EFFECTS OF EMULSIFIERS ON CRYSTAL BEHAVIOR OF PALM OIL BLENDS ON SLOW CRYSTALLIZATION

M.S. MISKANDAR1,2, Y.B. CHE MAN1,4, R. ABDUL RAHMAN1, I. NOR AINI2 and M.S.A. YUSOFF3 Department of Food Technology Faculty of Food Science and Technology Universiti Putra Malaysia 43400 UPM, Serdang, Selangor, D.E., Malaysia Malaysian Palm Oil Board No. 6 Persiaran Institusi Bandar Baru Bangi Kajang, Selangor, D. E., Malaysia Golden Hope Research Banting Selangor, Malaysia
Submitted for Publication April 13, 2006 Revised Received and Accepted July 20, 2006
3 2 1

ABSTRACT The effects of sorbitan tristearate (STS) and soy lecithin on blends of palm oil (PO) and olein by slow crystallization were studied. The blends of PO and olein were melted at 80C for 30 min and slowly cooled at a rate of 0.7C/min for 32 min and at 20 0.1C for 48 min. Nuclear magnetic resonance was used to measure the solid fat content (SFC) development. Crystallization without emulsier was inuenced by trisaturated and disaturated triacylglycerol content of PO manifesting signicant (P < 0.05) changes in SFC, crystal dispersion and viscosity, but emulsiers in the blends disturbed these behaviors. The reaction of lecithin was very selective and was determined that at 0.03%, it generally served as a crystal promoter, while at 0.060.09%, it was a crystal inhibitor. Viscosity was closely related to the crystal dispersion in the liquid. The blends had low viscosity with 0.03% lecithin, while blends with high trisaturate content had high viscosity with 0.06% lecithin. STS was generally a crystal inhibitor, although at various levels, it was a crystal promoter for the middle-range saturates. Slow crystallization process of PO and olein blends with 0.03% lecithin produced homogenous crystals with low SFC and viscosity for uidized products.
4

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Journal of Food Lipids 14 (2007) 118. All Rights Reserved. 2007, The Author(s) Journal compilation 2007, Blackwell Publishing

M.S. MISKANDAR ET AL.

INTRODUCTION The physical state at which hard fat crystallizes is important (OBrien 2000). However, it is not an ultimate effect of the current crystallization conditions alone, but depends on the entire history of the crystallization process (Blaurock 1999; Jahaniaval et al. 2000; Miskandar et al. 2002). Hot oil that is rapidly cooled to a temperature below a melting point would most probably crystallize in a form followed by the formation of b and b crystals (Blaurock 1999). However, on slow cooling, b crystal would rst form followed by the a crystal surrounding the b crystal that acts as nuclei for crystallization (Blaurock 1999). Besides various temperature conditions, emulsier with different hydrophobic properties would also affect fat properties by accelerating or retarding crystallization and polymorphic transformation (Garti 2002; Miskandar et al. 2002). Emulsiers are important ingredients in bakery shortening, although only a small amount is used, and typically at <0.5% can contribute to signicant product qualities (Stauffer 1996). According to Stauffer (1996), Nash and Lawrence (1972) and Chrysam (1985), emulsiers in food products are multifunctional and contribute to the nal product properties. For the purpose of certain functionalities, uid shortening can act as the carrier for these emulsiers and later becomes an ingredient for the production of food products such as bread and cake, dough strengtheners and antistaling agent (OBrien 2000). Emulsiers are associated with triacylglycerol (TAG) by their hydrophobic groups (fatty acid moieties), specically the acylacyl interaction (Katsuragi 1999). The acyl group of emulsiers determines its functionality with respect to the TAG. The major effects of emulsiers on fat crystal occur in the area of fat nucleation, transformation of polymorphism and crystal growth. These effects alter the physical properties of fat such as crystal size, solid fat content (SFC) and crystal arrangements. The question whether an emulsier will promote or retard crystallization in oils and fats is very subjective and depends on various factors. However, Katsuragi (1999) suggested that similar acyl groups promote crystallization, while different acyl groups retard crystal development. Seeding effect could be another phenomenon on the effect of emulsiers in uid shortening by promoting crystallization (OBrien 2000). Sorbitan tristearate (STS) is a hydrophobic emulsier with a hydrophobic lipophilic balance (HLB) value of 2.1 (Kamel 1997). The molecular structure of STS is very similar to that of TAG, thus enabling STS to cocrystallize with fats and form solid solutions (Krog and Last 1995). Lecithin, on the other hand, is a complex phospholipid that has hydrophilic and hydrophobic properties, with an HLB of 3.5 (OBrien 2000). The main function of phosphatide is to emulsify fats. The long-chain fatty acid moieties that contribute the

