Bioprocess and Biosystems Engineering

https://doi.org/10.1007/s00449-019-02251-1

RESEARCH PAPER

Addition of glyceryl monostearate affects the crystallization behavior

and polymorphism of palm stearin
Liyan Liu1 · Lin Li1,2 · Liting Wan1 · Linlu Mao1 · Bing Li1 · Xia Zhang1

Received: 16 September 2019 / Accepted: 8 November 2019

© The Author(s) 2019

Abstract
Low crystallization-rate and formation of crystalline clusters makes palm stearin unpopular in fat-based products especially in
their post-processing stage. Addition of emulsifiers is commonly used to overcome these drawbacks, since they are believed to
induce or stabilize specific polymorphs of palm stearin. Glyceryl monostearate (GMS) was applied in palm stearin (1%, 2%,
and 4% w/w) in this study, and the mechanisms on crystallization of palm stearin were investigated by means of differential
scanning calorimetry (DSC), X-ray diffraction (XRD), and polarized light microscopic (PLM) method. Data showed that
GMS prompted the isothermal crystallization (15–30 °C) in a dose-dependent manner. Crystallization turned to low super-
cooling sporadic nucleation at 30 °C. Besides, GMS led to an earlier onset of crystallization during cooling. GMS-palm
stearin blends crystallized to form α polymorphs at first and subsequently underwent polymorphic transition to become β′
polymorphs. Addition of 4% w/w GMS in palm stearin significantly decreased the size of crystals, which is helpful to reduce
the grainy mouth feel of fat products in practice.

Keywords Palm stearin · Glyceryl monostearate · Crystallization · Polymorphism

Introduction events during crystallization, and the transition from α

Palm oil is the world’s second largest consumed vegetable
oil owing to its distinct properties such as high productiv-
ity, low price, high thermal and oxidative stability, plastic-
ity at room temperature, and accessibility to fractionation.
Besides, it forms a desirable hard stock to be used in trans
fat-free shortening [1]. However, compared with other
natural fats, palm oil exhibits a slower crystallization-rate
and a longer α-lifetime [2], which hinders its application in
industrial processing. Palm stearin with heterogeneous tria-
cylglycerol (TAG) profile undergoes different polymorphic
* Bing Li
bli@scut.edu.cn
* Xia Zhang
cexzhang@scut.edu.cn
1
School of Food Science and Engineering, Guangdong
Province Key Laboratory for Green Processing of Natural
Products and Product Safety, South China University
of Technology, Guangzhou 510640, China
2
School of Chemical Engineering and Energy Technology,
Dongguan University of Technology, College Road 1,
Dongguan 523808, China
crystals to β′ crystals is very slow. Slow crystallization-rate
affects the hardness, texture, rheology, and spreadability of
lipid-based solid products [3]. In practice, addition of emul-
sifiers, such as monoglycerides, diglycerides, and sucrose
esters/sorbitan esters, is an effective way to alter the crystal-
lization behavior of fats [4, 5].
An emulsifier comprises of amphiphilic molecules con-
taining both hydrophobic and hydrophilic moieties. It affects
the nucleation and/or growth of crystallization of fat prod-
ucts. The effect of an emulsifier on nucleation includes alter-
ation of nucleation time, shift of nucleation temperature, and
change in the number and nature of nuclei [6]. Stimulation
or retardation of nucleation can be observed when different
emulsifiers are employed [7]. Research sheds light on the
initial crystals (seeds) after addition of emulsifiers [8]. Loi-
sel et al., found that tristearoylglycerol prompted the initial
crystallization peak of chocolate appearing early and big.
However, it did not affect the onset or the rate of the main
crystallization step. Besides, distearoylglycerol and stearic
acid showed little influence on the initial crystallization [9].
It was revealed that three polymorphic forms, namely the
sub-α, α, and β polymorphs, turned up for saturated mono-
glycerides with a chain length below 18 carbon atoms.

