Professional Documents
Culture Documents
Early production of margarine was dependent distinct from butter, and it prohibited the extend-
upon the availability of the oleomargarine from ing of butter products by incorporation of small
beef tallow to provide the desired consistency. proportions of margarine. In the United States,
However, two inventions soon opened the way to the addition of color to margarine to give it a
a wide range of natural fats as potential raw more butter-like appearance was long prohibited,
materials for margarine manufacture: hardening and manufacturers had to resort to including
and interesterification. capsules of color with the packs of margarine,
which consumers could blend in to their own
Hardening, or hydrogenation, consists of satisfaction.
reactions of unsaturated fats with hydrogen, Despite such legislation, the relative cheap-
thereby raising their melting points and in ness of margarine soon made it a major compo-
some cases increasing their oxidative stability. nent of the diet, especially for the poorer mem-
This procedure was introduced by NORMANN in bers of society, and enlightened governments
1903 [4]. quickly foresaw the dangers of malnutrition if
nutritional standards were not laid down and
Interesterification involves the exchange of maintained. The proportion of water was thus
fatty acid moieties between or within glycerides controlled at no more than 15 % in most coun-
to create new glyceride components. The ex- tries, and the addition of vitamins A and D was
change of acid moieties between esters had been made compulsory in order to maintain margarine
demonstrated by FRIEDEL and CRAFTS [5] as early at a nutritional standard comparable with that of
as 1865, and its potential application to natural butter.
fats was demonstrated by NORMANN in the 1920s Recent technical advances and new insights
[6]. Because of the required high temperatures into nutrition and health have enabled
(> 200 C) and long reaction times (several margarine manufacturers to exploit more fully
hours), however, the process was of no interest the flexibility inherent in the formulation of
to margarine manufacturers until ECKEY intro- margarine. As a result, margarine is now a
duced alkali-metal catalysts in 1948 [7]. The product in its own right, not simply a cheap
original conditions are not only economically substitute for butter. For example, wider usage
prohibitive, they are also deleterious with respect of domestic refrigerators has produced a
to the fat. Using alkali-metal catalysts the reac- demand for products plastic enough to spread
tion can be carried to completion below 60 C at low temperatures, a demand that has been
within minutes. met by the so-called soft blend margarines.
A third major development in the manufacture These contain fats chosen in such a way that the
of margarine was the introduction of the product retains a spreadable plasticity over a
votator system in 1936, permitting the ingredi- wide range of temperatures. A high level of fat
ents (i.e., fat, the aqueous phase, and minor in the diet, especially saturated fat, is now con-
components) to be premixed and then sidered undesirable, and this has led to the devel-
subjected to simultaneous rapid shearing and opment of low-fat spreads and to the use of fat
cooling. This not only causes the aqueous phase blends with a high proportion of polyunsaturated
to be finely and uniformly dispersed throughout fatty acids (PUFA). The early protective legisla-
the fat phase but also gives the processor a greater tion has also come under pressure from respon-
degree of control over the final texture of the sible nutritional authorities, who have urged that
product. margarine manufacturers be permitted more flex-
Margarine was first conceived as a substitute ibility. Consumers now have a wide choice of
for butter, and from the start it was seen as a margarine-type products, covering the whole
commercial threat by the dairy industry. Marga- gamut of fat contents from conventional marga-
rine manufacture was soon controlled by legisla- rine at 85 % down to very low fat spreads at ca.
tion designed to protect the dairy interest. Sup- 20 %, and including various melanges with dairy
pression of the name ‘‘butterine’’ was considered products such as low calorie and high PUFA
to be an early victory for the dairy farmers in this ‘‘butters’’.
long standing ‘‘war’’. Other legislation soon Brand names for the various types of marga-
decreed that margarine must be sold as a product rine are listed in Table 1.
Vol. 22 Margarines and Shortenings 247
Table 1. Some typical margarines and other spreads with brand names 2. Objective properties measured with laborato-
in use at the time of writing (1989)
ry instruments
Fat content, Brand
wt % name Manufacturer Country
2.1. Subjective Properties
Conventional Margarines
General
Purpose The most obvious subjective property is appear-
ca. 80 Stork Unilever UK ance, which comes into play as soon as the
ca. 80 Imperial Unilever USA consumer opens the package. First, the product
ca. 80 Rama Unilever FRG
ca. 80 Lesieur Lesieur Alim. France
must have an attractive color. This has tradition-
Soft Blend (i.e., spread at refrigerator temperature) ally meant a yellow color similar to that of
ca. 80 Stork S.B. Unilever UK butter. Margarine must also have a smooth,
ca. 80 Blue Band Unilever UK creamy-looking texture; i.e., it should not appear
PUFA (i.e., high in polyunsaturates)
ca. 80 Flora Unilever UK
grainy or greasy. When the consumer applies
ca. 80 Becel Unilever Netherlands, the margarine to a piece of bread or biscuit, it
FRG should have good ‘‘spreadability’’; i.e., it should
ca. 80 Vitelma Vandemoortele Belgium be soft enough to spread smoothly and easily
ca. 80 Sense Van Dijk Netherlands
ca. 80 Vitalite Kraft UK
without breaking into lumps, exuding water, or
Reduced Fat Spreads dragging the bread surface. Furthermore, the
72 Promise Unilever USA margarine must have an acceptable flavor and
70 Krona Unilever UK ‘‘mouthfeel’’.
60 Stork Light Unilever UK
60 Light Soft Fleischmann USA
For Europe and many other parts of the
52 Country Crock Unilever USA world the standard for good flavor is fresh
40 Delight Unilever UK butter, and much research has been devoted to
40 Gold St Ivel UK creating flavor cocktails imparting a butter-like
40 Blue Band Unilever Netherlands
27.5 Outline Unilever UK
taste. In some places, however, other flavors are
25 Gold Lowest St Ivel UK preferred. Thus, in parts of South America fruit
Melanges (i.e., mixtures of butter fat and vegetable fats) flavors such as pineapple are appreciated, while
78 Willow Dairy Crest UK in some African countries fish flavors are
75 Golden Churn Kraft UK
75 Clover Dairy Crest UK
popular.