EFFECTS OF EMULSIFIERS ON PO

hydrophobic property are counterbalanced by the polar or hydrophilic properties of the phosphate moiety. Emulsiers can also act as wetting agents in uid shortening systems by reducing the interfacial tension between the liquid and solid surfaces that cause the liquid to spread more evenly over surfaces. As agglomeration of crystal is not desired for a stable uid shortening, emulsiers can be used to control the fat particle coagulation (OBrien 2000). The aim of this study was to determine the crystallization properties of 11 different blends of palm oil (PO) and palm olein using STS and lecithin.

MATERIALS AND METHODS Materials Rened, bleached and deodorized (RBD) PO and palm olein were obtained from the Malaysian Palm Oil Board, Malaysia. STS was from Danisco Malaysia Sdn. Bhd., Penang, Malaysia, and lecithin was bought from Euro Chemopharma Sdn. Bhd., Shah Alam, Selangor, Malaysia. Physical Analyses RBD PO and palm olein were melted at 80C in a Memmert drying oven (model 854 UL 80; Memmert GmbH, Schwabach, Germany). STS and lecithin were dissolved in PO before mixing in the blends to assist homogeneity. Eleven blends of PO and palm olein were prepared in three replications in the ratios of 100:0, 90:10, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 20:80, 10:90 and 0:100 (w/w), and these were represented by the letters A, B, C, D, E, F, G, H, J, K and L, where A and L were 100% PO and palm olein, respectively. The experimental preparation was for the study of the effects of STS and lecithin at 0, 0.03, 0.06 and 0.09% by slow crystallization. Each sample was lled in nuclear magnetic resonance (NMR) tube of 8-mm diameter to a height of 30 mm for SFC measurement and tall-formed beaker (69-mm internal diameter, 130-mm height) to a height of 45 mm for viscosity tests. The tubes and beakers were placed in the water bath at 80C for 30 min to destroy all the crystal memory (De Man et al. 1989). SFC measurement took an average of 2.5 s, while viscosity measurement needed 35 s per sample (included in the time was sample preparation and measurement). The rest of the tubes and beakers were immediately transferred into the cooling bath at crystallization temperature (Tc) of 20C for crystallization time (Tm) of 80 min (cycle 1). The average time for the temperature to drop from 80 to 20C was 32.08 2.0 min (0.70C/min). The SFC at the end of the study was determined by pulse NMR (model NMS120, Minispec Bruker, Rheinstetten, Silberstreifen, Germany, with refer-

M.S. MISKANDAR ET AL.

ence samples of triolein and tristearin also in NMR tubes). Previous studies had shown that the crystallization Tc 20C for Tm 80 min was sufcient for full crystallization of PO: olein blends with 50% and more PO. The viscosity test was carried out by a Brookeld digital viscometer (model DV11, Brookeld Engineering Laboratories, Inc., Stoughton, MA) using a speed of 50 rpm for 25 s. The viscosity of the samples in centipoises was taken at the end of each tempering session. Microscopic examination for crystal distribution was measured by placing a drop of the tempered samples, from the same sample set previously mentioned, on a glass slide. A glass cover slip was placed on top of the sample, and the sample was immediately viewed under a polarized microscope (Olympus model BH-2, Olympus Corporation, Tokyo, Japan) attached to a video color camera. Leica (Leica Q500mc Qwin vol 0.02; Leica Cambridge Ltd, Cambridge, U.K.) for windows was used to analyze the images. TAG composition was determined by high-performance liquid chromatography according to the American Oil Chemist Society (AOCS 1989) method. The mobile phase used was acetone/acetonitrile (75:25, v/v). The sample was diluted in acetone to make up to 10% sample concentration. A volume of 10 mL was injected into a Waters C18 column (3.9 300.0 mm). The oven temperature was set at 35C, and the ow rate of the solvent was 1.5 mL/min. All sample determinations were carried out in duplicate. Statistical Analysis Analysis of variance at 95% condence level and multiple comparisons by Duncan was determined in statistical software package SPSS for Windows version 11.5. Arrangement of data for the statistical analysis was done in Microsoft Excel 2000 (Microsoft Corporation, Redmond, WA).