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 Bioprocess and Biosystems Engineering

Besides, the second sub-α form was found for saturated
monoglycerides with a chain length more than 18 carbon-
atoms. However, only the most stable β polymorphs formed
in unsaturated monoglycerides [10].
Effects of emulsifiers on palm oil crystallization were
reported as well. Verstringe et al., showed that morphology
of the palm oil crystals was oriented by crystallized mono-
palmitin additives, and the palmitic acid played an important
role as a template [11, 12]. Another study on the isothermal
crystallization proved that triacylglycerols containing longer
aliphatic chains (C16:0, C18:0 and C22:0) decreased the
nucleation time and changed the polymorphism of palm oil.
The blends of palm kernel, palm and cottonseed hard-fats
produced exclusively β′ form crystals whereas a mixture of
β and β′ crystals were observed in palm oil with soy and
crambe hard-fats [13]. A commercial monoacylglycerol
(MAG) advanced the onset of the non-isothermal crystal-
lization of palm oil probably by means of a template effect
and an effect on the crystal structure coarseness [14].
Despite the consensus on acceleration of palm oil crys-
tallization by monoglycerides, non-isothermal polymorphic
transition and crystallization behavior during cooling pro-
cess need further investigation. Understanding the crystalli-
zation mechanism during cooling will be a promising advan-
tage in fat processing, since a more rational strategy helps to
yield higher quality-products and lower operation-cost than
the traditional empirical method does. Given that glyceryl
monostearate (GMS) is the most widely used emulsifier in
food and cosmetics, it was chosen in this study to modify the
crystallization behavior of palm stearin during cooling pro-
cess. The nucleation, crystal growth, and polymorphic tran-
sition were investigated by means of differential scanning
calorimetry, X-ray diffraction, and polarized light micro-
scopic (PLM) method. The aim is to provide knowledge on
reasonable use of GMS in palm fat processing.
Results and discussion
Crystallization isotherms
Fat crystallization experiences four typical stages, namely
a crystal-free period, formation of nuclei, rapid accumula-
tion of crystals, and endgame stage representing slowdown
speed of crystallization, and maximal solid fat content (SFC)
[15]. A crystallization isotherm consisting of the profiles
of SFC versus treating time depicts the mechanism involv-
ing in the crystallization of a specific fat material [16]. The
crystallization isotherms of PlmSn with or without addition
of GMS were determined to further understand the complex
crystallization behavior.
GMS was well mixed with PlmSn prior to analysis and
the blends were subjected to heating at 80 °C to eliminate
the nuclei in the samples. All samples were quickly cooled
down to presetting temperature, and the crystallization iso-
therms were recorded against time and shown in Fig. 1. The

Fig. 1  Solid fat content (SFC) 60

(A) 40 (B)
profile of palm stearin samples
during isothermal crystalliza- 50
tion (Palm stearin samples con- 30
40
taining different amount of glyc-
SFC (%)

SFC (%)

eryl monostearate (filled square 30 20

0%, filled circle 1%w/w, upward
filled triangle 2%w/w, down- 20
10
ward filled triangle 4%w/w)
crystallized at 15 °C (a) 20 °C 10
(b) 25 °C (c), and 30 °C (d), 0
0
respectively. The SFC level was 0 20 40 60 0 20 40 60
monitored by pulsed nuclear Time (min)
Time (min)
magnetic resonance (pNMR)
analyzer. Data represent the
mean value of each test) 30 (C) (D)
20

20
SFC (%)

SFC (%)

10
10

0 0
0 20 40 60 0 20 40 60
Time (min) Time (min)

