%) A2 (%) k (min−1)

100 CB 80.4 (±0.1)A 56.5 (±0.5)E 0.28 (±0.01)A

10 CO 71.0 (±0.2)F 53.7 (±0.6)F 0.19 (±0.00)B
PKO 71.8 (±0.2)E 55.7 (±0.7)E 0.18 (±0.00)B
FPKO 76.6 (±0.2)D 60.4 (±0.6)C 0.16 (±0.00)C
20 CO 69.8 (±0.2)G 58.8 (±0.5)D 0.12 (±0.00)E
PKO 70.7 (±0.2)F 59.8 (±0.5)CD 0.13 (±0.00)D
FPKO 78.5 (±0.4)C 67.7 (±0.4)B 0.12 (±0.00)E
30 CO 68.6 (±0.2)H 61.8 (±0.4)C 0.08 (±0.00)H
PKO 68.8 (±0.2)H 61.1 (±0.5)C 0.09 (±0.00)G
FPKO 79.1 (±0.1)B 72.6 (±0.4)A 0.11 (±0.00)F
15 °C % in blend Fat A1 A2 k
A BC
100 CB 73.4 (±0.2) 48.0 (±0.7) 0.17 (±0.00)B
10 CO 61.5 (±0.1)E 46.2 (±0.5)D 0.17 (±0.00)B
PKO 61.9 (±0.2)D 45.6 (±0.6)D 0.19 (±0.01)A
FPKO 66.0 (±0.2)C 49.3 (±0.4)B 0.11 (±0.00)C
20 CO 55.1 (±0.3)H 43.3 (±0.6)E 0.08 (±0.00)D
PKO 58.7 (±0.1)F 48.0 (±0.2)C 0.08 (±0.00)E
FPKO 69.4 (±0.4)B 58.4 (±0.6)A 0.07 (±0.00)F
30 CO 53.0 (±0.7)I 45.3 (±0.7)D 0.04 (±0.00)H
PKO 56.9 (±0.2)G 49.3 (±0.3)B 0.05 (±0.00)G
FPKO 67.8 (±1.0)BC 57.5 (±1.2)A 0.04 (±0.00)H
20 °C % in blend Fat A1 A2 k

100 CB 64.4 (±0.2)A 42.2 (±0.4)A 0.12 (±0.00)A

10 CO 51.3 (±0.1)B 35.1 (±0.2)C 0.09 (±0.00)C
PKO 51.3 (±0.1)B 35.5 (±0.3)C 0.10 (±0.00)B
FPKO 51.7 (±0.2)B 35.1 (±0.4)C 0.09 (±0.00)C
20 CO 41.2 (±0.4)D 29.8 (±0.5)D 0.06 (±0.00)D
PKO 41.8 (±0.1)D 31.5 (±0.2)D 0.06 (±0.00)D
FPKO 50.9 (±0.7)B 40.6 (±0.6)B 0.04 (±0.00)E
30 CO 34.2 (±0.3)E 26.9 (±0.3)E 0.04 (±0.00)F
PKO 36.2 (±1.8)E 28.7 (±1.6)DE 0.03 (±0.01)FG
FPKO 47.9 (±1.0)C 40.2 (±0.9)B 0.03 (±0.00)G

Kinetic parameters were obtained by fitting the model equation (Eq. 1) to data. Different letters denote significant differences (p < 0.05) within
columns. Standard error is located in parenthesis next to each mean value

the continuous lipid phase. Dissimilarities in chain length
introduced some degree of disorder during crystal network
formation [19]. Conversely, for FPKO, increasing concentra-
tion increased equilibrium SFC at 10 °C. At all temperatures,
the order of equilibrium SFC value was as follows: CB (great-
est), FPKO, CO or PKO (least). Pre-exponential factor (A2),
the parameter that describes the inflection of the exponential
model, increased for each blend with increasing addition level
of lauric fat at 10 °C, indicating less-defined curvature of
crystallization curves with increasing lauric fat concentration.
Rate parameter (k) correlates to the period of crystal growth
or initial region of the SFC cooling curves. Blends with
higher concentrations of lauric fats had lower rate parameter
values, indicating delayed crystal growth of the blends rela-
tive to CB. In confectionery applications, crystallization delay
is highly undesirable, as slower crystallization can advance
fat bloom formation [9]. Kinetic parameters of crystallization
were also compared across the three cooling temperatures.
As temperature was increased from 10 to 20 °C, significant
reductions in both A1 and k values were observed, ratifying
slower growth rates and diminished equilibrium SFC of the
fats. Also, at high temperatures, intact PKO and CO displayed