40 Clover Light Dairy Crest UK Mouthfeel is a reflection of the physical
40 St Hubert 4 I St Hubert France changes that take place as margarine melts
Dairies and breaks down under the action of teeth and
40 St Florigny Unilever France
40 Tartine Lesieur Alim. France
tongue and mixes with saliva in the warm envi-
Reduced Fat Butters rons of the mouth. This melt-down can take place
40 Half Fat Anchor Foods UK smoothly or lumpily. The melt-down may be
Anchor complete, or some unmelted fat may remain
40 Die Leichte Unilever FRG
40 Sylphide Fromagerie Bel France
and be perceived as a waxy coating around the
40 Vive la Vie Unilever France tongue and palate. The melted product can feel
40 Balade Corman-France France creamy or thin and watery. In some circum-
stances, a cool sensation is perceived, perhaps
due to a rapidly melting fat blend. The flavor
release pattern is also affected by the way in
which margarine breaks down, releasing flavor
2. Properties of Margarine components to the palate at different rates, which
may in turn influence the consumer’s overall
The properties of margarine can be considered perception of flavor.
under two headings: All these effects can be related, in theory at
least, to such physical properties of the margarine
1. Subjective properties that are assessed by the as melting characteristics or emulsion stability,
reaction of a consumer when presented with a but it is not possible to measure all of them
sample of the margarine directly with laboratory instruments.
248 Margarines and Shortenings Vol. 22
2.2. Objective Properties Section 2.1). A fat blend, and indeed a natural fat,
consists of a complex mixture of glycerides, each
2.2.1. Color with its own characteristic melting point and each
influencing and influenced by the melting of
The color of margarine is defined in terms of the other glycerides in the mixture through the for-
tristimulus concept, which postulates that any mation of solutions and eutectics. As a result, a
color can be specified in terms of the three solid fat does not show a single sharp melting
primary colors red, yellow, and blue. In practice, point, but rather a gradual softening over a wide
the color of light reflected from the surface of a range of temperature. The melting character of a
margarine sample is matched against that of light fat must therefore be defined in terms of the solids
which has passed through a series of filters based content of the fat at a given temperature.
on the primary colors. The color is then defined in
terms of the density of each of the filter colors Dilatation. Traditionally, solids content
required to give a match. A suitable commercial was measured by dilatation [9]. A completely
instrument for this purpose is the Lovibond Tint- solid fat, like any other solid, shows a small
ometer [8]. increase of volume with increasing temperature.
Color is primarily dependent on the amount of A fully liquid oil also expands when heated,
coloring material added to the margarine mix- slightly more than does a solid fat. However,
ture, but it is also affected by the physical nature when the solid melts to a liquid, a considerably
of the margarine (e.g., by the ratio of solid fat to greater volume change is observed. Therefore,
liquid oil in the fat phase, the amount of the water the increase in volume in the course of heating
phase, and the size and distribution of water between two temperatures is essentially a mea-
droplets). sure of the proportion of the sample that melts
over that temperature range. In practice the
change is measured with a dilatometer, which
2.2.2. Gloss consists of a glass bulb containing the fat sample
connected to a graduated capillary tube contain-
Gloss is a measure of the efficiency with which ing a marker liquid. As the volume of fat in the
light is reflected from the surface of the marga- bulb increases the marker liquid is pushed up the
rine. A mirror surface reflects a beam of light at capillary, permitting the volume change to be
the same angle at which the beam strikes the quantified. Such a bulb is immersed sequentially
surface, with little or no scattering. A matt sur- in a series of water baths at different temperatures
face scatters the beam so that the intensity of the and for each bath the level of liquid in the
reflected light is uniform over a wide angle of capillary is noted. After correcting for expansion
reflection. A glossy surface falls between these of the glass and the liquid oil it is then possible to
two extremes: a portion of the light is reflected calculate the proportion of fat melted at each
along the angle of incidence, but some is scat- temperature.
tered. Glossiness can therefore be measured by
comparing the intensity of incident light with that Nuclear Magnetic Resonance. Today it is
of reflected light at predetermined angles. generally more convenient to use a nuclear mag-
Like color, gloss is dependent upon the physi- netic resonance (NMR) technique to measure
cal nature of the margarine; i.e., upon the pro- solid fat content [10]. This is possible because
portion and distribution of solid fat crystals and a proton within a molecule responds differently
water droplets. to a strong magnetic field depending on whether
it is held rigidly in a solid crystal matrix or only
restrained in a liquid substrate. NMR instruments
2.2.3. Melting Properties especially designed for this application are com-
mercially available.
The melting characteristics of a margarine are
essentially those of the fat blend used in its Polymorphism. One factor that can confuse
composition, and they are responsible for many the measurement of solid fat content by either
of the product’s subjective characteristics (see dilatation or NMR is the phenomenon of poly-
Vol. 22 Margarines and Shortenings 249
morphism [11]. Thus, many compounds are ca- droplet size is 5 – 10 mm. In conventional mar-
pable of assuming any of a number of different garines, drop size is an important factor in con-
physical forms, each with a different melting trolling the biological stability of the product.
point. This phenomenon is especially evident in Most microorganisms can only develop in an
the behavior of fats. When a melted fat is cooled aqueous environment and their growth through-
rapidly below its melting range, it usually crystal- out the product is therefore inhibited if water is
lizes in an unstable form known as the a modifi- present only in very small drops. In the case of
cation. On standing, this rearranges into a more low-fat spreads (where water constitutes 60 % or
stable b or b0 form (cf. Section 3.1.1). Stable more of the total composition) the droplet size
modifications can also be achieved by slow cool- can also affect such subjective properties
ing or by crystallization from a solvent. The as hardness, mouthfeel and flavor release, but
solid content of a particular sample depends on these considerations are less critical in conven-
the relative proportions of these various poly- tional margarines (with only ca. 15 % water
morphs and therefore on the way in which the content).
sample has been prepared. For quantitative com- Drop size can be measured directly with an
parisons, samples must therefore be subjected to optical microscope or indirectly by NMR tech-
a standard regime before their solids content is niques [13]. Both methods are subject to diffi-
measured. culties of interpretation because the droplets in a
given sample have a range of sizes and are not
necessarily spherical.