RESULTS AND DISCUSSION Crystallization of Fat Blend without Emulsiers When blends of PO and olein were slowly cooled from 80 to 20C, they underwent an average temperature change of 0.7C/min for the rst 33 min and 20.0 0.1C for the rest of 47 min (cycle 1), and created the condition of slow crystallization, even to blends with high trisaturate and disaturate TAGs (Miskandar et al. 2004). No signicant change on the temperature of the blend and water bath was recorded during the crystallization process. The change in the temperature was so slow, which caused slow crystallization, and any temperature changes due to crystallization were not signicant.

EFFECTS OF EMULSIFIERS ON PO

NMR was used to determine the crystallization properties of blends AL in this study owing to its ability for direct SFC measurement. Blaurock (1999), Buseld and Proshogo (1990) and Sugimoto et al. (2001) had shown that NMR provides an important tool for measuring fat crystallization. Albeit studies on fat crystallization had used X-ray diffraction and differential scanning calorimeter in trilaurin and tripalmitin crystallization, X-ray diffraction could not be used under the present experimental conditions because of the uid nature of most of the samples. Controlling the Tc is an important procedure in crystal development. The PO and olein blends in this study were tempered at Tc of 80C for Tm 30 min to provide an environment that was free of crystal memory and with the same starting history of 0% SFC. According to Blaurock (1999), crystallization history of the fat is considered an important step in fat product preparation, as it contributes to the nal crystal type. As the fat underwent cooling treatment for Tm 80 min, crystallization started to occur when the supercooling temperature was low enough for the highest melting crystals to create the nuclei for the centers of crystallization (Faur 1996; Ghotra et al. 2002). The greater the number of nuclei formed, the more rapid the whole bulk will crystallize. According to Blaurock (1999), in an instantaneous cooling of melted oil to a temperature below the melting of a type of crystal, the crystallization will be of that type of crystal. The cooling rate of 0.7C/min was a slow cooling process that initiated the high melting crystal types to crystallize rst, and because the cooling time was sufciently long, big crystal aggregates were formed. Slow crystallization at 0.7C/min for cooling time Tm 80 min in an earlier study had provided sufcient crystallization time for blends with high SSS (Miskandar et al. 2004). The condition was suitable for PO and olein blends with no emulsiers. However, the presence of emulsiers in these blends had inuenced their crystallization behaviors, as shown by change of SFC (Table 1). The SFC of blends of PO, from 0 (Blend L) to 100% (Blend A) ranged from 1.52 to 8.92%, in a nonlinear fashion as shown by the equation of SFC = -0.0202X3 + 0.03476X2 - 0.5313X% PO and R2 = 0.9846. As the content of PO was reduced to lower than 40%, the changes in SFC were not signicant (P > 0.05) because the blends with and without emulsiers at that level were practically in the liquid form. Crystallization behavior and solid fat development in blends with more than 40% PO, however, were dependent on the PO content, in agreement with ndings of Martini et al. (2002) on crystallization with high melting TAGs. Crystal Distribution without Emulsiers The formation of crystals at the end of cycle 1 showed that vigorous crystal development had occurred in blends without emulsiers as shown

TABLE 1. THE EFFECTS OF EMULSIFIERS ON THE SOLID FAT CONTENT OF PALM OIL AND OLEIN BLENDS BY CYCLE 1 Different emulsiers Lecithin (% w/w) 0.06 9.1 0.10Bg 8.5 0.07Bfg 7.8 0.06Aef 7.6 0.15BCe 6.1 0.44Ad 5.4 0.25ABd 3.5 0.40Ac 2.1 0.12CDb 0.1 0.01Aa 0.1 0.06Aa 0.1 0.02Aa 8.8 0.07Abi 8.3 0.13Abh 7.9 0.02Ag 7.3 0.10Abf 6.7 0.02Bce 6.3 0.09CDd 5.5 0.10Dc 2.5 0.21Deb 0.1 0.03Aa 0.1 0.01Aa 0.1 0.01Aa 9.8 0.14CDg 9.2 0.12CDf 8.1 0.23Abe 7.8 0.14Cde 6.7 0.69BCd 6.4 0.08CDd 4.7 0.35CDc 2.6 0.27DEb 0.1 0.02Aa 0.1 0.02Aa 0.1 0.02Aa 0.09 0.03 0.06 9.4 0.04BCg 8.8 0.22BCf 8.0 0.23Abe 7.5 0.09Bd 6.4 0.73Abc 5.9 0.23Cc 4.2 0.10BCb 0.1 0.00Aa 0.1 0.01Aa 0.1 0.01Aa 0.1 0.02Aa Sorbitan tristearate (% w/w) 0.09 9.4 0.16BCh 8.4 0.25Abg 7.7 0.13Af 7.0 0.19Ae 6.3 0.46Abd 5.2 0.12Abc 4.3 0.07BCb 0.1 0.01Aa 0.1 0.05Aa 0.1 0.07Aa 0.1 0.01Aa M.S. MISKANDAR ET AL.

