Eur. J. Lipid Sci. Technol.

103 (2001) 729–734 729

Wai Lin Siew Crystallisation and melting behaviour of palm

kernel oil and related products by differential
Malaysian Palm Oil board scanning calorimetry
(MPOB)
Lauric oils are valuable sources for oils suitable for various food applications. They are
particularly useful as cocoa butter substitutes for which steep solid fat content profiles
are required. Palm kernel oil is one such fat, which upon fractionation and/or hydro-
genation provides a variety of oil fractions with different oil composition and properties.
The stearins have excellent properties for confectionery fats, while the oleins can be
further hydrogenated to improve their properties. This paper gives an overview of the
properties of products of palm kernel oil, produced from fractionation and hydrogena-
tion. The melting and crystallisation properties from differential scanning calorimetry
studies are discussed in relation to the triacylglycerols of the oils.

Keywords: Crystallisation, melting, differential scanning calorimetry, palm kernel oil

products.

1 Introduction however, scarce information in the literature on the crys-

Lauric oils such as coconut, palm kernel, babassu are
used extensively both in the food industry and in the oleo-
chemical industry. The high demand for lauric oils and
their price variation has caused considerable interest and
hence research is carried out to look for alternative
sources via gene manipulation. Nature has endowed the
coconut and the oil palm to produce oils with a high con-
tent of medium-chain triacylglycerols. In the case of the oil
palm, two types of oil are extracted from the fruits. The
outer mesocarp gives palm oil while the inner kernel pro-
duces the kernel oil. Palm kernel oil (PKO) can be frac-
tionated to produce a harder fraction, palm kernel stearin
tallisation and melting behaviour of these oils. This paper
examines the crystallisation and melting behaviour of
some of these products using differential scanning
calorimetry (DSC) and nuclear magnetic resonance
(NMR).
2 Materials and methods
2.1 Materials
PKO and its fractions were obtained from local refineries

(PKS), used as cocoa butter substitute and a liquid frac-
tion, palm kernel olein (PKOO). These products and the
kernel oil are hydrogenated to various degrees to further
reduce the iodine value of the oil. The chemical composi-
tion and physical properties of some of these products
have been documented [1, 2]. Earlier works by Bezard
[3], Bezard et al. [4] and Cornelius [5] have documented
the composition of palm kernel oil only. In the trade, the
oils are characterised by their respective iodine value,
which is an important parameter to specify the oil compo-
sition and quality. The iodine value of PKO lies for exam-
ple between 16 and 19 and the end users often scrutinise
samples having higher iodine values for probable conta-
mination. On the other hand, PKS specifications are
based on a maximum iodine value of 8. While there is
enough information on the composition of the oils, there is
Correspondence: Wai Lin Siew, Malaysian Palm Oil board
(MPOB), P.O.Box 10620, 50720 Kuala Lumpur, Malaysia.
Phone: +603-8928-2430, Fax: +603-8925-9446; e-mail:
siew@mpob.gov.my
Research Paper
– Southern Edible Oil Sdn Bhd and Soctek Sdn Bhd,
PKOO and PKS from dry fractionation processes. The
hydrogenated oils (HPKO, HPKOO and HPKS) were ob-
tained by hydrogenation of the respective oils. All chemi-
cals used were either of analytical or high-performance
liquid chromatography grade.
2.2 DSC analysis
DSC analyses of the oils were performed with a Perkin
Elmer 7 DSC (Perkin Elmer, Norwalk, CN, USA). Prior to
weighing (10 mg) each sample was completely melted at
80 °C into an aluminium pan, which was then sealed us-
ing a sample pan crimper. Heating the samples to 80 °C
in the DSC instrument and keeping it for 10 min at this
temperature erased the previous history of the sample.
The samples were cooled to –30 °C at a rate of
–40 °C/min. At the end of the period, the sample was
heated in steps of 5 °C/min to 80 °C for 10 min and then
cooled again in steps of 5 °C/min to –30 °C. The melting
and cooling thermograms were recorded.