2.2.4. Penetration
1. Emulsion instability results in the coalescence Polyunsaturated fatty acids are more susceptible
of dispersed water droplets and visible sepa- than monounsaturated acids, which in turn are
ration of water from the product. Provided a more susceptible than saturated acids. Fish oils
suitable emulsifier has been chosen and the are highly unsaturated, with up to six double
product has been correctly processed, this bonds per fatty acid chain, and these are particu-
only becomes a problem if the product is larly prone to autoxidation. They have the added
subjected to extreme changes of temperature. disadvantage that their autoxidation products
2. Oily exudation indicates a breakdown of the have characteristic rancid, fishy flavors unac-
crystal network in the fat phase of the product, ceptable in a margarine product. For this reason
and there is visible separation of liquid oil at fish oils are only used in margarine formulations
the surface (i.e., between the paper and the after the number of double bonds has been re-
product in a wrapped margarine, or between duced by hardening.
the walls of the tub and the product in a tub- In general, autoxidation can be controlled by
filled margarine). Exudation may arise as a efficient refining (see Section 3.1.1). Refining not
result of inappropriate choice of fat composi- only removes indigenous flavors from natural
tion, but in an established product it is more oils or fats but also reduces the level of any
often an effect of exposure to extreme tem- pro-oxidants present. If a blend contains predom-
peratures or to mechanical mishandling. inantly animal fats, further protection by antiox-
3. Sandiness or graininess is due either to con- idants may be required. This precaution is not
tinued growth of individual crystals or to normally necessary for vegetable fats and oils, as
aggregation of crystals after processing. The these contain adequate quantities of natural anti-
effect can be detected visually (by an exces- oxidants in the form of tocopherols.
sively matt or granular surface appearance) or
by mouthfeel [14]. Certain fats or fat blends Hydrolytic Rancidity occurs when the ester
(notably those containing palm oil and lard) linkage joining the fatty acid moiety to glycerol is
are particularly prone to this fault due to the split, leading to the release of free fatty acid. This
presence of large quantities of single species can be a result of autoxidation, but it is more
of glycerides, oleodipalmitins, or palmitodio- likely to be caused by hydrolysis. Long-chain
leins, which readily form compound crystals. fatty acids ( C16) are virtually flavorless,
Critical proportions of these fats should be so their release does not produce a flavor prob-
avoided. Interesterification can also be used to lem. On the other hand, short-chain fatty acids
reduce the concentration of individual trigly- ( C12) have quite intense intrinsic flavors, and
cerides responsible for the effect. their release causes the off-flavors variously
described as rancid, soapy, or cheesey. Since
Chemical Changes. Chemical changes af- butter contains a relatively high proportion of
fect the flavor of a product, causing rancidity such short-chain acids it is more prone than
through either autoxidation or hydrolysis. most margarines to this form of off-flavor
development.
Autoxidation refers to reaction between fatty
acid chains and atmospheric oxygen. The first Biological Changes. Biological changes are
step is removal of a hydrogen atom from the the result of microbial contamination of a mar-
hydrocarbon chain of the fatty acid and its re- garine. If allowed to develop, microorganisms
placement by a hydroperoxide group. The latter can render a product unsightly and unwholesome
then reacts further by addition to double bonds or as well as subject to physical and chemical
by chain cleavage to give a complex mixture of changes. The primary means of controlling mi-
aldehydes, ketones, and short-chain fatty acids. croorganisms is strict attention to hygiene during
Many of these products are highly flavor-inten- storage of ingredients, processing, and packag-
sive, only a few parts per million being sufficient ing, but preservatives are sometimes used to
to impart a detectable flavor. Hydrogen atoms on protect the stored product after packaging. Be-
carbon atoms adjacent to double bonds, and to a cause of their high water content, low-fat spreads
lesser extent those adjacent to ester groups, are are more susceptible than conventional margar-
most labile and therefore most readily attacked. ines to this type of deterioration.
Vol. 22 Margarines and Shortenings 251
Soybean USA and South America widely used as a cheap source of PUFA (linoleic acid) also, after
hardening, as a hardstock
Cottonseed USA and Eastern Mediterranean in margarine mainly used after hardening as a hardstock espe-
cially in USA
Rapeseed North America and Northern Europe since the development of low-erucic varieties, this has been
increasingly used as a replacement for soya bean oil in Europe and
Canada
Sunflower widely distributed in warmer temperature zones main source of PUFA (linoleic acid)
Safflower USA, Central America, North Africa, and India richer in PUFA than sunflower but more expensive
Groundnut widely distributed in semitropical areas formerly one of the basic commodity oils for margarine, both as a
liquid oil and, after hardening, as a hardstock but now relatively
expensive
Palm Malaysia and Central Africa widely used both as the whole oil and after fractionation or
interesterification when melting characteristics are important
Lard widely distributed where pigs are raised, mainly used in similar contexts to palm oil but only in circumstances
USA and Europe where the animal source is not important
Beef tallow USA, Europe, and Australasia limited use of the olein in margarines, especially those products
where texture is more important than health appeal
Palm kernel as for palm oil widely used as a hardstock because of its relatively sharp melting
range at about mouth temperature
Coconut Pacific Islands, West Indies, and Southern Indian as for palm kernel
Continent
Fish
Herring North Atlantic South very cheap source of oil but because of flavor problems can only
Menhaden Atlantic North be used in food products after hardening; however, increased
Pilchard Pacific South exploitation as source of essential fatty acids and sale as such
Anchovy Pacific through pharmacies and health food stores may alter this pattern
of use
*
PUFA ¼ polyunsaturated fatty acids
wide range of natural oils and fats but only about tallization characteristics discussed above.