Blend

0%

0.03

A B C D E F G H J K L

9.5 0.24Cj 9.2 0.23Di 8.0 0.22Abh 7.6 0.05BCg 6.4 0.57Abf 5.5 0.36Bbe 4.2 0.09BCd 1.6 0.15Bc 0.3 0.02Ab 0.3 0.12Ab 0.1 0.08Aa

9.7 0.14CDg 9.1 0.10DCf 8.4 0.15Bef 7.9 0.30Def 6.9 0.50Cd 6.7 0.25Dd 5.7 0.35Dc 2.6 0.74DEb 0.1 0.02Aa 0.1 0.01Aa 0.1 0.02Aa

Mean of three determinations SD. AE Mean with different letters within each row is signicantly different (P < 0.05). aj Mean with different letters within each column is signicantly different (P < 0.05). Cycle 1, treatment temperature and time of 80C (30 min) 20C (80 min).

EFFECTS OF EMULSIFIERS ON PO

50 m

A
FIG. 1. PHOTOMICROGRAPH OF CRYSTAL DISPERSION OF PALM OIL AND OLEIN BLEND ON SLOW CRYSTALLIZATION (10 10 MAGNIFICATION) A and B are Blends B and E, respectively, without emulsier.

under a polarized light microscope (PLM) in Fig. 1A,B. Complete crystallization had occurred in Blend B at Tm 80 min, as shown by the formation of mixtures of crystal sizes and shapes covering the whole range of the slide (Fig. 1A). The study showed that crystallization not assisted by stirring had created the conditions for crystallization that favored the nearest nuclei. The nuclei could be any foreign matter, the high melting TAGs or other already formed crystals. Blend E containing high oleic acid was a 1:1 mixture of PO and olein. As shown in Fig. 1B, ne crystals were distributed more evenly in this blend than in Blend B. The liquid TAGs (triunsaturated TAG and diunsaturated TAG) were in bigger quantity in Blend E, thus inuencing crystals to move more freely and creating more crystallization sites that improved the rate of crystallization. The condition had caused crystals to be nely formed and homogeneously distributed throughout the blend. As the ratio of the liquid TAGs in Blends G, H, I, J and K was increased, crystallization was not apparent under PLM. It showed that in cycle 1, Tc and Tm were insufcient to start crystallization and crystal development. Thus, Tc should be reduced and Tm increased. SFC, Viscosity and Crystal Behavior without Emulsier The solid fat development of Blends B and E followed the same trend as their viscosities and crystal dispersions in the absence of an emulsier. Crystal formations were greatly affected by the content of PO in the blend. As PO was reduced from 100 to 0% in Blends AL, the SFC and viscosity were reduced

M.S. MISKANDAR ET AL.

10

1200

8 SFC VISC R2 = 0.9846 SFC (%) 4

1000

800 Viscosity (cps)

600

R2 = 0.9689

400

0 A -2 PO Blend with 0% emulsifier B C D E F G H I J K

200

FIG. 2. SOLID FAT CONTENT (SFC) (%) AND VISCOSITY (VISC, CPS) AS A FUNCTION OF PALM OIL (PO) AND PALM OLEIN BLENDS AT SLOW CRYSTALLIZATION