© WILEY-VCH Verlag GmbH, 69451 Weinheim, 2001 0931-5985/2001/1111-0729 $17.50+.50/0

730 Wai Lin Siew Eur. J. Lipid Sci. Technol. 103 (2001) 729–734

2.3 Fatty acid composition 2.5 Solid fat content by NMR

The methyl esters were prepared by transesterification
of the sample with 1 M sodium methoxide [6]. 0.95 ml
n-hexane were added to the oil sample (6 drops or
50 mg) in a 2 ml vial using a graduated pipette. The mix-
ture was well shaken and 0.5 ml sodium methoxide were
added. The vial was shaken vigorously for 5 s with the
help of a vortex mixer. At first the mixture appeared clear,
but it turned turbid when sodium glyceroxide precipitated.
After 5 min the clear upper layer of methyl ester was
pipetted off for GC analysis.
Quantification of the peak areas was carried out with a
Hewlett-Packard HP5890 II gas chromatograph. The
analysis conditions corresponded to those described by
Siew and Ng [7]. A correction based on analysis of a ref-
erence mixture or methyl esters of known composition
(20A from Nuchek Prep Inc., Nuchek, Elysian, MN, USA)
was used for calculation of the weight percentage of the
total mass.
2.4 Triacylglycerol (TAG) composition by high
performance liquid chromatography (HPLC)
TAG analyses were performed with Gilson 303 and 302
pumps, a Waters 410 differential refractometer and a
Hewlett Packard 3396A integrator. The two columns were
25 cm long, had an i.d. of 4 mm and were packed with
5 m Lichrosphere RP18 (Merck, Darmstadt, Germany).
The columns were kept in an oven at 30 °C. The mobile
phase was acetonitrile : acetone (65:35, v/v) at a flow rate
of 1.0 ml/min. Injection was achieved through a Rheo-
dyne valve fitted with a 20 µl loop. Samples were injected
as 10% (w/v) solutions in warm acetone. Identification of
the TAGs was made by comparison with those of avail-
able standards, purchased through Sigma Chemicals.
The TAGs were expressed as equivalent carbon number
(ECN) in weight percentage of the total TAGs.
The samples were melted and filled into the sample tubes
(10 mm o.d. x 75 mm length) up to a height of 3 cm. Prior
to measurement the samples were melted at 70 °C for
30 min, chilled at 0 °C for 90 min and then held at 10 °C
for 30 min. One tube was held at each measuring tem-
perature for 30 min. The measuring temperatures were
10, 15, 20 and 25 °C. The instrument used was a Bruker
Minispec PC 120 pulsed NMR. The percentage of solids
determined by pulsed NMR may be defined as the ratio of
the response obtained from the hydrogen nuclei in the
solid phase and the response arising from all the hydro-
gen nucleic in the sample. The direct display method
was employed during the measurements. In the direct
method, magnetisation is sampled at two time intervals –
one shortly (11 µs) after excitation of the magnetisation
and another one after a longer interval (70 µs). The mea-
surement after the short interval provides the magnetisa-
tion of both liquid and solid phase. The repeatability of
measurements for the direct method is 1.0.
3 Results and discussion
3.1 Fatty acid and triacylglycerols
The fatty acids and TAGs composition of the oils used in
this study are presented in Tabs. 1 and 2. The found
compositions are consistent with that given by Siew and
Berger [1] and Tang et al. [2]. Thus the oil used in this
study can be regarded as representative of the oils gen-
erally obtained in Malaysia. The fractionated products,
the kernel olein and stearin have compositions reflecting
the more liquid or solid nature of the oil. The main differ-
ence between PKO and PKOO is the lower content of lau-
ric and myristic acids and the higher content of oleic acid
in the latter. In contrast the content of other acids, includ-
ing palmitic acid, is roughly the same. Similarly, the main
difference between PKS and PKO is the content of the
fatty acids, lauric, myristic and oleic acids, which is higher
for the two former acids and lower for the latter. Hydro-
genated samples are easily distinguished by their high
stearic acid content and by the absence of unsaturated
acids. The differences between hydrogenated and non-

Tab. 1. Fatty acid composition of palm kernel oil products.