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identical crystallization profiles and the same values of A1 crystallization of CB releases latent heat to balance cool-
and k. Lower temperatures shifted the crystallization behavior ing and maintain constant temperature briefly (the plateau
of the lauric fat blends more closely to that of pure CB and in the tempermeter curve), followed by another decrease in
accelerated crystal growth. In general, the addition of lauric temperature as solidification continues [20]. Furthermore,
fat had an inhibitory effect on crystallization, but the extent of the rheometer controlled temperature using a cooling ramp
this effect depended on the temperature of cooling. at a set rate of 0.3 °C/min, so all chocolate systems were
cooled at a constant rate. This contrasts with the crystal-
Rheology of Chocolate Systems lization of the model systems that was performed under
temperature-hold conditions that resulted in variable cool-
Chocolate blends required proper tempering prior to rhe- ing profiles. These discrepancies resulted in differently
ological analysis. Each blend was subjected to an indi- shaped G′ curves, and possibly influenced crystallization
vidualized tempering profile with two temperature cycles curves as well, of the chocolate and model systems. A sec-
to ensure proper pre-crystallization (Table 2). The exact ond explanation for the unusual curves might be based on
temperatures of tempering steps differed slightly among the mechanism of seed crystal growth during cooling of
blends. In general, blends with higher lauric fat contents tempered CB. Spherulites grow uninhibitedly at first, but
required lower temperatures in order to achieve good increasingly begin to overlap with each other. This overlap
temper, confirming the results from the model systems in consequently slows further growth as the liquid phase is
which lauric fats inhibited CB crystallization. Also, in the squeezed out between spherulites, then crystallization lev-
SFC cooling curves, equilibrium SFC values were lower at els off at equilibrium [21]. The implications of this mecha-
a given cooling temperature for blends with greater lauric nism may be reflected in the G′ curves. After a lag period, a
fat levels, as these blends required lower temperatures than critical time was reached (t1) at which G′ rapidly increased.
CB to achieve stable crystallization during cooling. Repre- This initial rapid burst (Δ1) would correspond to an ini-
sentative tempermeter curves indicated that chocolate and tial, unimpeded 3D growth of spherulites. As growth pro-
the lauric fat blends were properly tempered. ceeds, a crystallization rate change occurs at a later point
Figure  5a–d shows examples of G′ curves obtained for (t2), signifying a region of impeded 3D growth (Δ2) where
(a) chocolate and blends with (b) 10%, (c) 20%, and (d) spherulites butt into each other. Once the liquid phase has
30% PKO added. G′ increased relative to G″ over time for been depleted between spherulites, G′ slows to an equilib-
all systems, reflecting an increase in solid character due rium (G′max). Variations arose between chocolate blends in
to the formation of a crystal network, but multiple slopes the kinetics of these curve stages. In the final portion of the
were observed over the crystal growth period. Choco- curve, chocolate showed a stable G′ that was clearly greater
late (Fig. 5a) exhibited a multi-step increase in G′: a lag than G″, which decreased slightly as the liquid phase was
phase, initial rapid growth (Δ1), secondary gradual growth incorporated into the crystal matrix. Both 10 and 20% lau-
(Δ1), and equilibrium. The unusually shaped curve was ric fat (Fig. 5b, c) depicted multi-step crystallization simi-
due to the temper step prior to rheological testing. Cool- lar to chocolate. As lauric fat level was increased in a blend
ing causes the temperature of chocolate to decrease, but the (10–30%), the final portion of a curve was less defined,
decrease in G″ was less evident, and stable G′ was reached
Table 2  Temperatures for tempering profiles of blends of chocolate later during cooling or not at all. Blends with 30% lauric
(CHOC) with 10, 20, and 30% addition levels of coconut oil (CO), fat did not reach stable G′ or clear equilibria after 60 min
palm kernel oil (PKO), and fractionated palm kernel oil (FPKO)
had elapsed (Fig. 5d), indicating incomplete crystallization
% in blend Fat T1 T2 T3 T4 within the 60-min cooling study. Furthermore, these results
confirm the changes to cooling curve shape and behavior
100 CHOC 25.5 29.5 28.0 31.0
that were observed in model systems, confirming that high
10 CO 25.0 29.0 27.5 31.0
concentrations of lauric fat can dramatically alter the over-
PKO 25.0 29.0 27.5 31.0
all crystallization of both model and chocolate systems.
FPKO 25.0 29.0 27.5 31.0
G′ curves were evaluated according to regions of ini-
20 CO 24.5 28.5 27.0 31.0
tial onset time (t1), initial growth slope (Δ1), secondary
PKO 24.5 28.5 27.0 31.0
onset time (t2), slope of secondary growth phase (Δ2), and
FPKO 24.5 28.5 27.0 31.0
maximum G′ (G′max). Kinetic parameters for crystalliza-
30 CO 24.0 28.0 26.5 31.0
tion of chocolate and blends are tabulated in Table 3. Initial
PKO 24.0 28.0 26.5 31.0
onset time (t1) was determined from the point of inflection
FPKO 24.0 28.0 26.5 31.0 where the lag period transitioned into a sharp increase in
T1 is initial cooling temperature, T2 is warming temperature, T3 is G′. The highest t1 values were observed in 30% CO and
recooling temperature, and T4 is final holding temperature PKO, suggesting that the two blends required the longest