almost linearly as shown in Fig. 2. The high PO content had created viscosity with high centipoise in Table 2 as well as densely packed crystals as shown in Fig. 1A. In the same respect, the crystal dispersion became loosely packed as the proportion of olein was increased in Blend E (Fig. 1B), and this was followed by a signicant drop in viscosity from 832 to 485 cps. Effect of Lecithin on Crystal Behavior The optimum amount of STS and lecithin effectively retarding or promoting crystal growth of Blends AL was inuenced by Tc and Tm. In general, at 0.03% level, lecithin had caused SFC to increase, but at 0.06 and 0.09%, lecithin caused SFC to decrease. As shown in Table 1, lecithin had caused an increase (P < 0.05) in the SFCs of Blends CH, but no signicant change was observed in the SFCs of A, B, J, K and L at 0.03%. Increasing the lecithin level to 0.06% caused a reduction (P < 0.05) in the SFCs of Blends A, B, G and H, but no signicant change in other blends was observed. At 0.09% lecithin, SFCs were reduced in Blends AH, while other blends remained unchanged. Table 1 shows that there was possible preference in the interaction of lecithin at its phosphate ends with the acyl ends of TAGs (Katsuragi 1999). It was suggested that at 0.03% lecithin, the phosphate ends had interacted with a low

EFFECTS OF EMULSIFIERS ON PO

TABLE 2. THE EFFECTS OF LECITHIN ON THE VISCOSITY (CPS) OF PALMOIL AND OLEIN BLENDS BY CYCLE 1 Blend 0 B E G 832 55Cc 485 102Bb 138 9Ca 0.03 394 64Ab 112 0Aa 101 9Aa % Lecithin 0.06 725 56Bc 384 27Bb 117 9Ba 0.09 1343 28Db 186 24Aa 112 0ABa

Mean of three determinations SD. AD Mean with different letters within each row is signicantly different (P < 0.05). ac Mean with different letters within each column is signicantly different (P < 0.05). Cycle 1, treatment temperatures and time of 80C (30 min) 20C (80 min).

number of acyl groups of the TAGs that retarded the crystallization and growth of the infected surface and crystal, but allowed the uninfected surface and crystals to grow as the blend was cooled. Crystal growth and crystal size was enhanced, as the infected crystals became the centers of crystallization. In general, it was noted that the SFC increase was only in blends containing 0.641.03% trisaturates (middle range of trisaturates), while no signicant change was noted in blends with a high range of trisaturates. At 0.06 and 0.09% lecithin, increasing points of interaction had occurred on more acyl ends, allowing less crystallization to take place. Retardation of crystal growth had occurred in most blends as shown by the reducing SFCs as lecithin was increased from 0.06 to 0.09% in the experiments as shown in Table 1. The signicant change in crystal development, as shown by the SFCs, was well correlated with crystal distribution. It was densely formed in Blend B without emulsier, but the addition of lecithin had reduced the crystal size (Fig. 3AC) due to physical and chemical interactions. The presence of 0.09% lecithin had induced the formation of the most crystal in comparison to the rest of the combinations in Blend B. As more liquid was present in Blend E, crystal arrangement became loosely packed in relation to the reducing amount of trisaturates in the blends. Lecithin had greatly reduced the crystal size of the blends; however, the amount of lecithin added into the blend had increased the crystal growth as shown by the crowdedness of the crystal under PLM (Fig. 3DF). Zaki et al. (1997) determined that tripalmitoyl-glycerol (PPP), sn-1myristoyl-2,3-dipalmitoyl-glycerol (MPP) and sn-1,2-dipalmitoyl-3-stearoylglycerol (PPS) are responsible for inuencing crystallization in palm

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M.S. MISKANDAR ET AL.

FIG. 3. PHOTOMICROGRAPH OF EFFECT OF LECITHIN ON CRYSTAL DISPERSION OF PALM OIL AND OLEIN BLENDS AT SLOW CRYSTALLIZATION (10 10 MAGNIFICATION) A, B and C are Blend B with 0.03, 0.06 and 0.09% lecithin, respectively; D, E and F are Blend E with 0.03, 0.06 and 0.09% lecithin, respectively.