C6:0 C8:0 C10:0 C12:0 C14:0 C16:0 C18:0 C18:1 C18:2
[wt-%]
PKO 0.3 3.9 3.4 49.9 16.5 8.1 2.8 12.9 2.1
PKOO 0.1 4.0 3.6 45.6 14.4 8.2 2.3 18.6 3.1
PKS 0.1 2.0 2.8 58.1 22.1 7.4 1.6 5.0 0.8
HPKO 0.1 3.0 3.2 49.1 16.7 8.6 19.2 – –
HPKOO 0.2 4.4 3.5 44.3 14.1 8.3 25.1 – –
HPKS 0.1 1.9 2.8 56.6 22.0 7.9 8.6 – –
Eur. J. Lipid Sci. Technol. 103 (2001) 729–734 Crystallisation and melting behaviour of palm kernel oil 731

Tab. 2. Triglyceride Composition of palm kernel products.

Triglycerides PKO PKOo PKS HPKO HPKOo HPKS
ECN : n
[wt-%]
C26 1.07 0.71 0.51 0.82 1.4 2.2
C28 0.64 0.85 0.45 0.71 0.99 1.32
C30:2 – 0.44 – – – –
C30:1 – 0.91 – – – –
C30 1.41 1.11 0.51 1.44 1.92 0.95
C32 6.11 7.63 3.52 6.76 8.36 3.67
C34:1 0.54 0.74 – – – –
C34 8.36 9.32 6.85 8.62 9.69 6.56
C36 21.35 18.61 28.21 21.68 18.63 26.04
C38:2 0.62 1.03 – – – –
C38:1 0.8 1.38 – – – –
C38 15.23 10.57 24.42 16.39 12.33 22.93
C40:2 0.88 – – – – –
C40:1 4.55 7.62 2.71 – – –
C40 8.64 5.41 14.32 9.62 7.16 13.7
C42:2 0.84 1.21 – – – –
C42:1 5.12 6.66 2.44 – – –
C42 4.11 2.75 6.7 9.61 9.68 9.11
C44:1 3.44 4.5 – – – –
C44 4.39 5.25 0.95 7.06 8.08 5.24
C46:2 2.38 2.06 2.04 – – –
C46:1 1.78 2.3 2.8 – – –
C46 2.01 2.44 0.93 5.54 6.86 3.37
C48:3 1.92 2.05 1.34 – – –
C48:2 1.78 2.19 0.49 – – –
C48:1 0.97 1.25 0.43 – – –
C48 0.24 0.59 0.38 6.46 8.51 2.85
C50:2 0.47 – – – – –
C50:1 0.34 0.41 – – – –
C50 – – – 2.67 3.43 1.35
C52 – – – 2.61 2.97 0.69

hydrogenated samples become apparent from the ab- process produces further a stearin where the content of
sence of triacylglycerols containing double bonds. PKO, solids is enhanced at low temperatures which shows a
PKOO and PKS include only 4%, 2.8% and 6.7%, of ECN steep melting curve and complete melting at 35 °C.
42, respectively, whereas the hydrogenated samples in-
Thus this product is highly valued in the confectionery in-
clude at least 9% of that TAG. Similarly the hydrogenated
dustry. The low content of solids of PKOO can be further
samples contain about 3–4% more ECN 44 TAG than
increased by hydrogenation. Among the hydrogenated
non-hydrogenated samples. The highest difference is
samples, the sharpest melting profile is shown by HPKS,
found for ECN 48, which is mainly due to contributions of
followed by HPKO. HPKOO tends to be softer at lower
C18:0, C18:0, C12:0 and C14:0, C16:0, C18:0. Two new
temperatures and also has some tailing of solids at higher
TAGs are present in the hydrogenated samples, ECN 50
temperatures. The observed lower tailing in the HPKS is a
and ECN 52, likely originating from. C16:0, C16:0, C18:0
reflection of the lower ECN 48 to ECN52 content in the oil.
and C16:0, C18:0, C18:0, respectively. These TAGs are
only present at levels of less than 3%.
3.3 DSC analyses

3.2 Solid fat contents Tab. 4 shows the data of the DSC analyses of palm kernel
oil products while the thermograms are illustrated in
PKO (Tab. 3) has a high content of solids at low tempera- Figs. 1 and 2. When PKO is cooled at steps of 5 °C/min to
tures but a low one at 25 °C. A simple fractionation sub ambient temperatures, it crystallises rapidly at tem-
732 Wai Lin Siew Eur. J. Lipid Sci. Technol. 103 (2001) 729–734

Tab. 3. Solid fat content of palm kernel oil products.