13

Fig. 5  The storage modulus (G′) and loss modulus (G″)
for crystallization of a chocolate with b 10%, c 20%, and d 30%
palm kernel oil (PKO). Each G′ curve was divided into phases and
ascribed parameters related to different stages of crystallization: ini-
cooling time to initiate rapid crystal growth and validat-
ing what was seen in the crystallization of CB/lauric fat
model systems. Despite parallels between data sets, some
contradictions were evident. Chocolate had the highest t1
and t2 values behind only 30% CO and PKO. In princi-
ple, pure chocolate would be expected to have the short-
est t1 and t2, or fastest times, given the homogeneity of its
13
J Am Oil Chem Soc
tial onset time (t1), initial growth slope (Δ1), secondary onset time
(t2), secondary growth slope (Δ2), and maximum G′ (G′max). Data
represent means of triplicate measurements with error bars indicating
standard deviation
triacylglycerol chain lengths relative to those of the lauric
fat blends. In the model systems, pure CB consistently dis-
played stronger crystallization characteristics than any mix-
ture. Chocolate did show the highest value for secondary
growth slope (Δ2), but its maximum G′ (G′max) was not the
absolute highest as would be expected. The superior crys-
tallization properties that differentiated pure CB from its
J Am Oil Chem Soc

Table 3  Initial onset time % Fat t1 (min) Δ1 [log(Pa)/min] t2 (min) Δ2 [log(Pa)/min] G′max [log(Pa)]
(t1), initial growth slope (Δ1),
secondary onset time (t2), 100 CB 19.1 (±0.5)B 0.47 (±0.01)D 24.6 (±0.4)B 0.14 (±0.02)B 7.40 (±0.01)A
secondary growth slope (Δ2),
10 CO 14.4 (±0.4)DE 0.58 (±0.02)AB 19.6 (±0.6)D 0.09 (±0.07)C 7.40 (±0.05)A
and maximum G′ (G′max) for
crystallization of chocolate PKO 14.9 (±0.2)CDE 0.62 (±0.03)A 19.4 (±0.3)D 0.07 (±0.03)CD 7.39 (±0.02)A
with cocoa butter (CB) added FPKO 14.0 (±0.8)E 0.56 (±0.04)ABC 19.5 (±0.9)D 0.07 (±0.02)CD 7.40 (±0.05)A
and blends of 10, 20, and 30% 20 CO 17.1 (±1.4)BC 0.49 (±0.02)CD 21.3 (±1.3)C 0.07 (±0.02)CD 7.35 (±0.02)A
coconut oil (CO), palm kernel
oil (PKO), and fractionated PKO 16.8 (±0.8)BCD 0.52 (±0.04)BCD 20.5 (±0.7)C 0.07 (±0.01)CD 7.35 (±0.01)A
palm kernel oil (FPKO) FPKO 18.4 (±0.6)B 0.45 (±0.01)D 22.8 (±0.5)C 0.06 (±0.04)D 7.28 (±0.07)AB
30 CO 24.1 (±1.1)A 0.44 (±0.02)D 30.2 (±1.6)A 0.06 (±0.09)E 7.10 (±0.02)C*
PKO 23.3 (±0.3)A 0.45 (±0.04)D 28.3 (±0.8)B 0.16 (±0.01)A 7.17 (±0.08)BC*
FPKO 19.0 (±1.4)B 0.51 (±0.03)BCD 24.4 (±2.0)B 0.06 (±0.01)E 7.34 (±0.03)A*

Point values (t1, t2) were determined from inflection points on the cooling curves and used to calculate
slopes (Δ1, Δ2). Different letters denote significant differences (p < 0.05) within columns. The standard
deviation is located in parentheses next to each mean value
*
  G′max values that do not reflect equilibrium within 60 min of cooling