13
Bioprocess and Biosystems Engineering

results demonstrated that both degree of super-cooling and
GMS concentration remarkably affected the crystallization
behavior of PlmSn-GMS blends.
Figure 1 shows that the crystallization temperature
influenced SFC at the crystallization equilibrium period
(t > 50 min). The lower the temperature was, the higher the
SFC value became. The SFC at 15 °C multiplied comparing
with it at 30 °C. Interestingly, GMS had different impact on
SFC. The SFC value increased along with the increment
of GMS content in PlmSn-GMS blend at high temperature
(20–30 °C) whereas an opposite phenomenon was observed
at 15 °C. Furthermore, the results indicated that GMS was
more effective at high temperature (Fig. 1d) to facilitate the
formation of PlmSn crystals.
When PlmSn without GMS was tested, different isotherm
profiles were observed at various temperatures. A sigmoidal-
shaped isotherm curve was recorded at 30 °C for PlmSn,
indicating a uniform crystallization process which complies
with the direct forming of β’ morph [17]. However, second-
ary crystallization behavior was detected at low temperature
(15–25 °C), since a plateau-like area emerged behind the
initial increment of SFC level and was followed by another
quickly increased area in the SFC plot. A “cut-off” tempera-
ture (ca. 25 °C) between primary- and secondary crystal-
lization existed in this analysis, which shows similarity to
previous reports on palm oil samples [18]. The “cut-off”
temperature determined by DSC, PLM, rheometer, or pNMR
varied from 22–25 °C for palm oil in literature. Deep super-
cooling condition was thought to contribute to this phenom-
enon [19]. It is believed that super-cooling favors the quick
formation of α form of crystals and transition from α to β’
form was an important reason for the secondary crystalliza-
tion [17].
An evident change after addition of GMS was the shift
from primary to secondary crystallization at 30 °C. Besides,
the equilibrium time remarkably shortened, indicating a
positive role of GMS in this process. Since GMS has higher
melting point temperature (78 °C) than PlmSn does, GMS
tends to form nuclei during cooling easily and consequently
accelerates the process of crystallization of PlmSn-GMS
blends. The SFC level at the early stage (0–5 min) was pro-
portional to the GMS content, indicating the initiation effect
of GMS. Furthermore, existing of GMS may favor the pack-
ing of different TAG in the blends [20].
The well-defined Avrami model was adopted to depict
the isothermal crystallization mechanism on PlmSn sam-
ples. Table 1 lists the regression results of all analyses. High
correlation coefficient values imply that this model fits the
data successfully. The Avrami exponent (n) as a function of
time describes the crystal nucleation and growth mechanism
[21]. An n of 4 indicates a polyhedral crystal growth mecha-
nism while an n of 3 represents a plate-like growth, and an
n of 2 indicates a linear crystal growth. A rod-like growth
corresponds to a number of 1 [22]. At low temperature
(15–25 °C) PlmSn crystals were more likely to grow in rod-
like form whereas different growth mechanism was proposed
when the temperature was set at 30 °C. Besides, the index n
was close to unity after addition of 4% GMS, indicating the
change of growth behavior. The more GMS content was, the
lower the value of n became, which was in agreement with
isothermal plots (Fig. 1). The results suggest that addition
of GMS prompts the formation of SFC and increases the
equilibrium level of SFC at relatively high temperature. As
a result, it favors the operation of PlmSn in practice.
Apart from n in Avrami model, K and t1/2 indicate the
crystallization rate which is affected by cooling temperature.

Table 1  Isothermal Temperature/°C Sample n K/min−n t1/2/min R2

crystallization kinetic
parameters for PlmSn and its 15 PlmSn 0.827 ± 0.001 0.185 ± 0.000 4.947 ± 0.006 0.967
mixture with GMS
PlmSn + 1%GMS 0.848 ± 0.004 0.169 ± 0.001 5.289 ± 0.105 0.957
PlmSn + 2%GMS 0.849 ± 0.004 0.157 ± 0.007 5.771 ± 0.252 0.946
PlmSn + 4%GMS 0.791 ± 0.049 0.191 ± 0.025 5.117 ± 0.345 0.943
20 PlmSn 0.679 ± 0.015 0.292 ± 0.015 3.576 ± 0.165 0.941
PlmSn + 1%GMS 0.681 ± 0.008 0.278 ± 0.006 3.824 ± 0.041 0.978
PlmSn + 2%GMS 0.687 ± 0.002 0.271 ± 0.004 3.927 ± 0.099 0.972
PlmSn + 4%GMS 0.661 ± 0.008 0.289 ± 0.001 3.744 ± 0.076 0.935
25 PlmSn 0.800 ± 0.001 0.218 ± 0.013 4.268 ± 0.337 0.920
PlmSn + 1%GMS 0.749 ± 0.043 0.264 ± 0.035 3.643 ± 0.387 0.903
PlmSn + 2%GMS 0.715 ± 0.019 0.289 ± 0.012 3.394 ± 0.083 0.971
PlmSn + 4%GMS 0.663 ± 0.003 0.359 ± 0.011 2.701 ± 0.114 0.976
30 PlmSn 2.398 ± 0.168 0.002 ± 0.001 23.536 ± 1.518 0.961
PlmSn + 1%GMS 1.692 ± 0.506 0.017 ± 0.020 12.187 ± 2.633 0. 977
PlmSn + 2%GMS 1.536 ± 0.371 0.023 ± 0.023 11.715 ± 3.109 0.904
PlmSn + 4%GMS 1.074 ± 0.084 0.089 ± 0.023 6.854 ± 0.580 0. 988

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 Bioprocess and Biosystems Engineering

