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756

Biotechnol. Prog. 1998, 14, 756765

The Behavior of Hydrocolloid Coatings on Vegetative Materials


V. Hershko and A. Nussinovitch*
Institute of Biochemistry, Food Science and Nutrition, The Hebrew University of Jerusalem,
Faculty of Agricultural, Food and Environmental Quality Sciences, P.O. Box 12, Rehovot 76100, Israel

Coating vegetative materials by gelling agents is a process characterized by four


different time scales. After wetting and penetration of the vegetative skin by the gum
solution, adhesion of the viscous solution to the outer layer (skin) of the coated material
is possible. The gelled film (coating) collapses during further drying and adheres to
the vegetative tissue. Critical surface tensions of the solid object to be coated, its
apparent and real roughness, wettability of the surfaces by the gum solution, the
composition and polarity of the films designed to coat the solid, and the surface tension
of gum coating solutions are among the critical properties that need to be explored
and changed for a successful coating process. The critical surface tensions of garlic
peel and gellan and alginate films (coatings) were evaluated by Zisman plots. Garlic
skin has a low surface tension compared with those of synthetic films such as
polystyrene and polyethylene. A spreading technique was used to determine the
surface tension of the dry film and the solid garlic skin. Surface tension was divided
into dispersive and polar components. The similarity between the coating solution
and the object to be coated in values of dispersive and polar components influences
the spreadability of the coating gum solutions. Better compatibility between the coated
object and the coating films can be achieved by incorporating surface-active agents
within the coating gum solution. From the compatibility requirements detailed above,
it can be concluded that tailor-made hydrocolloid coatings for different vegetative
materials can only be achieved by further exploring the chemical and physical
properties of the coating solutions and the coated objects.

Introduction
Coatings of fruits and vegetables have been known for
many years. The advantages of such coatings have been
reviewed elsewhere (Kester and Fennema, 1986; Nussinovitch and Lurie, 1995; Krochta and De MulderJohnson, 1997; Nussinovitch, 1997). It is estimated that
25-80% of freshly harvested fruit and vegetables are lost
due to spoilage (Wills et al., 1981). One method of
extending postharvest shelf life is to coat fruits and
vegetables with edible films, semipermeable barriers to
water vapor and gas exchange (CO2 and O2) (Baldwin,
1994). Edible coatings can enhance or even replace many
of the techniques used to preserve fresh commodities,
such as controlled atmosphere (CA) or modified atmosphere (MA) (Barkai-Golan, 1990; Smith et al., 1987).
Coatings also improve the mechanical handling properties of fruit and vegetables (Mellenthin et al., 1982), help
maintain structural integrity, help retain volatile flavor
compounds (Nisperos-Carriedo et al., 1990), and can
serve as carriers of additives such as antioxidants and
antimicrobial agents (Kester and Fennema, 1986).
To mimic the natural coating of fruits and vegetables,
wax coatings were developed. However these coatings
inhibited respiratory gas exchange to such an extent that
fermentation was induced. Hardenburg (1967) lists the
commercial uses of wax preparations, e.g. polyethylene
* Corresponding author. Fax: 972-8-947-6189. E-mail: Nussi@
agri.huji.ac.il.
S8756-7938(98)00075-7 CCC: $15.00

wax used to make emulsion coatings for citrus (Kaplan,


1986). A few water-soluble composite coatings composed
of carboxymethylcellulose (CMC) with fatty acid ester
emulsifiers are used for fruits such as pears and bananas
(Drake et al., 1987; Banks, 1984a,b). Sodium alginate
and gellan-based coatings have been investigated by us
(Nussinovitch and Kampf, 1993; Nussinovitch et al, 1994;
Nussinovitch and Hershko, 1996; Hershko and Nussinovitch, 1998a; Kampf and Nussinovitch, 1998). These
hydrocolloid coatings postponed the drying of mushroom
tissue, thereby preventing changes in its texture during
short periods of storage. Coated mushrooms were also
found to have a better appearance and gloss. Coatings
on garlic and onion conferred similar advantages (Nussinovitch and Hershko, 1996; Hershko and Nussinovitch,
1997). Incorporation of ingredients that can be found
naturally in garlic skin (such as -sitosterol) or are
chemically similar to these into the gum solution before
coating improved the adhesion of the film to the surface
of the coated commodity (de-Bruyne, 1939; Nussinovitch
et al., 1994). The strengths of adhesion in such cases
were found to be 25% higher than in those recorded
for a film made of gum and cross-linking agent alone
(Nussinovitch and Hershko, 1996).
In most cases fruits and vegetables are immersed in
gum solutions that are later dried to form a film that
coats the commodity (Banks, 1984b). Not much knowledge is available on coatings based on hydrocolloid
solutions that tend to undergo gelification. In these
cases, the fruit, vegetable, or other food products such