blends in model systems did not always translate to choco-
late in the rheology data. This may be due to differences in
cooling rate and control of cooling between rheology and
NMR studies. The rheometer used in the study of chocolate
cooled all blends at a set ramp of 0.3 °C/min, while CB/
lauric fat model systems were cooled at slower rates overall
that ranged from 0.06 to 0.1 °C/min depending on crystalli-
zation temperature. Moreover, the model systems were not
cooled at a ramp; the temperature-hold conditions under
which crystallization was performed led to variable cooling
profiles.
The time of secondary onset was computed from the
point of curve inflection succeeding the linear Δ1 region.
Like t1, the highest values of t2 were for the systems made
with 30% CO and 30% PKO, and t2 increased with increas-
ing amount of lauric fat. For both t1 and t2, no relationship
could be identified between type of fat and onset of crys-
tallization stages, which challenged the general order of
FPKO-PKO-CO crystallization that was manifested in CB/
lauric fat model systems. Therefore, in chocolate systems,
the addition level of lauric fat is a more influential factor on
crystallization kinetics and behavior than specific fat type
added. A similar conclusion was reached by Baldino et al.
[11], who investigated the rheological properties of choco-
late in blends with anhydrous milkfats of different melting
points and found that addition level had a more signifi-
cant impact on chocolate crystallization than the variety of
milkfat used. While milkfat is not a lauric fat, similarities
exist between the two fats in their properties in chocolate
systems, as milkfat also forms eutectics with CB and can
impede its crystallization [17].
The slope of the initial growth phase (Δ1) was defined as
the slope of the linear region of the curve between the t1 and
t2 inflection points. The three 10% blends along with 20%
CO and PKO showed higher slopes than pure chocolate,
indicating that the addition of lauric fat appeared to accel-
erate initial crystallization rate. This result was unexpected
as it goes against the inhibition theory. For CO and PKO,
as the amount of lauric fat was increased from 10 to 30%,
slope values decreased, verifying the slower crystallization
rates with greater addition levels of lauric fat observed in
the model systems.
The slope of the secondary growth phase (Δ2) was cal-
culated for the region between t2 and the next inflection
point in a curve. These results were more complimentary
overall to the results of the model systems and the expected
effects of lauric fat on crystallization behavior. Aside from
30% CO, chocolate had the highest Δ2 of 0.14 log(Pa)/min,
which was significantly higher than any of the blends with
0.06–0.09 log(Pa)/min. This ratifies previous findings that
the addition of lauric fat resulted in slower rates of crys-
tal growth and the consequent interference on the solidi-
fication process of chocolate. Thus, the inhibition theory
applied during the secondary growth phase, with higher
lauric fat levels corresponding to slower rates of secondary
crystallization and pure chocolate showing the overall fast-
est secondary growth rate. However, the exception was the
unusually high Δ2 value for 30% PKO. As discussed, the
cooling curve for 30% PKO did not reach a final equilib-
rium and appeared to be still in the process of crystallizing
after 60 min had elapsed, which could impact its Δ2 value.
This might be because 30% PKO was still undergoing rapid
crystallization during its secondary growth phase, while
the secondary growth rates of the other blends had slowed
down because their crystallization processes were nearer to
completion.
G′max described the maximum G′ reached by each blend
after crystallization had elapsed for 60 min. In fat systems,
G′max is often correlated directly to equilibrium SFC [22].
G′ is listed in units of log(Pa) in Table 3 for clarity and ease

13

of comparison. G′max was a stable value for blends with
lower lauric fat contents. However, the G′max of the 30%
blends do not reflect final equilibrium values and cannot be
compared as indicated in Table 3. Chocolate and all blends
reached relatively high G′max of 7.10–7.40 log(Pa), indi-
cating more solid-like than liquid-like character with high
hardness. The high G′max value of chocolate was expected
given the equilibrium SFC of pure CB in model systems.
These results also can be related to the isosolid diagrams,
which were used to analyze the equilibrium conditions in
blends of lauric fat with CB. The isosolid diagrams showed
that pure CB had the highest equilibrium SFC at a given
temperature than any of the lauric fat blends. In rheology
data, the outliers with significantly lower G′max were 30%
CO and PKO. This authenticates the data from the model
systems, in which 30% CO and PKO reached the low-
est equilibrium SFC at 10 °C. Additionally, in the isosolid
diagrams, 30% blends had lower SFC across the range of
measurement temperatures than 10 or 20%. Therefore, par-
allels can be drawn between phase behavior of model sys-
tems, crystallization kinetics of model systems, and crystal-
lization kinetics of chocolate systems studied by rheology,
particularly in terms of equilibrium SFC/G′max and the influ-
ence of lauric fat on final equilibrium.
Conclusions
Delayed crystal growth and reduction in equilibrium SFC
by higher lauric fat levels were manifested in both model
and chocolate systems, effectively bolstering the claim that
the use of lauric fat in cocoa butter systems is commercially
limited. Solidification kinetics of the cocoa butter model
systems adhered to an exponential model. Thus, although
a sigmoidal model may be suitable for untempered fats, an
exponential model is most fitting for tempered fats. By con-
trast, chocolate systems displayed multi-step crystalliza-
tion behavior that precluded the fitting of a singular math-
ematical model. When applied to chocolate crystallization
kinetics, oscillatory rheology can shed light on fat matrix
formation under different conditions and model real-world
processing in a controlled cooling environment. Therefore,
the results for chocolate crystallization measured by oscil-
latory rheology are more translatable to industrial processes
and useful in product development applications.
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