Remarkable change of these two parameters was found at (A) a

0
30 °C comparing with those at 15–25 °C (Table 1). The crys- -10 °C/min

Heat Flow Endo Up (mW)

tallization rate at 30 °C was much slower, which attributes -3
to the small driving force for crystallization at high tempera-
-6
ture. Interestingly, addition of GMS accelerated the crys-
tallization rate. The highest value of K was achieved when -9
PlmSn
4% GMS was used. Since GMS has a higher melting point -12 B
PlmSn+1% GMS
PlmSn+2% GMS
than PlmSn, formation of GMS nuclei at high temperature A PlmSn+4% GMS
-15
(30 °C) should be a possible reason for prompting the crys- -20 -10 0 10 20 30 40 50 60 70
tallization of PlmSn. On the other hand, the super-cooling T (°C)
condition at low temperature produced high driving force for
crystallization and made PlmSn insensitive to GMS. b 30 onset point
10
peak value
28 8
Crystallization behavior during cooling
26 6

T (°C)

T (°C)
Since unsaturated long-chain fatty acids show different melt-
24 4
ing behavior from the saturated ones, the triacylglycerols
(TAGs) consisting of both saturated and unsaturated moie- 22 2
ties, such as palm oil, will experience a complex crystal- Peak A Peak B
20 0
lization process under cooling-down treatment. Given that 0 1 2 3 4 0 1 2 3 4
glyceryl monostearate (GMS) has a higher melting tempera- GMS concentration (%, w/w)
ture than palm oil, addition of GMS will further alter the
crystallization behavior of palm stearin.
(B)
Figure 2a shows the crystallization profiles of palm oil PO+4% GMS

samples with or without addition of GMS when they were

PO+2% GMS
cooled down from 80 to − 40 °C. Two exothermic peaks
Heat Flow Endo Up (mW)

(A and B) successively appeared during cooling, indicating

two components with high- and low melting-point, respec-
tively. The first one (A) was recorded in the DSC thermo-
gram above 21 °C corresponding to the saturated TAGs, the
stearin component. The onset of peak B was below 7.5 °C,
which represents the crystallization process of the compo-
nent consisting of the unsaturated TAGs, namely, the olein
fraction. This phenomenon is in accordance with the fact
that the saturated TAGs crystalize at higher temperature
than the unsaturated ones due to the stronger intermolecular
forces. Similar results were observed when different types
of palm oil cooled down [23]. Besides, the crystallization
temperature of both A and B increased along with the addi-
tion of GMS (Fig. 2b).
Figure 2b shows that addition of GMS accelerated the
crystallization process of PlmSn. Moreover, shift of peak A
was larger than peak B, which indicates that the saturated
TAGs were prone to be affected by GMS. When 4% (w/w)
GMS was added, the crystallization temperature of peak A
rose up to 4.73 °C while a 0.59 °C increase was detected in
peak B. However, the change of energy releasing in palm
oil during crystallization was not significant after addition
of GMS (less than 2.3%, data not shown).
This is consistent with the previous results of crystalliza-
tion kinetics in this research, that is, the addition of GMS
at 30 °C significantly increased the crystallization rate of
PlmSn, and with the increase of the concentration of GMS,
PO+1% GMS
PO
-20 -10 0 10 20 30 40
Temperature (°C)
Fig. 2  a Crystallization thermograms of PlmSn (PlmSn, palm stea-
rin. GMS, glyceryl monostearate. Samples were cooled down from 80
to – 40 °C at 10 °C/min. The curves show one out of three parallel
tests.), b the onset and peak temperature of two exothermic peaks in
crystallization thermograms of PlmSn. (GMS glyceryl monostearate.
Data were expressed as mean ± SD)
the maximum crystallization rate of PlmSn appeared earlier,
because of the higher melting point of GMS, which played
a leading role in nucleation. The crystallization tempera-
ture of the crystallization peak A starts gradually at 30 °C,
so the effect of GMS on accelerating the crystallization of
peak A is obvious. The crystallization temperature of peak
B is lower than 10 °C. The crystallization kinetics study
shows that the super-cooling plays a major role in the crys-
tallization process at low temperature, so GMS has little
effect on the crystallization at peak B. Adding 4% GMS

