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Palm Oil Crystallisation: A Review

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 REVIEW ARTICLES

Journal of Oil Palm Research Vol. 27 (2) June 2015 p. 97-106

PALM OIL CRYSTALLISATION: A REVIEW

ZALIHA OMAR*; ELINA HISHAMUDDIN*; MISKANDAR MAT SAHRI*; SITI HAZIRAH MOHAMAD
FAUZI*; NOOR LIDA HABI MAT DIAN*; MUHAMMAD RODDY RAMLI* and NORIZZAH ABD RASHID**

Abstract
Palm oil is one of the most traded oils in the world oils and fats market for food applications. This has led to
many studies on aspects such as nutritional, food design and formulation, and its crystallisation behaviour.
Palm oil crystallisation behaviour has important implications in the manufacture of food products such
as margarines and shortenings where physical properties depend largely on the fat crystals. This article
reviews the effects of chemical composition (fatty acid and mono-, di- and tri-acylglycerol composition),
crystallisation conditions and the presence of additives on the crystallisation of palm oil. In addition, the
crystallisation kinetics, thermal properties, polymorphism and recrystallisation of palm oil will also be
discussed.

Keywords: crystallisation, palm oil, fat crystals, polymorphism, thermal properties.

Date received: 12 June 2014; Sent for revision: 13 July 2014; Received in final form: 28 November 2014; Accepted: 18 February 2015.

Introduction in many diverse areas with both edible and non-

edible usages.
Palm oil is derived from the outer pulp (mesocarp) of Fractionation process is necessary to meet
the fruits of oil palm, Elaeis guineensis. The mesocarp specific uses, which separates the palm oil into
contains almost 49% palm oil, and the kernel consists fractions with different melting properties. For
of about 50% palm kernel oil (Pantzaris, 2000). edible purposes, palm oil and its fractions are used
They have many applications with new potential in the manufacturing of margarines, vanaspati,
uses currently being explored. Palm oil is 50% shortening, spreads, ice creams, whipped topping,
unsaturated and contains mainly oleic (C18:1) and mayonnaise and salad dressing, filled milk, coffee
palmitic (C16:0) acids with an iodine value of about creamer, cheese and coconut milk substitutes
52 (Wahid et al., 2011). (Miskandar et al., 2011). The oil is also very suitable
In 2013, the world production of palm oil for commercial deep frying because of its good non-
reached 58.4 million tonnes from 30 million foaming property and oxidative stability (Pantzaris,
tonnes in 2004 (USDA, 2014). This accounted for 2000; Ismail, 2005; Ahmad Tarmizi and Siew, 2008;
more than 34% of the world production of major Ahmad Tarmizi and Ismail, 2008; 2014). For non-
vegetable oils in 2013. The remarkable increase in edible purposes, palm oil is mainly used in the soap
palm oil production in the last decade signifies its industry and fatty acids manufacturing.
importance as one of the world’s main commodity
crops. Various modification processes such as FACTORS AFFECTING THE PALM OIL
blending, hydrogenation, fractional crystallisation CRYSTALLISATION
and interesterification allow palm oil to be applied

* Malaysian Palm Oil Board,

Fatty Acid and Triacylglycerol Composition of
6 Persiaran Institusi, Bandar Baru Bangi, Palm Oil
43000 Kajang, Selangor, Malaysia.
E-mail: elina@mpob.gov.my Fatty acids are the starting points in lipid

** Faculty of Applied Sciences, Universiti Teknologi MARA,
structure. They are the main components that form
40450 Shah Alam, Selangor, Malaysia. triacylglycerols (TAG), monoacylglycerols (MAG)

97
Journal of Oil Palm Research 27 (2) (JUNE 2015)

and diacylglycerols (DAG) in oils and fats. There are TABLE 2. TRIACYLGLYCEROL COMPOSITION OF PALM
OIL
nine major fatty acids present in palm oil. Palmitic
acid and oleic acid account for about 44% and 40% of
the total fatty acid content of palm oil, respectively Triacylglycerol Weight (%)
(Wahid et al., 2011). Other fatty acid constituents of OLL 0.6
palm oil include myristic, stearic and linoleic acids PLL 1.9
with trace amounts of lauric, palmitoleic, linolenic MLP 0.9
and arachidic acids as tabulated in Table 1.
OLO 2.0
PLO 10.8
TABLE 1. FATTY ACID COMPOSITION OF PALM OIL
PLP 8.9