EFFECTS OF EMULSIFIERS ON PO

11

olein. These high melting TAGs, especially the PPP, crystallize before the other TAGs do, thus forming a new liquid and solid interface on the surface of the crystal (De Man et al. 1989; Stauffer 1996; Zaki et al. 1997). The increment in the SFCs of Blends JL (0.1% SFC), E and F (6.76.9% SFC), and BD (7.99.1%) followed the same trend as the increment of PO in Blends AL at 0.03% lecithin. Except for Blends JL, the increase in the SFCs was signicant with changes in PO content with 0.06 and 0.09% lecithin. As shown in Table 1, insignicant SFCs in some of these blends indicates that lecithin was also more effective in promoting crystal growth in one blend over the other. Lecithin at 0.03% was more effective in promoting crystal growth in Blends D than C, and F than E, and L than J and K. However, lecithin was more of a crystal inhibitor at 0.06 and 0.09% in Blends AH. Insignicant increase in the SFCs of Blends JL with 0.030.09% lecithin indicated that the low content of SSS in the blends did not create sufcient crystals. Viscosity, SFC Relationship with Lecithin Viscosity is caused by the gelling effect of oil during the cooling process (Faur 1996). The increase in viscosity during crystallization process may have caused several implications, such as low heat conductivity and slowness in heat transfer through the mass that led to the crystal growth selective only to the high melting crystals (Faur 1996). The gelling properties due to the molecular arrangements of the crystals had developed constraints on crystal mobility and led to the minimum interactions between the crystals. Consequently, it retarded the crystal growth leading to the low solid. However, slow crystallization of PO and palm olein was contradictory with that of Faur (1996). The increases of SFC during slow crystallization of Blends GL with 0.06% lecithin (Fig. 4A) and DL with 0.09% lecithin (Fig. 4B) were not followed by an increase of viscosity. On the other hand, the reduction in the viscosity was more of a general effect of lecithin (comparing Fig. 4A,B). The viscosities of Blends DL with lecithin at 0.03% were below 200 cps, and the viscosities of Blends GL with 0.06% lecithin were also below 200 cps (Fig. 4A). However, the increase in trisaturated fatty acids content had caused the increased in SFCs that was followed by the increase in viscosity of Blends AF (Fig. 4A) and AC (Fig. 4B) for lecithin contents of 0.06 and 0.09%, respectively. The viscosity of the blends with lecithin was closely related to the crystal dispersion in the liquid as shown in Fig. 3. Variation in the crowdedness of the crystal distribution in Blend B with 0.03, 0.06 and 0.09% lecithin had viscosities of 394, 725 and 1,343 cps, respectively, as shown in Table 2. The viscosities of Blend E of the same lecithin content were 112, 384, and 186 cps, and Blend G had viscosities of 101, 117 and 112 cps with the same lecithin content, respectively.

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M.S. MISKANDAR ET AL.

10

1200

A
8 SFC VISC 1000

6 SFC (%)

800 Viscosity (cps) Viscosity (cps)

R2 = 0.9869

600

R2 = 0.9757

400

0 A -2 PO Blend with 0.06% Lecithin B C D E F G H I J K

200

10

2000

B
8 SFC VISC

1800 1600 1400 1200

6 SFC (%)

1000 800

600 400 A B C D E F G H RI = 0.9543 J K 200 R2 = 0.962 0

2

-2 PO Blend with 0.09% lecithin

FIG. 4. SOLID FAT CONTENT (SFC) (%) AND VISCOSITY (VISC, CPS) AS A FUNCTION OF PALM OIL (PO) AND PALM OLEIN BLENDS WITH 0.06% (A) AND 0.09% (B) LECITHIN AT SLOW CRYSTALLIZATION

EFFECTS OF EMULSIFIERS ON PO

13

Effects of STS on Crystal Behavior STS in PO and olein blends was generally a crystal inhibitor, as shown by its insignicant effect on the SFC except for few blends. Addition of STS at 0.03% level into the fat Blends GL did not signicantly (P > 0.05) change the SFC of the blends (except for Blends E, F and H) at the end of cycle 1 (Table 1). The SFC of Blends E, F and H had increased (P < 0.05) from 6.4 to 6.7, from 5.5 to 6.4 and from 1.6 to 2.6%, respectively. The increase in SFC indicated that STS was a crystal promoter in these blends. As 0.06% STS was added into the fat blends, no signicant changes occurred on the SFCs except for a few blends. The SFC decreased (P < 0.05) in A, B and H, but an increase in F was noted. At 0.09% STS, the SFC decreased (P < 0.05) in B, D, F and H. Table 1 shows that STS had promoted the crystal growth of a few blends, but inhibited growth of most of the blends. These ndings are in agreement with those of Garti (1988) on the inhibition of the effect of STS at 0.3% in sunower oil margarine, although this study used lower percentages of STS. SFC, Viscosity Relationship with STS SFC did not show a linear relationship with viscosity in blends with STS (Fig. 5A,B). The results show that STS was only effective in lowering the viscosities of the low-melting blends (Blends FL). The viscosities were maintained at below 200 cps in Blends GL with 0.03% STS, FL with 0.06% STS (Fig. 5A) and GL with 0.09% STS (Fig. 5B). It was also noted that increase of viscosities was only at region of SFC > 4% in Blends AF, AC (Fig. 5A) and AF (Fig. 5B) with STS content of 0.03, 0.06 and 0.09%, respectively. Addition of emulsier altered the chemical composition of PO and palm olein blends, hence their physical properties. The interaction of the fatty acids of the TAG and the acyl groups of the emulsier was selective and led to different rates of retardation and acceleration of crystal growth (Katsuragi 1999). Acceleration of crystal growth occurred when the emulsiers were adsorbed by the kinks of TAG molecules. STS seemed to have some of the acyl ends preference toward other similar acyl ends belonging to the TAGs forming the crystal, and were adsorbed to them, resulting in the retardation in growth of that crystal type, but at the same time allowing other crystals to continue growing and causing SFC to increase (Garti 1988; Katsuragi 1999). The preference of the acyl ends of STS and TAG was manifested by the homogeneous crystal distribution of even sizes in Blends B and E at 0.03% STS, respectively (Fig. 6). It is suggested that STS preferred blends with trisaturated fatty acids, and the interaction of acylacyl groups had enhanced the formation of homogeneous crystal sizes. The low trisaturate content in