13
Bioprocess and Biosystems Engineering

and cooling rate of 10 °C/min can significantly increase the
initial crystallization temperature, shorten the induction time
and reduce the industrial cost.
Polymorphism of palm stearin at different
temperature
Polymorphism is one of the most representative characters
of natural TAGs owing to their heterogeneous composition
[24]. Since crystallization performance is of crucial impor-
tance for a fat both in operation processes and as a final
product for consumers, a better understanding of the mecha-
nism in microscopic scale seems indispensable. An analysis
taking anhydrous milk fat as the subject revealed that slow
cooling-rate prompted the direct formation of βʹ polymorph
due to the sufficient time for dense packing of TAGs. On
the contrary, the unstable α-polymorph was prone to pro-
duction at high cooling rate [25]. Similar results were also
observed in other TAGs [6]. Given that high cooling-rate is
a preferential selection to enhance the throughput, a quick
transformation from α to β’ polymorph which is much stable
should be considered.
Two separate exothermic peaks were detected in PlmSn
samples during quick cooling, which as above stated indi-
cates two types of crystallization behavior. Therefore, the
polymorphism at the end of each peak (10 °C and − 10 °C,
respectively) was analyzed by means of XRD technique.
Figure 3 illustrates the SAXS and WAXD profiles of PlmSn
with or without addition of GMS. At high temperature
(10 °C) an irregular sharp peak (4.13 Å) showed in WAXD
plot for PlmSn. This pattern agrees to the reported α poly-
morph [26]. The bump which was adjacent to the α peak was

40.48Å
4.13Å

(A) (B)
45.97Å

PlmSn+4% GMS
Intensity (a.u.)

Intensity (a.u.)

PlmSn+4% GMS PlmSn+2% GMS

PlmSn+2% GMS
PlmSn+1% GMS
PlmSn+1% GMS

PlmSn PlmSn

2 3 4 5 10 15 20 25 30
2θ ( ° ) 2θ ( ° )

4.16Å
40.89Å

45.97Å (C) (D)

3.80Å

PlmSn+4% GMS
Intensity (a.u.)
Intensity (a.u.)

PlmSn+4% GMS

PlmSn+2% GMS
PlmSn+2% GMS

PlmSn+1% GMS PlmSn+1% GMS

PlmSn PlmSn

2 3 4 5 10 15 20 25 30
2θ ( ° ) 2θ ( ° )

Fig. 3  X-ray diffraction patterns of PlmSn samples at different temperature (PlmSn, palm stearin. GMS, glyceryl monostearate. Plot A and B are
SAXS and WAXD patterns at 10 °C, respectively, and plot C and D are at − 10 °C)