Fatty acid Carbon number Amount (wt%) MPP 0.7

Lauric 12:0 0.0 - 0.4 OOO 3.9

Myristic 14:0 0.5 - 2.0 POO 24.3

Palmitic 16:0 40.1 - 47.5 POP 27.7

Palmitoleic 16:1 0.0 PPP 5.1

Stearic 18:0 3.5 - 6.0 SOO 2.1

Oleic 18:1 36.0 - 44.0 POS 4.6

Linoleic 18:2 6.5 - 12.0 PPS 0.8

Linolenic 18:3 0.0 - 0.5 SOS 0.3

Arachidic 20:0 0.0 - 1.0 *Note: M = myristic; P = palmitic; S = stearic; O = oleic;

L = linoleic.
Source: Wahid et al. (2011). Source: Adapted from Hishamuddin (2009).

Fats and oils are mainly mixtures of TAG and relationship between TAG composition, melting
palm oil consists of about 93% - 95% TAG. Palm properties and polymorphic behaviour of palm oil
oil also contains appreciable amounts of DAG and fractions after analysing a series of palm oil,
(5% - 8%) and free fatty acids, which can have a solid and liquid fractions (stearins, mid fractions,
substantial effect on its physical properties. The two oleins and superoleins). Three major endotherms
dominant TAG are POP (28%) and POO (24%) with namely low-melting, high-melting and very high-
significant amounts of PLO, PLP, PPP (5%), POS and melting peaks (LMP, HMP and VHMP) were
OOO. The remaining TAG are present at less than detected in the differential scanning calorimetry
3% (Hishamuddin, 2009). Table 2 tabulates the TAG (DSC) melting profiles (5°C min-1). The VHMP
composition of palm oil (positional isomers are not was only recorded for palm stearin which contains
separated). more trisaturated (SSS) components. The HMP
Crystallisation of palm oil has been extensively contribution was weak for palm olein and was not
investigated due to its importance in controlling observed for palm super oleins. The LMP is usually
product quality. Crystallisation can be generally made up of triunsaturated (UUU), diunsaturated-
classified into two steps: nucleation, followed by saturated (SUU) and disaturated-unsaturated (SUS)
crystal growth. Before nucleation occurs, the solution components. The SUS components were reported to
must be under supercooling or supersaturation be present in both LMP and HMP. The HMP is also
conditions. The driving force for a supercooled made up of some SSS, except for palm oleins and
melt to undergo crystallisation is determined by super oleins.
the degree of supercooling (the difference between DAG have also been shown to inhibit the
the process value and the slip melting point (SMP) nucleation process and retard crystal growth rates
(Ghostra et al., 2002). Palm oil crystallisation is known of palm oil TAG, particularly of the saturated
to be a rather complex process (Jacobsberg and Oh, dipamitoylglycerol species. This behaviour was
1976; Kawamura, 1979; 1980; van Putte and Bakker, more effective at concentrations higher than 5%
1987; Berger, 1989) due to the slow crystallisation and at lower degrees of supercooling (Siew and
behaviour that leads to post-hardening (Timms, Ng, 1999). Saberi et al. (2011) studied the effects of
1984; Duns, 1985; Ward, 1998; Zaliha et al., 2004; different concentrations (2%, 5%, 10%, 30% and 50%
2005; Hishamuddin et al., 2011). w/w) of palm-based diacylglycerols (PB-DAG) on
Chemical composition such as TAG, DAG, free the crystallisation kinetics of palm oil. The isothermal
fatty acid (FFA) and additives has been shown to crystallisation properties of palm oil were dependent
influence palm oil crystallisation. Braipson-Danthine on the concentration of PB-DAG. Addition of 5%
and Gibon (2007) reported that there was a clear PB-DAG decreased significantly (p<0.05) nucleation