1998 American Chemical Society and American Institute of Chemical Engineers


Published on Web 08/29/1998

Biotechnol. Prog., 1998, Vol. 14, No. 5

as meat, dates, raisins, nuts, and cheese analogue are


coated with thin layers of hydrocolloid viscous solutions.
After the gel sets around the coated object, it undergoes
air dehydration to dry the wet film and adhere it to the
coated commodity, to form an intimate contact between
the produced film and the coated object (Allen et al., 1963;
Earle, 1968, Williams et al., 1978; Torres et al., 1985).
In such cases, the gel, during dehydration, also undergoes
irreversible collapse and tends to shrink in a manner
similar to what was described by Tanaka (1981) and by
Ward and Nussinovitch (1997).
The permeability of coatings, coating techniques, and
compositions of polysaccharide formulations have already
been discussed in the food literature (Greener and
Fennema, 1989; Kamper and Fennema, 1984; Koelsch
and Labuza, 1992; Debeaufort et al., 1993; Krochta and
De Mulder-Johnson, 1997; Nussinovitch, 1997). Less is
known about the relationships between the surface
properties of food and the character of different coating
solutions.
Many theories regarding wetting, surface properties,
contact angles, and surface tension were developed by
chemists and physicists. The idea of measuring surface
tension was introduced to science by Young (1805). We
are familiar with reports relating to food from as early
as 1935 by Mack, who measured contact angles on apple
surfaces, and Hall (1966), who also measured contact
angles on pieces of apple-peel surfaces and briefly
discussed the wettability of plant and fruit surfaces.
These reports and a later manuscripts by Hagenmaier
and Baker (1993) and Hershko and Nussinovitch (1998b)
continue to use these approaches in the area of food
coatings.
The objectives of this study were, therefore, to investigate the surface characteristics of a vegetable skin
(garlic) by examining its macro structure properties, to
estimate its surface free energy, to examine the surface
tension of the coating hydrocolloid solutions before gelification, and to compute the interfacial tension between
the coating solution and the surface of the object to be
coated. To our knowledge, such determinations are
either rare or cannot be found in the food literature,
especially with relation to the art of coating. Such
information is critical for designing a useful coating.

Materials and Methods


Coating Solution. Sodium alginate powder, MW
70 000-80 000, 61% mannuronic acid, and 39% guluronic
acid contents (Nutrasweet Kelco Co., a unit of Monsanto
Co., San Diego, CA) were dissolved in distilled water and
stirred on a magnetic stirrer for 5 h at 20 C. Gellan
(Nutrasweet Kelco Co., a unit of Monsanto Co., San
Diego, CA) was dissolved in distilled water at about 90
C. Dialysis of alginate or gellan solutions against doubly
distilled water was performed using sodium acetate
sleeves (Medicell Int. Ltd., London, England), with a
molecular cutoff of 10 000 Da. Separate solutions were
prepared by dissolving -sitosterol (24-ethylcholesterol,
C29H50O) (Sigma Chemical CO., St. Louis, MO) in the
alginate or gellan solution after it had been dissolved in
5 mL of warm ethanol (at 60 C) (Frutarom Laboratory
Chemicals, Haifa, Israel) and homogenized using an
ultratorex T-25, (Janke and Kunkel, Germany) at 13 500
rpm.
Preparation of Specimens for Contact Angle
Measurements. A. Garlic Skin. Fresh garlic (Allium
sativum) skins, 10 h after harvest, were peeled and
adhered to rectangular pieces of glass (2 cm 6 cm,

757

Figure 1. Schematic representation of contact angle: SV, solid


surface tension; LV, liquid surface tension; SL, interfacial
tension between solid and liquid.