13

attributed to the liquid phase [27]. Besides, transformation
happened at low temperature (− 10 °C) during cooling. Two
peaks, 4.16 Å and 3.80 Å, instead of 4.13 Å appeared in
WAXD plot, which corresponds to the typical characteristic
of βʹ polymorph [28]. Direct formation of β’ polymorph was
not observed. These results comply with the previous reports
on TAGs crystallization behavior at high cooling rate [12].
The α polymorph has a lower critical activation free energy
for nucleation and a higher nucleation-rate than the βʹ and
β polymorphs [29]. Therefore, α polymorph is kinetically
favored and starts to crystallize at quick cooling rate, while
βʹ polymorph behaves as time consuming process. Conclu-
sions were drawn elsewhere as the α crystals of palm oil
act as nucleation sites for the formation of the β′ crystals
[30]. Besides, despite little impact on transformation of the
polymorphs, addition of GMS accelerated the crystallization
rate of PlmSn (Fig. 1).
Since crystal network with different spacing allows the
assignment of double (2L) or triple (3L) layers of TAGs
depending on their molecular moieties and packaging angle,
this network provides essential information on the micro-
structure of PlmSn [31]. The SAXS analysis was performed
on PlmSn at quick cooling-rate (10 °C/min). However, an
evident peak (40.48 Å at 10 °C, 40.89 Å at − 10 °C) was
observed when high content of GMS existed in PlmSn blend.
The results show that effect of GMS on the crystallization
behavior was dose-dependent. High content GMS facilitated
the formation of 2Lβ′ polymorph. In practice the double-
chain length structure of TAGs is much desirable in the
process of industrial shortening preparation, since the 3L
structure was linked to the sandy taste and loss of gloss in
the end products [32]. Therefore, enhancing 2Lβ′ polymorph
by addition of GMS may be a promising method for improv-
ing the quality of products containing PlmSn ingredient.
Microstructure of fats depends on the composition of
TAGs and their crystallization behavior, which in turn affects
the physical property of fats. In this study the microstructure
alteration caused by GMS was visualized by polarized light
microscopic (PLM) method. Light field in PLM represents
the clusters of individual crystals [33]. PlmSn samples were
prepared in light of industrial process for shortening and
then analyzed by PLM.
Figure 4 illustrates the morphology variation of crystals
between PlmSn and PlmSn with 4% GMS. PlmSn showed
a fascicular type structure consisting of large crystals with
unevenly distributed empty space. Unsurprisingly, addition
of 4% GMS significantly lowered the size of crystals and
increased the density and uniformity of the spherules type
crystals. This morphology helps prevent grainy mouth feel
of fats for food product. Besides, the crystal dispersion of
fats with a large number of small crystals can provide desir-
able properties such as good spread ability.
13
Bioprocess and Biosystems Engineering
100um 100um
PlmSn PlmSn + 4% GMS
Fig. 4  PLM image (×500) of PlmSn and its mixture with 4% GMS
Given the improvement brought out by addition of small
amount of GMS it is suggested that the cost for processing
of PlmSn will be cut down by tuning the operation time and
temperature. However, the mouth feel, stability, even prod-
uct appearance should be carefully investigated in future to
provide comprehensive assessment on PlmSn-GMS perfor-
mance in food.
Material and methods
Material
Palm stearin (PlmSn, The sliding melting point is 43.06 °C)
was obtained from Excel Sior Technology Co., Ltd. (Shenz-
hen, China). The fatty acid composition and TAG contents of
PlmSn are listed in Tables 2 and 3, respectively. PlmSn was
stored at 4 °C prior to use. Glyceryl monostearate (GMS)
(analytical pure) was obtained from kermel Co., Ltd. (Tian-
jin, China).
Preparation of the blends of PlmSn and GMS
At first PlmSn was stirred with a magnetic stirrer at
80 ± 0.5 °C for 30 min, then GMS was dispersed in melted
PlmSn until a homogeneous blend was obtained. Based on
the industrial practice, the final concentration of GMS was
set as 1%, 2%, or 4% w/w.
Isothermal crystallization and crystallization
kinetics
Isothermal crystallization was performed in a Bruker PC20
series pulsed nuclear magnetic resonance (pNMR) analyzer
(Bruker, Mississauga, ON, Canada). Accurate control of
temperature was realized by a water bath (DC-3006, XinZhi
Instrument Company, Ningbo, China). The sample in a NMR
tube was heated to 80 °C and held for 30 min to eliminate
any thermal history before measurement, and then it was
crystallized at 15 °C, 20 °C, 25 °C, and 30 °C, respectively.
Bioprocess and Biosystems Engineering
Table 2  Fatty acid composition C12:0 C14:0
(%) of PlmSn
0.64 ± 0.01 1.26 ± 0.03
Table 3  TAG composition (%) of PlmSn
PPPa PPS POP POS PLP
4.09 ± 0.24 1.65 ± 0.11 25.81 ± 1.08 11.44 ± 0.80 5.98 ± 0.17 29.21 ± 0.63 2.41 ± 0.07 5.51 ± 0.28 6.98 ± 0.06 1.07 ± 0.03 5.85 ± 0.11
a
P, S, O, L, and E correspond to palmitic acid, stearic acid, oleic acid, linoleic acid, and elaidic acid, respectively
The levels of solid fat content (SFC, %) were measured in
every minute. All tests were performed in duplicate.
The isothermal crystallization kinetics was fitted into
Avrami equation which succeeded in describing crystalli-
zation kinetics of various polymers and other material [34].
Isothermal Avrami kinetics is concerned with the overall
crystallization, including nucleation and growth. Its primary
form is:
n system was adopted to monitor the polymorphs of palm crys-
1 − Xt = exp(−kt ) ,
where Xt is the relative crystallization level at time t, n is
the Avrami exponent, K is the Avrami rate constant (min-n).
Equation 1 can be linearized by logarithmic transformation
of [−ln(1−X)] and t. K and n were calculated from intercept
and slope, respectively. The value of Xt was calculated by
integration of the isothermal crystallization:
X(t) = SFC(t)∕SFC(∞),
where SFC(t) describes the SFC as a function of time t,
SFC(∞) is the limiting SFC as time approaches infinity.
Half time of crystallization (t1/2) which expresses the mag-
nitude of the Avrami constant was calculated by Eq. 3. The
numerical value of K is directly related to the half time of
crystallization:
t1∕2 = (0.693∕K)1∕n .
Crystallization behavior analysis during cooling
by differential scanning calorimetry (DSC)
The thermal properties of PlmSn were measured using a
DSC with a refrigerated cooling system (Texas Instruments,
Diamond-1, PerkinElmer, Dallas, TA, USA). Nitrogen was
used to purge the thermal analysis system at a flow rate of
1 mL/min. The melted sample (5–6 mg) was weighed into
an aluminum pan and sealed. An empty hermetically sealed
aluminum sample pan was used as the reference.
Before analysis the samples were heated to 80 °C with the
rate of 30 °C/min and held for 10 min to ensure that the fats
C16:0 C18:0 C18:1 C18:2 Others
49.61 ± 0.16 6.41 ± 0.04 34.15 ± 0.21 7.15 ± 0.03 0.79 ± 0.01
POO SOO POL OOO OOL others
were totally melted and all the nuclei were destroyed. Then,
the samples were cooled down to − 40 °C at the cooling rate
of 10 °C/min and held for 20 min until fully crystallized.
Polymorphism analysis by X‑ray diffraction
spectroscopy (XRD)
A Smartlab XRD (Rigaku, Japan) with a temperature control
(1) tals using Cu KR radiation with a Ni filter (40 kV, 40 mA).
The samples were heated to 80 °C at first at the rate of 30 °C/
min and held for 10 min to ensure that all the nuclei were
destroyed. Then, the samples were cooled to − 10 °C at the
cooling rate of 10 °C/min. In the process of cooling, samples
were scanned from 5° to 30° (2θ scale) at a rate of 10°/min
and scanned from 1° to 10° (2θ scale) at a rate of 0.6°/min
at the temperature of 10 °C and − 10 °C, respectively. The
(2) calculations were performed by MDI Jade 5.0 software. All
tests were performed in duplicate.
Morphology visualization by polarized light
microscopy (PLM)
The morphology of sample crystals was observed using
PLM (Olympus, BX51, Japan) with an attached Gimaging
digital camera (Gimaging, Micropublisher 3.3 RTV, Can-
(3)
ada). Fifty mg of sample was placed on a carrier glass slide
at 25 °C. Then, a cover slip was placed above the sample to
ensure its uniformity and thickness. The photomicrograph
was recorded at a 500-fold magnification. Several repre-
sentative regions in each sample were scanned to obtain a
number of images with high resolution.
Conclusions
GMS has been widely used as an emulsifier in food and
cosmetics due to its high yield and low price. GMS in PlmSn
blends accelerated the isothermal crystallization, especially
it turned to low super-cooling sporadic nucleation at 30 °C.
Besides, 4% w/w GMS had the most significant effect on
13