10 °C 15 °C 20 °C 25 °C 30 °C 35 °C 40 °C SMP [°C]
[%]
PKO 69.4 57.1 36.0 12.3 - - - 28.2
PKOO 54.8 36.8 17.2 - - - - 24.0
PKS 91.8 89.6 83.1 67.1 30.8 - - 31.5
HPKO 94.6 93.6 87.6 64.6 34.9 13.0 7.2 40.0
HPKOO 93.6 90.1 79.4 59.6 38.9 19.9 0.6 41.1
HPKS 95.4 94.9 94.1 84.8 38.9 4.2 0.5 34.5

peratures slightly below its melting point. On the DSC sation is shifted to 18 °C instead of 12 °C and the crys-
cooling curve (Fig. 1) the first crystallisation peak appears tallisation peak to 11.8 °C instead of 10.7 °C. The melting
at 5.6 °C while the second exotherm is at 2.8 °C. Initial peak is at 32.5 °C.
crystallisation appears at 10 °C. When melted the crys-
tallised sample shows a small endotherm at –15 °C and a In the case of the olein hydrogenation generally leads to a
larger broader one from 10 °C to 30 °C (Fig. 2). The liquid changed crystallisation and melting behaviour. HPKOO
fraction, palm kernel olein shows similar DSC profiles crystallises at a much higher temperature than PKOO, the
having the first exotherm at 2.2 °C and the second at first exotherm is observed at 29.7 °C (small) and the sec-
–3 °C. The melting profile (Fig. 2) is also similar to PKO in ond (bigger) at 20 °C. By way of contrast the exotherms
having a broad endotherm for melting at 27 °C. The crys- of PKOO are observed at 2.2 and –3 °C. When HPKOO is
tallisation profiles of PKO and PKOO are modulated by
the presence of mixtures of high molecular weight TAGs
containing double bonds. On the other hand PKS gives a
sharp crystallisation peak at 10.7 °C with a slight shoulder
at 12 °C. In fact, this crystallisation profile is similar to that
of trilaurin under similar DSC conditions. The sample
melts in a sharp endothermic peak at 33.1 °C. The rela-
tively sharp peaks indicate the sharp melting behaviour of
the stearin. There is no correlation between the DSC
melting temperature and the slip melting point of the oil.

The DSC curves of HPKO show two exotherms and a

broad endotherm for melting. Crystallisation occurs at a
temperature of 27 °C, where a small exotherm is ob-
served. The second crystallisation peak occurs at 19 °C.
The melting thermogram shows high melting at 50 °C. In
contrast to PKO where the oil melts at 30 °C the en-
dotherm of HPKO shows some high melting fractions in
the region of 42–50 °C. Thus, as expected the solid pro-
file also reflects this property. HPKS shows a sharp type
of profile similar to PKS except that the onset of crystalli-

Tab. 4. DSC analyses of palm kernel oil products.