width by length). The circumference area of each piece


was adhered to the glass using a magic tape (Scotch, St.
Paul, MN).
B. Dry Coating Films. Dry films of alginate and
gellan cross-linked by calcium and magnesium, respectively (see below), and combinations of these hydrocolloids with the addition of -sitosterol (0.2% w/w) were
obtained by pouring the hydrocolloid solutions 2.0% (w/
w) into a Petri dish to form layers of 0.15 mm thickness.
The cross-linking agent solutions were sprayed on the
alginate or gellan solutions by a custom-made sprayer
using compressed dry air at a working pressure of 2.5
atm. After 2.0% CaCl2 (Frutarom Laboratory Chemicals,
Haifa, Israel) or 0.2% MgCl2 (Merck, Darmstadt, West
Germany) solutions were sprayed on the surface of the
hydrocolloid solutions for 30 s, the solutions were left for
further cross-linking reactions. After 15 h, the wet
gelled films were taken from the Petri dishes and dried
using a desiccator against saturated solutions of LiCl
H2O (aw ) 0.15) (Labuza et al., 1976) to achieve a
moisture content of 10-15%. Residual moisture was
checked routinely by drying the films at 105 C overnight.
Moisture content was calculated from the weight of the
dry films and expressed as percentage of original film.
Critical Surface Tension of Garlic Skin and Dry
Coating Films. Estimation of the critical surface tension c of garlic skin and dry coating films was attained
by two methods: contact angle measurements followed
by extrapolation from Zisman plots and a spreading
technique. Zisman plots were obtained by plotting the
cosine of the contact angles of pure liquids or binary
mixtures on a solid surface, to be studied against the
surface tension of the same series of liquids (Zisman,
1964). To perform the measurements of the contact
angles, a syringe was filled with 5 L of a particular test
solution after it had been cleaned a few times with the
same solution, and a drop was placed on top of the
specimen. The contact angles ((5) were measured by a
goniometer (NRL C.A. Model 100, Rame Hart Inc., NJ).
A schematic representation of a contact angle () is
demonstrated in Figure 1. All measurements were
conducted in an atmosphere of 60% relative humidity
(RH) and 23 C within 10 s of placing each drop on the
tested garlic skin or film surfaces followed by a second
measurement 60 s later (Allan, 1959; Bikerman, 1970).
The studied liquids for garlic specimens included
water, ethanol, glycerol, ethylene glycol (Frutarom Laboratory Chemicals, Haifa, Israel), 2-ethoxyethanol (Sigma
Chemical Co., St. Louis, MO), binary mixtures of ethanol/
water in volume percentage of 10:90 and binary mixtures
of ethylene glycol/2-ethoxyethanol in volume percentage
of 20:80, 40:60, 60:40, 80:20, respectively, and binary
mixtures of formamide/2-ethoxyethanol in volume concentration of 19:81 and 2.5:97.5, respectively.

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Biotechnol. Prog., 1998, Vol. 14, No. 5

Table 1. Surface Tension Components of the Solutions Used for Characterization of the Garlic Skin and Dry Alginate
Films and Their Spreading Abilitiesa
liquid/solution
water (100%)
formamide
ethylene glycol
ethanol (100%)
2-ethoxyethanol
n-octane
ethanol/water
10/90
70/30
80/20
90/10
96/4
98/2
98.5/1.5
99/1
2-ethoxyethanol/ethylene glycol
20/80
80/20
2-ethoxyethanol/formamide
1/99
81/19
97.5/2.5
n-octane/ethanol
1/99
3/97
5/95
10/90

surface tension
(dyn/cm)

dispersion LVd
(dyn/cm)

polarity LVp
(dyn/cm)

spreading on
garlic skin

spreading on
alginate films

72.8
58.2
48.3
22.7
28.6
21.8

21.8
32.2
29.3
15.8
23.6
21.8

51.0
26.0
19.0
6.9
5.0
0

------+++
+++
+++

--+-+++++
+++

51.3
27.2
25.6
24.0
23.0
25.2
24.9
24.2

20.0
19.4
18.6
17.2
<17.8
<17.8
<17.8
<17.8

31.3
9.7
7.0
6.0
<6
<6.0
<6.0
<6.0

--+-+++++++++ + +***
+++

--+-+++ + +***

30.4
39.6

24.4
27.0

6.0
12.6

-----

+-+ + +***

56.4
31.3
28.8

31.6
24.5
24.0

24.8
6.8
4.8

--+++ + +***

NR
NR
NR
NR

+++
+++
+ + +***
+++

a Data adopted from Dann (1970), Panzer (1973), and Barton (1983). (+++) Total spreading. (- - -) Does not spread at all. (***) CSC,
critical spreading concentration. NR, no reported values.