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 PALM OIL CRYSTALLISATION: A REVIEW

rate, crystallisation rate and crystal growth mode temperature cycling were studied by Miskandar et al.
of palm oil (PO). On the other hand, the addition (2006). This study showed that the emulsifiers could
of 30% and 50% of PB-DAG increased significantly be useful agents for controlling crystallisation in
(p<0.05) nucleation rate, crystallisation rate and fluidised palm oil formulations. In 2007, Miskandar
crystal growth mode of PO. A recent study by de et al. determined the effect of STS and soya lecithin on
Oliveira et al. (2014) also indicated that naturally blends of PO and palm olein by slow crystallisation
occurring DAG in PO (6% - 8.5%) interfere with the (0.7°C min-1 for 32 min). Results indicated that STS
nucleation times and crystallisation rate of PO. acted as a crystal inhibitor (0.06% - 0.09%), while at
Siew and Ng (1996) investigated the effect of 0.03%, it was a crystal promoter. Slow crystallisation
different types of DAG on palm olein crystallisation process of the blends with 0.03% lecithin produced
and concluded that DAG have different effects on homogeneous crystals with low solid fat content
the crystallisation behaviour. The enhancing or (SFC) and viscosity for fluidised products.
retarding role of crystallisation depends on the
type of DAG as well as on the oil composition. Polymorphism
The crystallisation time of palm olein was reduced
rapidly with the addition of palm diacylglycerols. Polymorphism and phase behaviour have by far
Of the palm DAG, dipalmitoylglycerol in particular, the greatest influence on PO crystallisation. These
the 1, 3-isomer, was more effective in causing rapid two phenomena are closely linked together and
crystallisation of palm olein. On the other hand, a description of one of them is usually incomplete
the palmitoyloleoylglycerol appeared to have a without the other. Polymorphism is the ability of
retardation effect on the crystallisation time. compounds to crystallise in different crystalline
Basso et al. (2010) characterised the changes structures. They result from the stereochemical
induced in the crystallisation of PO by the addition configuration of the molecules of the crystal
of two different levels of tripalmitin and two which exhibits different orientations of the zigzag
different types of MAG. The addition of MAG led arrangement of the glyceridic chains (Jacobsberg
to the formation of a large number of crystallisation and Oh, 1976). The phase behaviour of the different
nuclei without changing the final solids content, TAG in the solid state usually affects the efficiency
accelerating the process of crystal formation, leading of the crystallisation process (Timms, 1984). Palm oil
to the formation of smaller crystals than those in also forms mixed crystals or solid solutions (Timms,
the refined palm oil. Higher levels of tripalmitin 1984; Berger, 1989). This tendency is ascribed partly to
produced larger crystals, reducing the induction the relatively high amount of symmetric monooleic
period and resulted in a higher level of solids at the disaturated TAG such as POP (Jacobsberg and Oh,
end of the crystallisation period. A recent study by 1976). It is also strongly enhanced by the presence
Verstringe et al. (2013; 2014) reported that the addition of asymmetric TAG such as partial glycerides as
of saturated MAG caused an earlier onset on both these act in increasing the α-lifetime and decreasing
isothermal and non-isothermal crystallisation of PO. the SFC (Knoester et al., 1972; Persmark et al., 1976;
A study on palm oil and palm stearin blend Berger, 2001; De Clercq et al., 2012). Intersolubility is
systems by Saadi et al. (2012) indicated that known as the mutual solubility of a TAG in another
high melting TAG namely, PPO/POP was the leading to the formation of solid solutions (Timms,
dominant component responsible for primary 1994). The formation of a solid solution is highly
crystal formations and aggregation. While Miura dependent on the chemical composition and the
and Konishi (2001) reported that POP was one the crystal structure of different TAG within a certain
major TAG existed in granular crystals of margarine mixture.
produced by an excess of palm oil. POP and POO The polymorphism and phase behaviour of PO
were found to be immiscible with each other, and its fractions have been reviewed to a certain
resulting in POP crystals surrounded by POO. extent (Persmark et al., 1976; Timms, 1984; Berger,
Additives also have been shown to play 1989; Braipson-Danthine and Gibon, 2007). The
some inhibitory effects in palm oil crystallisation. four polymorphic forms which have been well-
Kawamura (1980) investigated the retardation established for palm oil are the sub- α, α, βʹ and β. It
effect of sorbitan esters on the crystal polymorphic is well-known that PO is βʹ stable and of this type,
transformation in palm oil and found that sorbitan the stable sub-polymorph being β1ʹ. Persmark et al.
tristearate was the most effective in retarding the (1976) conducted an X-ray diffraction study on the
transformation from the unstable α and β´ crystal phase behaviour of PO and found the existence of
forms to the stable β at concentrations and heating three polymorphs, namely α, β1ʹ and β2ʹ. Utilising
rates greater than 1.5% and 5 K min-1, respectively. the diffraction-pattern-temperature (DPT) camera,
The effects of sorbitan tristearate (STS) and they observed X-ray diffraction patterns of the lower
soya lecithin on PO and on palm olein blends with melting βʹ, β2ʹ prevailing at subzero temperatures
low SMP for fluidised palm oil formulation by below -10°C upon rapid cooling. They further