a dozen are of commercial importance at any one Apart from lard, the only animal fat to find wide
time (Table 2). The list varies depending on application is beef tallow [61789-97-7], but, as
agricultural practice and availability, but the MeGE – MOURIES found (cf. Chap. 1), the high-
following applies at the time of writing (1989). melting stearin must be removed before beef
Of the liquid oils, soybean oil [8001-22-7] is the tallow can be used. Butter fat is of course incor-
most widely used, with rapeseed oil [8002-13-9] porated into melange products. The lauric fats
a close equivalent in Europe. Sunflower oil (palm kernel oil [8023-79-8] and coconut oil
[8001-21-6] is favored in high PUFA blends [8001-31-8]), so called because they contain
because of its high content of linoleic acid (ca. a high level of lauric acid, are also useful as
50 – 60 %) and the absence of the linolenic acid hardstock components since they have relatively
present in soybean oil, which reduces flavor sharp melting points near mouth temperature.
stability. Safflower oil [8001-23-8] is more ex- Marine oils are among the cheapest oils avail-
pensive than sunflower oil, but it is favored by able, but because of flavor problems they can
some manufacturers because it has an even high- only be used (after hardening) in cheaper,
er linoleic acid content and can therefore be used lower quality margarines. At one time this source
to maintain a high PUFA content with a higher was dominated by whale oil, but embargoes
level of hardstock. Peanut oil [8002-03-7] was at placed on whaling for conservation reasons have
one time widely favored because of its high caused whale oil to be replaced by oils derived
oxidative stability, but it is now more expensive from such oily fish as herring, menhaden,
than other liquid oils. Palm oil [8002-75-3] and and anchovy. For further information on the oils
lard [61789-99-9] are semiliquid oils whose us- and fats described in this section, see ! Fats and
age in unmodified form is restricted by the crys- Fatty Oils.
Vol. 22 Margarines and Shortenings 253
Selective hardening and trans hardening both of even more of the high-melting glycerides. This
favor a less complex mixture, resulting in a continues until no more high-melting acids re-
narrower melting range. Hardening also helps to main in the reaction mix. The result is segregation
stabilize a polyunsaturated oil against autoxida- of the higher melting acids into a stearin fraction,
tion. Thus, the linolenic acid in soybean oil (with which can be removed by fractionation. Applica-
three double bonds) is reduced in the course of tion of this technique to sunflower oil gives an oil
hardening, as are the highly unsaturated fatty with a lower content of saturated fatty acids and a
acids (with five or six double bonds) in fish oils. corresponding increase in polyunsaturated acids.
The use of sodium compounds as catalysts
3.1.2.3. Interesterification requires that the oil be dry, neutral, and protected
by an inert atmosphere, since water, fatty acids,
Interesterification alters the ester links in oils and and oxygen all deactivate the catalyst. A com-
fats joining fatty acid moieties and glycerol; thus, mon procedure calls for carrying out the reaction
one fatty acid residue from one of the three under vacuum so that water is removed rapidly. A
positions on glycerol is interchanged with anoth- sodium-based catalyst cannot be recovered from
er , either on the same molecule or on another the reaction mixture because it is ultimately
molecule (! Fats and Fatty Oils, ! Fats and converted to soap. Any active catalyst remaining
Fatty Oils). This process commonly results in a after interesterification is deactivated by the ad-
random fatty acid distribution over all the glyc- dition of a dilute acid (e.g., acetic acid). Sodium
eride molecules present (random interesterifica- salts and soaps are then removed by washing,
tion). In the case of a two-component blend, such which is followed by a light earth bleaching and
as a liquid oil and a solid fat, interesterification final deodorization.
gives a more complex spectrum of glycerides
than would be obtained by simple physical mix- 3.1.2.4. Fractionation
ing. The result is a plastic fat that melts gradually
over a wide temperature range rather than a Fractionation entails separating a fat into frac-
semisolid oil with high-melting components. tions with different melting ranges by crystalli-
Interesterification can also be used to eliminate zation and subsequent removal of the crystals
some triglyceride components that tend to domi- (! Fats and Fatty Oils, Chap. 7.). Such a process
nate the crystallization behavior of a mixture might be carried out for various reasons: to
(e.g., to remove troublesome triglyceride species remove very high melting components (e.g., the
from lard or palm oil, see Section 2.2.7). stearin from beef tallow), to concentrate PUFA
Interesterification is catalyzed by heavy-metal acids (as in removal of stearin from a directively
salts such as tin(II) chloride or by fatty-acid soaps interesterified sunflower oil), or to select a frac-
of the alkali metals. These are generally intro- tion with a relatively sharp melting range for use
duced at a level of about 2 %. For such catalysts to as a hardstock component. The latter objective
be effective, the reaction must be carried out at requires two-stage fractionation involving re-
about 200 C. More efficient catalysis is provided moval of both a stearin and an olein fraction to
by such compounds as the sodium salts of the leave a mid-fraction. The process has been ap-
short-chain alcohols (sodium methoxide or eth- plied to palm oil to obtain a fraction rich in
oxide), sodium glyceroxide, or anhydrous sodium monooleodipalmitin and also to interesterified
hydroxide, all at a level of about 0.5 % or less. blends of lauric-rich fats with fats rich in stearic
Reaction then proceeds at a much lower tempera- and palmitic residues, thereby producing a frac-
ture ( 60 C), reaching completion within a few tion rich in monolaurodipalmitin or -distearin
minutes. This is a much more efficient technique glycerides.