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M.S. MISKANDAR ET AL.

10

2200

A
8 6
SFC (%)

2000 1800

SFC VISC

1600
Viscosity (cps)

1400 1200 R2 = 0.9581

4 2 R2 = 0.9423 0 A -2 B C D E F G

1000 800 600 400

K 200 0

PO Blend with 0.06% STS

10

1600

B
1400 8 SFC 6 SFC (%) Visc Viscosity (cps) 1000 4 R2 = 0.9562 2 R2 = 0.9838 600 400 0 A -2 PO Blend with 0.09% STS B C D E F G H I J K 200 0 800 1200

FIG. 5. SOLID FAT CONTENT (SFC) (%) AND VISCOSITY (VISC, CPS) AS A FUNCTION OF PALM OIL (PO) AND PALM OLEIN BLENDS WITH 0.06% (A) AND 0.09% (B) SORBITAN TRISTEARATE (STS) AT SLOW CRYSTALLIZATION

Blend G may have caused development of hardly visible crystals in Blend G by normal microscope. The crystal dispersion micrograph showed that crystal migration had occurred toward a particular nucleus with STS 0.06 and 0.09% forming irregular crystal sizes. Blends with more PO content had more crystal

EFFECTS OF EMULSIFIERS ON PO

15

FIG. 6. PHOTOMICROGRAPH OF EFFECT OF SORBITAN TRISTEARATE (STS) ON CRYSTAL DISPERSION OF PALM OIL AND OLEIN BLEND AT SLOW CRYSTALLIZATION (10 10 MAGNIFICATION) A and B are Blend B with 0.03 and 0.09% STS, respectively; C and D are Blend E with 0.03 and 0.09% STS, respectively.

formation and in the same manner more dense crystal formation occurred in blends with 0.09% STS. The viscosity of the blends with STS was closely related to the crystal dispersion in the liquid as shown in Table 3 and Fig. 6, respectively. Variation in the crowdedness of the crystal distribution in Blend B with 0, 0.03, 0.06 and 0.09% STS had viscosities of 773, 960, 1,506 and 1,166 cps, respectively, as shown in Table 2. The crystals in Blend B (0% STS) formed into big agglomerates that separated from the liquid and led to the low viscosity. Blend B (0.03% STS) produced small but evenly dispersed crystals with the lowest viscosity. The blends with 0.09 and 0.06% STS had promoted big and closely

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M.S. MISKANDAR ET AL.