99
Journal of Oil Palm Research 27 (2) (JUNE 2015)

discovered a mixture of α and β1ʹ polymorphs The most comprehensive comparative study on
existing between -10°C and -5°C when the oil was the polymorphic behaviour of PO and its fractions
further heated slowly. At 7°C, the β1ʹ form was found was carried out by Braipson-Danthine and Gibon
to dominate. (2007). They examined the polymorphic behaviour
In another study, Jacobsberg and Oh (1976) of 24 samples of PO and its solid and liquid fractions,
revealed that fast cooling of PO produces a crystals, which included oleins, superoleins, stearins and mid
which are unstable, and when provided with fractions using DSC and powder XRD spectroscopy.
sufficient energy they are transformed into βʹ and b They observed that for PO, palm stearin, and mid
polymorphic forms. The easiest way to obtain these fractions, low melting peak components comprising
transitions is to keep the crystals at temperature mainly UUU, SUU and SUS TAG exhibited sub-a2,
slightly below the melting point of the required sub-a1 and a polymorphs in the DSC melting curves.
polymorphic form. Oh (1989) in his study indicated The high melting peaks which contained SUS and
that PO when crystallised from melt showed a SSS components were found to crystallise in βʹ2, βʹ1
polymorphic form of a single short spacing band and partially in β. Polymorphism for palm oleins and
at ca. 0.415 nm; βʹ of two short spacing at ca. 0.43 super oleins were found to be in the sub-a2, sub-a1,
nm and 0.38 nm, also sometimes at 0.40 nm medium a and βʹ2 for lower melting peaks (UUU, SUU and
or weak short spacing; and b form of a strong short SUS) while βʹ1 was observed for high melting peaks
spacing at ca. 0.45 nm or 0.46 nm with two or three only in palm oleins due to the higher content of SUS
strong or medium bands at 0.39, 0.38 and 0.37. TAG.
In a separate study carried out by Deffense Zaliha and Norizzah (2012) investigated the
and Tirtiaux (1989), β type crystals were observed physico-chemical properties of binary blends of PO
when PO was maintained or cooled slowly around products with deodorised cocoa butter (DCB) at
temperatures between 40°C and 45°C. These types levels ranging from 10% - 90% (w/w). The addition
of crystals were thought to originate from handling of DCB at all concentration with cocoa butter
and storage, thus necessitating melting the oil at equivalent (CBE) resulted in the formation of a
high temperatures to destroy all crystal memory strong β in a mixture of β+β´ polymorphic forms. On
upon proceeding with crystallisation. the other hand, when 10% - 20% palm mid fraction
Mazzanti et al. (2005) studied the influence (PMF) and CBE were mixed, a strong β´ in a mixture
of shear rates on phase transitions during PO of β+β´ polymorphic forms was obtained.
crystallisation at 17°C and 22°C. Applying different
shear rates from 0 to 2880 s-1, they discovered that Crystallisation Kinetics
the acceleration of the phase transition from α to βʹ
increased with increasing shear at both temperatures The kinetics of fat crystallisation is important in
of study. A simple model was developed in which controlling operations in the food industry in order
they describe that initially, the α phase nucleates to produce products of desired quality (Metin and
from the melt followed by nucleation of the βʹ phase Hartel, 1998; Himawan et al., 2006; Walstra, 1998).
on the α crystallites. They concluded that under Crystallisation kinetics on PO has been studied to
shear, small crystallites are formed from the α nuclei improve its processing and storage condition (Ng,
which easily transform to the βʹ form. A lower shear 1990; Ng and Oh, 1994; van Putte and Bakker, 1987;
retards the nucleation of the βʹ crystals since this Chen et al., 2002). Van Putte and Bakker (1987)
causes the α nuclei to aggregate and provide fewer investigated the kinetics of PO crystallisation and
nucleation sites per unit volume for the βʹ form to showed that PO crystallised in the βʹ-modification
nucleate. when cooled to between 21°C and 29°C and into the
In a study conducted by Chong et al. (2007) using β-modification when crystallised between 34°C and
coupled time-resolved synchrotron X-ray diffraction 46°C under non-stirring conditions. The amount
(XRDT) with high sensitivity DSC found that PO of SSS components present in the washed filtrate
in its crude form crystallises into two different was more than 55% for the former temperature
β polymorphs of double and triple chain length conditions and exceeded 75% for the latter. When
stacking when a cooling rate of 0.1°C min-1 was stirring condition was applied, PO crystals formed
applied. This was evident at temperatures below agglomerates of the β´ type consisting of spherulites
27°C and was revealed through the XRD peaks which with numerous needles growing from the centre.
displayed two β subcells developing successfully. Yap et al. (1989) used DSC and pNMR to
They also suggested that PO is composed of a three- estimate crystallisation kinetics of PO and modified
phase system involving a βʹ, a β and a liquid phase palm oils. DSC was found to be more sensitive and
(two solids and one liquid) rather than a single solid could differentiate between crystallisation during
and single liquid system due to the coexistence of cooling and isothermal conditions. They reported
stable βʹ plus β forms at high temperatures. that hydrogenated palm oils crystallised quickly