for random interesterification. Moreover, it per- Fractionation can be carried out either in a
mits directed interesterification, in which the solvent or ‘‘dry’’. Acetone, light hydrocarbons,
reaction is conducted at such a low temperature and methanol are used for solvent fractionation.
that the high-melting glycerides tend to crystallize The fat is first dissolved by heating it in the
during the reaction. The highest melting fatty solvent, after which the solution is cooled to a
acids are thus effectively removed, and equilibri- temperature at which crystallization takes place.
um is displaced toward the formation and removal The temperature required depends on the oil
Vol. 22 Margarines and Shortenings 255
being treated. In a typical palm-oil fractionation, 3.2.1. The Aqueous Phase in Conventional
for instance, an acetone solution of the oil is Margarines
cooled to ca. 20 C to precipitate the stearin, then
to 0 C to precipitate the mid-fraction. The re- In conventional margarine the aqueous phase
sulting fat crystals are removed by filtration and consists mainly of water, and its main function
solvent is recovered by distillation. Solvent frac- is as a carrier of flavoring components. In some
tionation gives a clean separation of the various parts of the world, special flavors are common
glycerides, but it is an expensive operation be- (cf. Section 2.1), but in the Western World
cause of the specialized equipment required for margarine is expected to taste as much like butter
the handling and recovery of highly flammable as possible. Considerable research has been de-
solvents. Normally it is applied only to fats for voted to achieving this end. Most of the effort has
products carrying a premium relative to ordinary focussed on identifying the natural flavor com-
margarine (e.g., confectionery fats). ponents in butter. This resulted initially in the
In dry fractionation, liquid components of introduction of diacetyl and short-chain fatty
the oil blend (i.e., the olein) act in effect as acids. Later work led to the use of the g- and
solvents for the solid components or stearin. This d-lactones of C8– C14 hydroxy fatty acids. Most
means that ‘‘solvent’’ occluded in the separated manufacturers now employ their own closely
stearin cannot be removed by distillation as in guarded ‘‘flavor cocktails’’. Butter-like flavor is
solvent fractionation. Instead, it remains as part enhanced by use in the aqueous phase of
of the stearin composition and the resulting skimmed milk that has been ripened with lactic
separations are less clear-cut than in solvent acid bacteria.
fractionation. In order to achieve maximum sep- Another flavor-contributing component of the
aration efficiency special care must be taken in aqueous phase is salt. The salt level must be
the choice of crystallization conditions. The rates carefully adjusted to correspond to the prefer-
of cooling and stirring are particularly critical for ences of a particular national market.
producing crystals with the best form for easy
separation.
Separation techniques other than filtration 3.2.2. The Aqueous Phase in Low-Fat
may also be used to maximize separation of the Spreads
olein. One such technique is pressing, in which
slabs of stearin are squeezed between the plates In low-fat spreads the aqueous phase not only
of a hydraulic press. This is particularly effective carries the flavor components but also contri-
for removing a small amount of olein from a large butes to the structure of the product. Thus, with a
amount of stearin, as in the preparation of palm fat content 40 % it is necessary to invoke
kernel stearin. Another valuable technique is the special techniques to ensure adequate rigidity.
Lanza separation. Here the crystal slurry is stirred Rigidity can be achieved in two ways. A spread in
with an aqueous detergent solution, typically which the aqueous phase is essentially water, can
sodium lauryl sulfate. The detergent solution be stiffened by the use of powerful emulsifiers
preferentially wets the solid fat crystals and which disperse the water more finely and stabi-
draws them into the aqueous phase. Olein is then lize the resultant droplets. Such stable, highly
separated from the aqueous phase by centrifuga- dispersed droplets augment the limited number
tion, leaving the stearin in the aqueous phase. The of fat crystals present in the system (cf. Chap. 4),
stearin is recovered by heating this mixed phase thereby increasing the effective size of the elastic
above the melting range of the stearin, followed crystal network. The extent to which this princi-
by further centrifugation. ple can be applied is limited, however; an emul-
sion that is too stable adversely affects the
mouthfeel of the product, producing an initial
3.2. The Aqueous Phase thick, heavy sensation that is followed by a rapid
watery breakdown. The alternative is to thicken
The aqueous phase comprises ca. 15 % of a the aqueous phase by adding components that
conventional margarine but it can account for either gel the water or increase its viscosity to
60 % or more in a low-fat spread. such an extent that the dispersed water droplets
256 Margarines and Shortenings Vol. 22
behave like semisolid particles. Components that emulsifiers to enhance particular end-use prop-
have been used for this purpose include gelatin, erties (see Section 5.1).
caseinates derived from milk proteins, water-
soluble carbohydrate gums (e.g., carrageen and
locust bean gum), and modified starches. Addi- 3.4. Minor Components
tives are introduced at levels of 5 – 15 % depend-
ing on type. Together with the processing con- Minor components added to margarines include
ditions such additives can significantly affect the antioxidants, coloring agents, preservatives, pH
mouthfeel of spreads, and the creamy breakdown regulators, and vitamins (! Foods, 3. Food Ad-
associated with conventional margarines is more ditives, Section 3.6).
easily achieved in low-fat spreads in which The preferred antioxidants are tocopherols,
thickeners have been used than in one with an which may be either synthetic or derived from
unthickened aqueous phase. natural sources, but synthetic compounds such as
butylated hydroxytoluene (BHT) or butylated
hydroxyanisole (BHA) are sometimes used in-
3.3. Emulsifiers stead. The antioxidants pick up or release free
radicals in the course of assuming stable quinone
Emulsifiers are essential to both conventional or hydroquinone configurations and thereby in-
margarines and low-fat spreads. They facilitate terrupt the chain of free radical reactions respon-
dispersion of the aqueous phase and also stabilize sible for autoxidation (! Antioxidants). Natural
the resulting dispersion. A typical emulsifier tocopherol antioxidants occur in most vegetable
contains both polar and nonpolar groups. Since oils, so that the use of antioxidants is generally
the affinities of these groups for the two phases limited to fat blends consisting primarily of ani-
differ, the emulsifier tends to concentrate at the mal fats.