the crystallization. Furthermore, addition of GMS led to an
earlier onset of crystallization during cooling. The higher
the concentration of GMS was, the earlier the onset of crys-
tallization became. According to the XRD analysis, PlmSn
and PlmSn-GMS mixture crystallized first as α polymorphs
and subsequently underwent a polymorphic transition to β′
polymorphs. Addition of 4% GMS into PlmSn changed the
crystallization state of aggregation and lowered the PlmSn-
GMS crystal size than the size of PlmSn crystals, which
potentially improves the mouth feel of food containing palm
stearin.
Acknowledgements This work is supported by the National Natural
Science Foundation of China (NSFC)-Guangdong Joint Foundation
Key Project (no. U1501214), the National Natural Science Founda-
tion of China (no. 31871758, 31401660), the Pearl River S&T Nova
Program of Guangzhou (no. 201806010144) and the Fundamental
Research Funds for the Central Universities, SCUT (no. 2017MS093).
Author contributions Data curation: LL; formal analysis: LL; method-
ology: LL, BL, and XZ; validation: LL, LW, and LM; writing—original
draft: LL; writing—review & editing: BL.
Compliance with ethical standards
Conflicts of interest The authors declare no conflict of interest. The
founding sponsors had no role in the design of the study; in the col-
lection, analyses, or interpretation of data; in the writing of the manu-
script, and in the decision to publish the results.
Open Access This article is licensed under a Creative Commons Attri-
bution 4.0 International License, which permits use, sharing, adapta-
tion, distribution and reproduction in any medium or format, as long
as you give appropriate credit to the original author(s) and the source,
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copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.
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