100
 PALM OIL CRYSTALLISATION: A REVIEW

and completely when cooled from 60°C to 20°C ENDO

RBD PALM OIL 17.7
while PO and fractionated palm stearin continued 92 20.5
36.9 47.2
Melting -0.6
to crystallise when held isothermally at 20°C. 54.0
Zhang et al. (2013) compared the thermal

Heat flow (wg)

behaviour of palm stearin (PS) and palm olein
29.5

(POo) by using DSC, the isothermal crystallisation Crystallisation

kinetics by pNMR and isothermal microstructure
by polarised light microscopy (PLM). Both PS and -16.5 32.8

POo had quite similar exotherms but PS had sharper 5.9 28.5
exotherms with respect to isothermal crystallisation. 12.4

The Avrami exponent (n) value in Avrami equation EXO

increased when the crystallisation temperature rose -40 -20 0 20 40 60
and the n values for both PS and POo were almost Temperature (oC)
the same at the same crystallisation temperature.
This could be due to the same kind of fatty acids Figure 1. Differential scanning calorimetry crystallisation and melting
thermogram of palm oil (adapted from Zaliha et al., 2004).
present in both PS and POo. Hence, both the PS
and POo had the same mechanism of nucleation
and crystal growth. However, PS showed different which comprises mainly of trisaturated TAG such
crystal morphology compared to POo at the same as PPP, PPS and MPP. These higher melting TAG
crystallisation temperature. start to crystallise at around 28.5°C. The other group
Abd Rashid et al. (2012) investigated the crystallising at lower temperatures mainly consists
isothermal crystallisation of PS, palm kernel olein of lower melting TAG which start crystallising at
and their blends at 10°C, 15°C and 20°C using DSC. around 12.4°C. The melting thermogram also shows
Based on the n obtained (Avrami, 1939; 1940; 1941) two broad peaks in the endotherm. These depict
PS and palm kernel olein have different nucleation the same two groups of TAG which have different
and crystallisation mechanisms. The suggested melting temperatures. The first endothermic peak
mechanism for palm kernel olein was high represents the lower melting TAG completely
nucleation rate at the beginning of crystallisation, melted at 29.5°C while the second broader peak
which decreased with time, and plate-like growth signifies the higher melting TAG melting between
(n = 2). On the other hand, the mechanism for PS was 36.9°C to 54.0°C. The presence of these two types of
instantaneous heterogeneous nucleation followed TAG groups is apparent when the oil forms a semi-
by spherulitic growth (n = 3). For blends of PS and solid solution when left at room temperature.
palm kernel olein, the mechanisms of crystallisation Busfield and Proschogo (1990) investigated
were 2 and 3 depending on the composition of the the thermal properties of PS and observed several
blends and crystallisation temperatures. thermal transitions within their DSC profiles.
The stearin melted as almost two independent
Thermal Properties components in separate temperature ranges. The
high-melting component, consisting mainly of
DSC is a useful tool for studying crystallisation POP (33%), PPP (≈15%), POS (4%) and PPS (2%),
of oils and fats (as well as their melting). Oh and crystallised initially in an α crystal form which
Berger (1983) proposed a routine procedure to char- rearranged on tempering successively to β′ and β
acterise the crystallisation and melting behaviours crystal forms. The lower-melting component was
of PO using DSC. The procedure requires PO sample mainly POO (14% overall), PLP (13% overall) and
to be melted at 80°C for 10 min, cooled to -50°C at SOO (1% overall). It crystallised initially in a sub
10°C min-1, held at -50°C for 10 min and finally heat- α form which rearranged to β′ when tempered at
ed to 80°C at 10°C min-1 for cooling thermogram. For 0°C, and to the β crystal form when tempered at
melting thermogram, the sample was held at -40°C 10°C. The liquid phase contained mainly PLO (8%
for 10 min before heating up to 80°C at a heating rate overall), OOO (6% overall), PLL (4% overall) and
of 5°C min-1. LOO (1% overall).
The crystallisation of PO was characterised Mihara et al. (2007) examined how PPP affected
by two easily distinguishable peak areas in the the crystallisation of POP and POO by DSC and
exotherms as depicted in Figure 1 (Kawamura, XRD on PPP/POP and PPP/POO mixtures. High
1979; 1980; Ng and Oh, 1994; Ng, 1990; Zaliha et al., and low temperature peaks were noted to appear on
2004; Braipson-Danthine and Gibon, 2007). These the DSC crystallisation curve for both mixtures. The
two peaks correspond to two different groups of high temperature peak was possibly due to PPP, and
TAG crystallising at different temperatures. One the low temperature peak corresponded to POP or
group is designated as the higher melting TAG POO. DSC isothermal analysis revealed that the rate