phase interface. This alters both the interfacial Coloring agents are usually carotenoids. Ex-
tension and the interfacial viscosity, thus aiding amples include b-carotene, either from palm oil
the formation and stabilization of droplets of or synthetic, and annatto, a mixture of bixins
one phase dispersed within the other. Whether derived from the Central American fruit of that
the dispersion is one of water in oil or oil in name.
water depends on the relative number and The most widely used preservative for the
nature of polar and nonpolar groups, the so-called control of biological activity is common salt, but
hydrophilic – lypophilic balance (HLB). Emul- in some circumstances potassium sorbate is
sions are discussed in detail elsewhere added, particularly in low-fat spreads where
(! Emulsions). increased water content favors microbial growth.
The emulsifiers most widely employed in Control of the pH may also be used to inhibit
margarine and other spreads are monoglycerides biological activity. Control of pH is also neces-
and lecithins. In monoglycerides, polar character sary in spreads in which the aqueous phase has
is provided by two free hydroxyl groups, and been thickened with proteins (e.g., caseinates)
nonpolar character by the long-chain fatty acid because the resulting viscosity or elasticity is a
moiety. Monoglycerides are prepared by inter- function of pH. Salts of weak acids (e.g., sodium
esterification of natural triglyceride oils with citrate or sodium phosphate) are used for this
glycerol and concentrated by distillation. purpose.
In lecithin, nonpolar character is again con- Most food control authorities require the ad-
ferred by long-chain fatty acid residues, but the dition of vitamins A (27 – 33 IU/g) and D
polar component is the phosphatidyl moiety at- (2.8 – 3.5 IU/g) to margarine as a means of
tached to the third hydroxyl group of glycerol assuring adequate nutritional value.
(! Lecithin). The lecithin most widely used in
margarine occurs as a natural component of
soybean oil and is separated from the oil at the 4. Processing
degumming stage of refining.
Margarines designed for special applications Margarine processing procedures are designed to
(e.g., pastry) may incorporate specially selected achieve three objectives:
Vol. 22 Margarines and Shortenings 257
mechanical processes include extrusion through tank to create a loose emulsion suitable for
a screw press, squeezing through a gap between pumping into the votator line. Alternatively, the
rollers, or agitation by rotating knife blades. components may be pumped from independent
holding vessels into the votator line through a
proportionating pump adjusted to produce the
4.2. Votator Process required volume ratio.
The combination of high shear and rapid
The term ‘‘Votator’’ was first coined by the cooling in the A unit results in a finely dispersed
Girdler Company in the United States to describe emulsion with an even distribution of fine fat
the continuous cooler – stirrer unit that they crystals. Low shear agitation in the C unit permits
introduced in 1936. A flow scheme for the votator further growth of these crystals without the for-
process is shown in Figure 3. Two votator units mation of an interacting crystal network. Only
are involved in margarine production, the A unit under subsequent quiescent conditions is further
and the C unit. crystal growth able to produce such a network.
The A unit consists of a jacketed tube fitted Thus, it is the C unit that controls the ultimate
with a rotating shaft that fills most of the cross plasticity of the product. If all the crystal nuclei
section of the tube, leaving an annulus of 5 – emerging from the A unit were allowed to grow
10 mm. This annulus is occupied by blades into crystals, all contributing to the crystal net-
attached to the rotating shaft and touching the work, then the product would be too brittle.
inner wall of the tube. The jacket is cooled by a A typical votator installation utilizes combi-
refrigerant such as liquid ammonia. The shaft is nations of A units and C units coupled in series.
rotated at high speed ( 500 rpm) and the prod- The manufacturer selects a set of temperatures,
uct mixture is forced through the annulus. It is residence times, and agitation conditions specifi-
thus subjected to rapid cooling by contact with cally tailored to the mixture composition and the
the refrigerated walls of the jacket as well as to required product type.
high shear. A further unit, the B unit, is necessary for
The C unit also consists of a jacketed tube with margarine that is to be packaged in a paper
a rotating shaft, but the shaft is smaller in diam- wrapper. This unit consists of an open tube
eter relative to the cross section of the tube, so the corresponding in cross-section to the final
annulus is much wider. Moreover, the shaft is wrapped slab. The tube is without a rotating
fitted not with wall-scraping blades but with a shaft, so product passes through with minimum
series of pegs. As the shaft rotates, the pegs move agitation. This not only molds the product into
between similar pegs attached to the inner wall of the required shape for packing but also provides
the tube, subjecting the contents of the C unit to the degree of product firmness necessary for
mixing at controlled temperature but not to the handling in a wrapping machine.
high shear conditions prevailing in the A unit. Product that is to be packaged in tubs or
The required proportions of fat and aqueous cartons is extruded directly into the container
phases may be continuously stirred in a premix from the last votator unit. Firming proceeds to
completion in the container during subsequent
storage. The success of this technique depends on
precise control of the degree of crystal network
formation in the processing line, i.e., on an
optimal balance of A- and C-unit working.