TABLE 3. THE EFFECTS OF SORBITAN TRISTEARATE (STS) ON THE VISCOSITY (CPS) OF PALM OILAND OLEIN BLENDS BY CYCLE 1 Blend 0 B E G 773 78Ac 496 235Bb 138 9Ba 0.03 960 160Ac 554 64Bb 122 9Aa % STS 0.06 1506 170Cb 202 46Aa 112 0Aa 0.09 1166 15Bc 416 27Bb 122 9Aa

Mean of three determinations SD. AC Mean with different letters within each row is signicantly different (P < 0.05). ac Mean with different letters within each column is signicantly different (P < 0.05). Cycle 1, treatment temperatures and time of 80C (30 min) 20C (80 min).

packed crystal agglomerates with a strong crystal network, leading to high product viscosity. The viscosities of Blend E were 496, 554, 202 and 416 cps, and Blend G had viscosities of 138, 122, 112 and 122 cps with the same STS content, respectively. The trisaturate content of Blend E was lower than B; thus, crystal network formation was lesser in strength and lower in viscosity because of the dramatic increase in crystal size, but signicantly decreased in crystal number (Martini et al. 2002). The phenomenon suggested that as more STS was present in the blend, nuclei formation took place much earlier during cooling. The undesirable nuclei formation had enhanced crystallization, leading to the formation of large crystal size. The concentration of these crystals at limited numbers of centers was undesirable as crystal network would not be sufcient to bind the liquid, thus causing oil to separate from the solid. Table 3 shows that the viscosity in blends with 0.06 and 0.09% STS was greatly reduced because of oil separation.

CONCLUSIONS The Tm and Tc under slow crystallization conditions were sufcient for the PO and olein to crystallize without an emulsier. However, crystallization was affected by the presence of either lecithin or STS. These emulsiers, at specic amount and temperature, lead to crystal promotion or retardation. Under static condition, crystallization was toward the nearest nuclei. Heterogeneous crystals were formed in blends with high trisaturates, and homogeneous crystals were signicantly distributed in blends with more liquid phase. The slow crystallization process of PO and olein blends with 0.03% lecithin produced homogeneous crystals with low SFC and viscosity for uidized products.

EFFECTS OF EMULSIFIERS ON PO

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ACKNOWLEDGMENTS M.S. Miskandar thanks the Malaysian Palm Oil Board for permission to use the laboratory facilities. Special thanks to the Ministry of Science and Technology Malaysia for nancing the study and to Radzuan, Hanirah, Rosnah and Nor Haya for providing technical assistance. REFERENCES AOCS 1989. Ofcial and Tentative Methods of American Oil Chemist Society, 4th Ed., AOCS, Champaign, IL. BLAUROCK, A.E. 1999. Fundamental understanding of the crystallization of oils and fats. In Physical Properties of Fats, Oils, and Emulsiers, (N. Widlak, ed.) pp. 130, AOCS Press, Champaign, IL. BUSFIELD, W.K. and PROSHOGO, N.P. 1990. Isothermal analysis of palm stearin by DSC. J. Am. Oil Chem. Soc. 67, 171180. CHRYSAM, M.M. 1985. Table spreads and shortening. In Baileys Industrial Oil and Fat Products, Vol 3 (T. Applewhite, ed.) pp. 4283, John Wiley and Sons, Inc., New York, NY. DE MAN, L., DE MAN, J.M. and BLACKMAN, B. 1989. Polymorphic behavior of some fully hydrogenated oils and their mixtures with liquid oils. J. Am. Oil Chem. Soc. 66, 17771780. FAUR, L. 1996. Fractionation technology. In Oils and Fats Manual, Vol 2 (A. Karleskind, ed.) pp. 935951, Lovoisier Publishing, Paris, France. GARTI, N. 1988. Effects of surfactants on crystallization and polymorphic transformation of fats and fatty acids. In Crystallization and Polymorphism of Fats and Fatty Acids (N. Garti and K. Sato, eds.) pp. 267300, Marcel and Dekker, Inc., New York, NY. GARTI, N. 2002. Food emulsiers: Structure-reactivity relationships, design, and applications. In Physical Properties of Lipids (A.G. Marangoni and S.S. Narine, eds.) pp. 265340, Marcel and Dekker, Inc., New York, NY. GHOTRA, B.S., DYAL, S.D. and NARINE, S.S. 2002. Lipid shortening: A review. Food Res. Int. 35, 10151048. JAHANIAVAL, F., KAKUDA, Y. and ABRAHAM, V. 2000. Oil-binding capacity of plastic fats: Effects of intermediate melting point TAG. J. Am. Oil Chem. Soc. 79, 389394. KAMEL, B.S. 1997. Emulsiers. In Food Additive Users Handbook (J. Smith, ed.) pp. 170201, Blackie Academic & Professional, London, U.K. KATSURAGI, T. 1999. Interactions between surfactants and fats. In Physical Properties of Fats, Oils, and Emulsiers (N. Widlak, ed.) pp. 211219, AOCS Press, Champaign, IL.

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