101
Journal of Oil Palm Research 27 (2) (JUNE 2015)

of crystal growth of either mixture exceeded that of hence the energy consumed during fractionation.
pure POP or POO, crystal mixture structure also was The fractionated oleins exhibited better cloud point
complicated compared to the pure form. (between 7°C - 8°C). The crystal size was observed
to be homogeneous with majority at 100-300 µm
without posing any filtration difficulty.
FRACTIONATION

PO has a characteristic that makes it a versatile RECRYSTALLISATION OR POST-

ingredient in food products. By simple fractionation CRYSTALLISATION
process, PO can be resolved into a liquid, a solid and
intermediate fractionated palm olein (also known The post-crystallisation in PO-based products has
as palm mid fraction) and various grades of palm been ascribed to its slow crystallisation behaviour
stearin (Zaliha et al., 2004). Both olein and stearin hence leads to processing difficulties. Post-
have applications in certain margarine formulations. crystallisation of PO increases the hardness of
For example, olein is a useful source of liquid finished products several weeks after manufacturing.
oils, which is required in certain soft margarine According to Timms (1984) and Duns (1985), the
formulations while stearin is frequently used as a post-crystallisation might be due either to the
hard stock for palm-based margarine and vegetable transformation of b’ to b form or crystal networking
shortenings. after crystallisation. The transformation of b’ to b
The fractionation process has been extensively polymorph leads to coarse crystals, causing product
reviewed by several authors in the last decade graininess and unacceptable to the consumers. Ward
(Gibon and Tirtiaux, 2002; Timms, 2005, Kellens et (1998) reported that there is always a tendency for
al., 2007). The principle of fractionation is the partial the fat to be transformed to the most stable crystal
crystallisation of the oil followed by separation of form during storage if the stable crystal form has not
the crystallised phase from the remaining liquor by been achieved in the processing.
various filtration techniques. This process is largely Timms (1990) reported that post-hardening
based on the differences in the melting points of was caused by an increased interlocking of the
the constituent TAG in an oil or fat. The resulting crystals in addition to an increase in the solid phase.
products are a liquid phase and a solid phase which He also reported that recrystallisation or post-
are termed as olein and stearin, respectively. hardening process was due to the smallness of the
PO is the most fractionated oil worldwide, and crystals. When PO fractions are used in products,
the majority is fractionated via the dry fractionation a slow crystallisation or recrystallisation can take
process. This process has been reviewed as the place after manufacture. During production,
cheapest and most natural modification process cooling conditions may be applied that do not
compared to hydrogenation and interesterification lead to the thermodynamic equilibrium between
(Kellens, 1996; Deffense, 1998). This fractionation the composition of the solid and the liquid phases.
technique has the advantage of being a pure Recrystallisation can occur to form a new solid
modification process without the use of any phase as thermodynamic equilibrium is approached
chemicals or additives compared to the detergent (Smith et al., 1994).
and solvent routes. Hence, it is preferable over other Fat crystals can sinter, or in other words, link
fractionation processes due to the low processing together through bridges formed, apparently by
costs involved and the higher yield of liquid olein TAG with melting points between those of the
obtained, which is comparable to the solvent process. existing solid and liquid phases (Johansson et al.,