‘‘Over-working’’ (premature formation of a crys-
tal network, which is subsequently destroyed by
further mechanical working) produces a product
that is too liquid, because most of the crystalli-
zation takes place in the absence of an interactive
network. Such a product only becomes firm in the
Figure 3. Schematic diagram of a votator plant with pre-
tub after prolonged storage, if at all. At the other
crystallization and recycling (Unilever) a) High-pressure extreme, too much potential for crystal growth
metering pump; b) C unit; c) Pump; d) A unit; e) B unit in product leaving the line leads to excessive
Vol. 22 Margarines and Shortenings 259
posthardening and a birttle product. Neverthe- in bread mixes because fat levels > 3 % interfere
less, some posthardening must occur in the tub, with the development of gluten structure. In
since attempting to extrude stiffened product short crust pastry the aim is reversed. Long
would result in high back pressure along the line, protein chains are not allowed to develop, result-
which would in turn interfere with the mechani- ing in a product that is crumbly and, unlike
cal working of the system. bread, breaks easily into small fragments when
The votator system is intended for continuous bitten. This is achieved by giving the pastry
operation, but it is nonetheless subject to occa- mixture a relatively high fat content— ca. 30 %
sional stoppages, with breakdown of the packag- or more. Individual grains of flour thereby be-
ing equipment being the most common cause. come coated and the gluten structure cannot
Interruption of throughput typically results in extend from grain to grain. Baked pastry consists
product setting up in the votator line, with the essentially of an aggregate of partially gelati-
potential for considerable loss of product, time, nized starch granules cemented together with fat.
and energy. Consequently, the whole system (the The fat must therefore be easily and intimately
mixture composition and the lay-out of the pro- mixed into the flour, and it must also have suffi-
cessing units) is designed to facilitate recycling cient solid content to contribute to the rigid
without altering the nature of the final product or structure of the finished pastry. This calls for a
the settings of the processing parameters. fat blend containing relatively high-melting
A satisfactory production line must also in- components together with a reasonable propor-
clude provision for regular and rigorous cleaning tion of liquid fat, thereby providing plasticity
and sanitization to eliminate the possibility of over a wide temperature range. Animal fats such
microbial contamination. This entails pipelines as lard and beef suet have traditionally been used
for detergent solutions as well as steam lines for for this purpose, but more precise control of
equipment scalding. It is especially important to favorable properties is possible through the use
avoid dead pockets that might trap partially of blended oils, including palm oil and hydroge-
processed material and serve as isolated breeding nated vegetable oils. Water is essential only as a
grounds for microorganisms. flavor carrier. Indeed, too much water renders the
pastry sticky due to overgelatinization of the
starch. The final water content of a mix must
5. Specialty Margarines and usually be adjusted by the baker to suit a partic-
Shortenings ular flour, so margarine especially designed for
short crust pastry frequently contains less water
Most margarines are intended for spreading on than conventional margarines.
bread, but some are also used in cooked foods, The products referred to as shortenings con-
including cakes and pastries, as well as in the tain no water. Soft, pumpable shortenings
preparation of fried foods. Specialty margarines have been developed to meet the needs of
exist for commercial use in the latter large-scale bakers and confectioners, who must
applications. handle ingredients in bulk. Such shortenings are
collected from the votator line in bulk containers.
They are delivered in tankers and stored in bulk
5.1. Pastry Margarines storage tanks. Storage and transport containers
are held at 20 – 25 C to maintain a pumpable
Pastry margarines are mainly used for short crust consistency.
pastry, cake mixes, and flaky pastry; i.e., flour Cake mixes resemble short crust pastry mix-
confections in which fat is a major ingredient. tures in that they yield a product with a rigid, yet
Such baked goods differ considerably from easily fragmented texture. However, a cake mix
bread. In bread making, the object is to work must rise (i.e., expand) during baking to produce
the dough so that it develops a gluten structure; a foam of air bubbles entrapped in baked dough.
i.e., protein molecules within the flour grains are This effect depends upon the creaming power of
encouraged to link up to form long chains and the dough, i.e., its ability to entrap air during
extended sheets, providing the characteristic cel- the mixing process. Here the water phase is an
lular structure of bread. Fat is kept to a minimum asset: not only does water dissolve air during the
260 Margarines and Shortenings Vol. 22
mixing stage but it is also converted to steam have been made to use margarine for the same
during the baking stage, thus increasing the purpose. However, the performance of the two
number and volume of entrapped bubbles. Emul- substances in this application is not the same.
sifiers also enhance the creaming effect, so that Whereas butter can be heated without difficulty
cake margarines and shortenings often have a to the high temperatures required for frying
high monoglyceride content (2 – 5 % compared (140 – 200 C), margarine tends to spatter. Not
to 0.5 % in conventional margarines). This is the only does this cause anything in the vicinity of the
basis for the term high ratio shortenings [17]. frying pan to become covered with fat droplets,
Such a blend permits incorporation at a higher but spattering is also a potential fire hazard, since
level of water into the mix as well as a higher ratio the aerosol of fine fat droplets is highly
of sugar to flour, resulting not only in a greater flammable.
volume increase but also a tenderer crumb and Spattering occurs because the fat crystals that
one that is less liable to go stale on keeping. help to stabilize the emulsion disappear as the
The creaming effect is inhibited by fat blends margarine is heated above its melting range. The
that contain a preponderance of a single glyceride aqueous-phase droplets thus coalesce into rela-
species. Natural lard, for instance, is not ideal for tively large drops. During frying, water is heated
cake making because of its high oleodipalmitin well above its boiling point. Since the water
content, but its performance is greatly improved drops are suspended in liquid oil, there is little
if this glyceride is broken down by interesterifi- chance for the nucleation that would initiate
cation [18]. evaporation. Instead the drops become super-
The characteristic texture of flaky pastry in heated. When nucleation eventually does occur
which thin layers of pastry are separated by layers (e.g., by contact with the walls of the frying pan),
of air, results from a special cake structure in the drops vaporize very rapidly. The result is a
which air is present not in the form of spherical minor explosion as a small volume of liquid
bubbles but as laminae separating continuous water is converted to a significantly larger vol-
layers of pastry. To achieve this the margarine ume of steam over a very short period of time.
or shortening is not intimately mixed into the Spattering is a consequence of numerous drops
flour as in a normal cake mix but remains in undergoing this violent transition over a short
discrete, evenly distributed layers. In one process period of time.