The tested liquids for dried alginate films were water,


glycerol, ethylene glycol, formamide, methylene iodide
(Sigma), binary mixtures of ethanol/water in volume
percentage of 3:97 and 5:95, respectively, and a binary
mixture of formamide/2-ethoxy ethanol in volume concentration of 99:1, respectively. For the alginate-sitosterol films the tested liquids were water, ethylene
glycol, glycerol, binary mixtures of ethanol/water in
volume percentage of 5:95, 10:90, and 30:70, respectively,
and mixtures of ethylene glycol/2-ethoxyethanol in volume concentrations of 20:80, 40:60, and 60:40, respectively, as well as a mixture of formamide/2-ethoxyethanol
in volume concentration of 19:81, respectively. Each
contact angle measurement was repeated five times, and
the results are the means of these determinations. The
standard deviations were not greater than 5% of the
mean (Figures 2 and 3).
Characterization of the surface tensions of the solid
was also performed by the spreading technique (Marmur
et al., 1987). To perform such a test, a syringe precleaned
by the test solution was filled with 5 L of the same
particular test solution and a drop was placed on the
specimen (garlic skin specimens and dry hydrocolloid film
surfaces had been prepared as described above). The
drop was watched for continuous spreading defined as a
rapid advance of the drop periphery to the lowest possible
contact angle. Beginning with a binary mixture of high
polarity (ethanol/water (10/90) for the ethanol/water
series of liquids for example), the test was performed with
successively lower concentrations of water (in the water/
ethanol solutions), until continuous spreading occurred.
The minimal concentration of the polarless compound at
which continuous spreading was observed was recorded
(Marmur et al., 1980). The tested liquids were water,
ethanol (Frutarom), ethylene glycol (Merck), 2-ethoxyethanol, and formamide (Sigma). Binary mixtures were
composed of ethanol/water in percent concentrations of
10:90, 70:30, 80:20, 90:10, 96:4, 98:2, 98.5:1.5, and 99:1,

respectively. Mixtures of 2-ethoxyethanol/ethylene glycol


were in concentrations of 80:20 and 20:80, respectively.
Mixtures of 2-ethoxyethanol/formamide were in concentrations of 1:99, 81:19, and 97.5:2.5, respectively. Mixtures of n-octane/ethanol were in concentrations of 1:99,
3:97, 5:95, and 10:90, respectively (Table 1). All observations were repeated five times, and results were ranked
in accordance with their spreading as stated above. All
the previously mentioned liquid mixtures were stored in
sealed glass bottles of 1 mL volume to avoid evaporation
before testing.
Determination of the Interfacial Surface Tension
between Coating and Coated Surface. To estimate
the interfacial tension between the coating solution and
the solid skin, contact angles determinations of 1.0% and
2.0% alginate solutions on garlic skin were also used.
This method was applied to the coating solutions to
validate the results obtained from contact angle measurements. Determinations were performed by using the
Bikerman method (Bikerman, 1941). The contact angle
was calculated according to the equation

24 sin3
3
)
V
(2 - cos + cos 3)

(1)

in which is the mean diameter of a drop of a known


volume V. The ratio 3/v was extrapolated to v ) 0, and
the limiting volume was used to calculate the contact
angle ( < 90) from the equation above. These values
can also be derived from the appropriate tables (Bikerman, 1941). The contact angles of the alginate solutions
are also determined using the goniometer as described
previously.
Surface Tension of Coating Solution. The surface
tension of the alginate solutions LV were measured using
the Wilhelmy slide methods (Adamson, 1976). All tested
solutions (see details below) were filtered (0.22 mm