Zaliha et al. (2004) studied the crystallisation 1995). Thus b’ crystals are bridged by b’ solid and
behaviour of PO in relation to the dry fractionation b crystals by b solid. deMan and deMan (2001)
process and revealed that the physico-chemical have reported that temperature treatment of fats
properties of the fractions were affected by the can have a profound influence on the b’ polymorph
crystallisation temperatures. In another study, using stability in fats. The stable b’ polymorph in fats
polarised microscopy (PLM) and XRD, Chen et al. may transform wholly or partially to the b form
(2002) observed spherical crystals formed from the when subjected to temperature fluctuations during
first fraction were α form, while needle-like crystals storage. It is customary to temper shortenings for
nucleated later from the second fraction were β and several days, usually at a temperature above which
βʹ during a two-stage dry fractionation process of they are processed, but not higher than 28°C. They
PO below 295K. suggested that ideal tempering should not lead to
Kuriyama et al. (2011) improved the dry the formation of b crystals.
fractionation of PO using a series of Generally The crystal networking can be quantified by
Regarded as Safe (GRAS) Polyglycerol Fatty fractal dimension via rheological and image analysis
Acid Esters (PGE). This study revealed that the as suggested by Marangoni and Narine (2002) and
hydrophobic PGE reduced the fractionation time and Marangoni (2005). The quantification of the spatial

102
 PALM OIL CRYSTALLISATION: A REVIEW

distribution of microstructural elements within the olein and special quality palm olein. J. Amer. Oil
microstructures in fat-crystal networks has been Chem. Soc., 85 (3): 245-251. DOI: 10.1007/s11746-007-
studied using the relationship of the shear elastic 1184-8.
modulus (G’) to the volume fraction of solid fat (F)
via the mass fractal dimension (D) of the network. AHMAD TARMIZI, A H and ISMAIL (2014). Use
A study on the effects of storage temperatures of pilot plant scale continuous fryer to simulate
and time on the physico-chemical properties of industrial production of potato chips: thermal
refined bleached deodorised palm oil by Zaliha et properties of palm olein blends under continuous
al. (2004; 2005; 2006) showed that post-hardening frying conditions. Food Science & Nutrition, 2(1): 28-
had occurred upon storage without transformation 38. DOI: 10.1002/FSN3.76.
of polymorphic form from b’ to b. Hence, the post-
hardening phenomenon could be due to crystal AHMAD TARMIZI, A H and SIEW, W L (2008).
networking after crystallisation process. The fractal Quality assessment of palm products upon prolonged
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image analysis can be a good indicator for the http://dx.doi.org/10.5650/jos.57.639rg./10.5650/
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networks for palm-based products during storage.
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The polymorphism, phase behaviour and chemical
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ACKNOWLEDGEMENT 1185-1192. DOI: 10.1016/j.foodchem.2010.03.113.

The authors would like to thank the Director-General BERGER, K C (1989). Crystallisation behaviour
and the Director of Product Development and of palm oil. Proc. of the PORIM International Palm
Advisory Services (PDAS) of MPOB for permission Oil Development Conference, Module 3: Chemistry,
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to all PDAS staff for their assistance. The authors
would also like to acknowledge financial support BERGER, K G (2001). Palm Oil, Structured and
from the FRGS (FRGS/1/2013/SG01/UiTM/02/3) Modified Lipids (Gunstone, F D eds.). Marcel Dekker.
Grant MOHE, Malaysia. New York. p. 119-154.

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