the fat is added to the dough mix in small lumps. In butter the water droplets are stabilized by
The mixture is then rolled out, flattening the encapsulation in casein micelles. Coalescence is
lumps of fat into layers. In an alternative process thus inhibited and the droplets can diffuse to the
the dough is rolled out first and the margarine or surface, where they evaporate as foam. This
shortening is subsequently spread over its sur- desirable state can be approached in margarine
face. A further layer of dough is then rolled on by the use of suitable emulsifiers (e.g., the citrate
top, followed by another layer of fat, and so on. esters of mono- and diglycerides, fatty acid esters
During baking, air and water in the margarine of polyglycerol, and lecithin) [20].
layers expand, forcing the dough layers apart and Low-fat spreads are unsuitable for frying not
producing a flaky texture. Margarine designed only because of their high water content, but also
for this application must be plastic enough to be because the gums or proteins used as thickeners
spread or rolled into thin layers, but not so soft as are denatured at frying temperature and form
to diffuse into the surrounding dough layers unpleasant charred residues on the bottom of the
before starch gelatinization has set these into pan.
flakes. Thus, a fat blend is required that offers Shortenings and frying oils do not contain
a wide range of plasticity but a limited proportion an aqueous phase, so spattering problems do
of liquid oil [19]. not arise. Spattering occurs here only when
water is introduced along with the food that is
to be fried (e.g., as lumps of ice on frozen
5.2. Frying food). In these cases the physical and chemical
properties of the fat blend are thus the only
Butter has traditionally been a popular medium factors to be considered in the choice of a frying
for frying, so it is not surprising that attempts medium.
Vol. 22 Margarines and Shortenings 261
As noted in Section 2.2.7, liquid oils are Economic considerations are also important
unsaturated, and therefore more susceptible to for small-scale commercial fryers, such as res-
oxidation than saturated solid fats. Choice of a taurants, canteens, and fast-food shops. Howev-
suitable blend for frying is therefore reduced to er, a chef is in more direct contact with the frying
achieving a balance between the handling con- process than is the quality control manager of a
venience of a liquid oil and the oxidative stability large frying operation, permitting a quicker re-
of a solid fat. action to changes in product quality. The choice
The domestic user tends to favor liquid oil, of fat is therefore influenced heavily by personal
especially for deep frying. It is easier to heat a pan preference and local tradition.
of liquid oil on a domestic stove than to melt a
block of solid fat. Furthermore, the domestic user
is not overly concerned with oxidative stability, 6. Packaging
since a given batch of oil is only used for a limited
number of fryings. The favorable nutritional Packing units for margarine vary in size from the
properties of liquid oils also have a strong influ- very small individual packs used in restaurants
ence on domestic users. (containing only a few grams of product),
For the industrial fryer, on the other hand, through domestic packs (250, 500 g), larger
oxidative stability is of major importance packs (25, 50 kg) for commercial bakers and
because the useful lifetime of an oil is an impor- caterers, up to tanker loads of several tonnes for
tant economic factor. Industrial frying is a con- industrial users.
tinuous process and is thus dependent upon Wrapping materials for retail packs should
keeping the oxidative state of the oil at an ac- provide a barrier to both light and air to inhibit
ceptable level. Ideally, an equilibrium is attained autoxidative deterioration, and they must be
between removal of used oil from the fryer by impermeable to fat and water to prevent leakage
incorporation into the fried product and addition and consequent spoilage. For hard-blend margar-
of fresh oil; the level of oxidation products in the ines, greaseproof parchment paper adequately
oil in the fryer thus remains constant. The rate of serves the latter purpose, but aluminum foil is
oxidation must be equal to the rate of turnover of also widely used because of its impermeability to
the oil, a requirement that can to some extent be both light and air. Soft blend margarines and low-
met by proper design of the fryer and adjusting fat spreads require rigid containers such as tubs
the rate of throughput of product. Nevertheless, made from plastic or waxed cardboard. In all
the oxidative stability of the oil is also a major cases the packaging material must be devoid of
factor. potentially harmful components that might mi-
Thus, for the industrial fryer, the preferred grate into the contents. Thus, plastic containers or
frying medium is a solid or semisolid fat. Solid wrappers must not contain residual monomers,
fats present a minor inconvenience in that they fillers, or other harmful materials. Appropriate
are liable to congeal in pipelines and holding specifications and tests have been drawn up by
tanks, but this problem is readily overcome by the food regulation authorities (! Foods, 4. Food
installation of suitable heating equipment. Packaging, Chap. 8.).
1985 224 (20) 908 (80) 1132 1226 (44) 1569 (56) 2795
1986 207 (18) 919 (82) 1126 1189 (43) 1587 (57) 2776
1987 165 (15) 925 (85) 1090 1141 (42) 1599 (58) 2740
1988 155 (15) 907 (85) 1062 1081 (41) 1601 (60) 2682
1989 (projected) 147 (14) 900 (86) 1047 1030 (39) 1610 (61) 2640
*
Based on information from the Office of Agricultural Affairs, U.S. Embassy, London, and from Unilever Department of Statistics, Unilever
House, Rotterdam. Values in parentheses indicate percentages of total.
262 Margarines and Shortenings Vol. 22
Table 4. Weekly consumption of spreadable fats (grams per person) in the United Kingdom and the Netherlands*
Low-fat Low-fat
Year Butter Margarine Spreads Total Butter Margarine Spreads Total
F. D. Gunstone: Oils and Fats in the Food Industry, Black- R. D. O’Brien: Fats and Oils – Formulating and Processing for
well, Oxford 2008. Applications, 3rd ed., CRC Press, Boca Raton, FL 2009.
F. D. Gunstone (ed.): Rapeseed and Canola Oil, Blackwell F. Shahidi, A. E. Bailey (eds.): Bailey’s Industrial Oil & Fat
Pub, Oxford 2004. Products, 6th ed., Wiley-Interscience, New York 2005.