Sample Melting program Crystallisation program
Toffset [°C] ∆H [J/g] Tcry [°C]
PKO 30.9 100.6 2.8, 5.6
PKOO 27.6 82.1 2.9, 2.2
PKS 36.5 106.6 10.7
HPKO 49.5 120.3 18.9, 27.7
HPKOO 50.6 120.7 20.1, 29.7
HPKS 42.5 106.7 11.8 Fig. 1. DSC crystallisation thermogram of palm kernel oil
products (scan at 5 °C/min).
Eur. J. Lipid Sci. Technol. 103 (2001) 729–734
Fig. 2. DSC melting thermograms of palm kernel oil prod-
ucts (scan at 5 °C/min).
heated in steps of 5 °C/min the melting profile is broad
and ill-defined, finally melting at 50 °C. The slip melting
point for this oil is 41 °C.
Hydrogenation of palm kernel products results in more
products available to the confectionery industry. This is
established by Rossell’s work [8], which also shows the
differences in thermograms of HPKO hydrogenated to dif-
ferent degrees. In the present study the difference ob-
served between hydrogenated and non-hydrogenated
sample is the crystallisation temperature, which is 5.6 °C
for PKO and 27.7 °C for HPKO. In the thermogram of
HPKO the larger exotherm represents the lower melting
fraction. The fatty acid composition of PKOO and HPKOO
differs considerably, whereby the hydrogenated sample
contains much more stearic acid. It appears that a high
stearic acid content is not sufficient to allow sharp crys-
tallisation. The thermogram of the sample shows a high
melting and a lower melting exotherm instead. Probably
the sample could be refractionated to gain the required
properties.
Crystallisation and melting behaviour of palm kernel oil 733
The main TAGs involved in the crystallisation of PKS are
ECN 36, ECN 38 and ECN 40. Presumably ECN 40, melt-
ing at a higher temperature than ECN 36 and ECN 38, is
the major TAG involved in the crystal nucleation. Besides
ECN 42 and ECN 44 the above-mentioned TAGs are in-
volved in the crystallisation of PKO. Next in line assisting
cristallisation are the TAGs with one and two double
bonds. The high-melting and low-melting peaks of PKOO
reflect these TAGs and the composition of PKOO is now
more evenly spread between the saturated and unsatu-
rated TAGs. In the hydrogenated samples crystallisation
is effected by the high-melting TAGs ECN 48, ECN 50
and ECN 52 and is observed in the small crystallisation
exotherms of HPKO and HPKOO and to a lesser extent in
HPKS. Only about 4.9% of ECN 48, ECN 50 and ECN 52
are present in HPKS as compared with 12-15% in HPKO
and HPKOO. The DSC thermograms also revealed
relatively simple curves, characteristic of fats with little
forms of polymorphism. The X-ray data (Tab. 5) show
only β’ polymorphs for all samples, indicating the strong
β’ tendencies of such fats. The polymorphs were obtained
upon cooling oil samples from melting temperatures to
temperatures of 20, 30 and 40 °C and maintaining them
at these temperatures for 10 wk. The melting thermo-
grams of PKS and HPKS show polymorphic transforma-
tions at 20 and 25 °C, respectively, from the unstable form
to a more stable β’ form. The polymorphic forms for the re-
spective peaks shown in the DSC thermograms were not
determined.
4 Conclusions
The melting and crystallisation behaviour of PKO, PKOO
and PKS and their hydrogenated samples can be evalu-
ated from their TAG compositions. Two exotherms ob-
served for PKO, PKOO and the hydrogenated samples
reflect the higher and lower melting TAGs. In the hydro-
genated samples the higher melting TAGs are ECN 48 to
ECN 52 and for the natural PKO and its fractions the
TAGs are ECN 40 to ECN 44. The strong β’ polymorphs
shown for all samples suggest that these TAGs or their
combinations are strongly β’ in nature.
Acknowledgements
The authors thank the director general, MPOB for permis-
sion to publish this paper and Dr Chong Chiew Let and his
staff for kind assistance in NMR and DSC analyses.
References
[1] W. L. Siew, K. G. Berger: Malaysian palm kernel oil: Chemi-
cal and physical characteristics. PORIM Technology 6
(1986).
734 Wai Lin Siew
[2] T. S. Tang, C. L. Chong, M. S. A. Yusoff: Malaysian palm ker-
nel stearin, palm olein and hydrogenated products. PORIM
Technology 16 (1995).
[3] J. A. Bezard: The component triacylglycerols of palm kernel
oil. Lipids 6 (1971) 630–634.
[4] J. A. Bezard, J. P. Moretain, M. Bugaut: The saturated sn-2-
triacylglycerols of palm kernel oil. Fette Seifen Anstr. Mittel
79 (1977) 399–407.
[5] J. A. Cornelius: Palm kernel and palm kernel oil. Prog. Chem
Fats and other Lipids 15 (1977) 5–24.
Eur. J. Lipid Sci. Technol. 103 (2001) 729–734
[6] Malaysian Standard MS 252: Part 21: 1994 Animal and veg-
etable fats and oils: Rapid method for the preparation of
methyl esters of fatty acids.
[7] W. L. Siew, W. L. Ng: Characterisation of crystals in palm
olein. J. Sci Food Agric. 70 (1996) 212–216.
[8] J. B. Rossel: Fractionation of palm kernel oil. J Am. Oil
Chem. Soc. 62 (1985) 385–390.
[Received: February 20, 2001; accepted: July 24, 2001]