Biotechnol. Prog., 1998, Vol. 14, No. 5

759

Table 2. Surface Tension Results Using Tensiometer


Measurements
solution
alginate
alginate

concn %
(w/w)
1.0
2.0
1.0

alginate
alginate
alginate
alginate

alginate

2.0

dialyzed alginate
dialyzed alginate

1.0
1.0
2.0
2.0

additives

-sitosterol
60 ppm
200 ppm
lecithin
1000 ppm
ethanol
5%
10%
SDS
200 ppm
300 ppm
Tween 80
100 ppm
200 ppm
300 ppm
400 ppm
500 ppm
1000 ppm
ethanol
5%
10%
-sitosterol
2000 ppm
-sitosterol
2000 ppm

surface tension
(dyn/cm)a,b
60.9 ( 3.4
62.0 ( 1.2
56.9 ( 0.3
58.9 ( 0.6
55.6 ( 0.6
53.8 ( 0.6
50.0 ( 0.1
44.8 ( 0.2
41.4 ( 0.2
55.2 ( 0.3
43.9 ( 0.2
42.2 ( 0.2
43.9 ( 0.2
43.6 ( 0.3
36.9 ( 0.3

Figure 2. Zisman plot for garlic skin.

59.2 ( 0.3
53.4 ( 0.3
45.1 ( 0.1
32.7 ( 0.8
51.5 ( 0.2
31.1 ( 0.5

a All surface tension measurements were performed at 21.5 (


1 C. b Each result is the average of five determinations ( SD.

Millipore) to remove solid particles prior to measuring


surface tension. Surface tension was measured with the
Wilhelmy platinum plate (model K-10, Kruss, Hamburg,
Germany). Each sample was equilibrated for a minimum
of 24 h, until a constant value was obtained. The surface
tension readings were within the range of (1 dyn/cm.
To ascertain that the viscosity of the mixtures would not
affect results obtained by the tensiometer plate, measurements of glycerol (known to have a viscosity of 850
cP at 25 C) were performed under the same conditions
and the results were identical to those cited in the
literature (64.9 dyn/cm), indicating that a viscosity of
<850 cP does not affect surface tension measurements
with this technique (Garti and Reichman, 1994). Therefore care was taken to use mixtures with a viscosity of
<850 cP.
Alginate solutions in concentrations of 1.0 and 2.0%
were tested for surface tension, with and without the
addition of sitosterol before and after dialysis. Additives
such as 60 and 200 ppm -sitosterol, 1000 ppm lecithin
(Merck), 5 and 10% ethanol (Frutarom Laboratory Chemicals), 200 and 300 ppm SDS (sodium dodecyl sulfate,
BDH laboratory supplies, Poole, Dorset, England), and
Tween 80 (ethoxylated-20-sorbitan-monooleate, Riedel de
Haen, Seelze, Germany) at 100, 200, 300, 400, 500, and
1000 ppm were added to alginate 1.0% solutions. Additives tested for the alginate 2.0% solutions were 5 and
10% ethanol, and 2000 ppm -sitosterol was tested for
2% dialyzed alginate (see Table 2).
Surface tensions of 1.0 and 2.0% alginate solutions and
the combinations of this hydrocolloid with 0.2% (w/w)
-sitosterol were also tested using the pendent drop
method (Adamson 1976), as demonstrated in Figure 4.
Drops hanging from a capillary tube tip (3.0 mm outer
diameter) were photographed by a video camera (Sony,
Tokyo, Japan) attached to a PC with a video blaster

Figure 3. Zisman plot for dry alginate and alginate-sitosterol


films.

(Creative) RT-300. Data analysis was performed using


a Macintosh IIsi computer and the public domain NIH
Image Program (written by Wayne Rasband at the U.S.
National Institute of Health, Springfield, VA).
The density of the 1.0 and 2.0% alginate solutions was
estimated by a glass pycnometer. All measurements
were performed at 21.5 ( 1.0 C and in an atmosphere
of 60% RH.
Roughness was derived from atomic force microscope
(AFM) micrographs. AFM images were treated using the
public domain NIH-Image version 1.59 NTIS, 5285 Port
Royal Rd., Springfield, VA 22161, part no. PB93 (Hershko
et al., 1997).

Results and Discussion


Most of the studied coatings dealt with drying of a
solution in which the coated object was immersed. Here,
gelification of the coating before drying was performed
and conclusions regarding the time scales involved are
the result of many observations. The coating of a
vegetable skin by a gelling agent solution that requires
later cross-linking by cations involves a process that could
hypothetically be characterized by four successive steps
and time scales. Immersion of fresh produce (garlic
bulbs) in a gum coating solution (not including the
cationic cross-linking agent) could take between 15 s
and 2 min to gain a complete object coating. The
duration depends on the wettability, the concentration,
and the viscosity of the hydrocolloid solution, as well as
on the roughness of the surface and the possible penetra-

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Biotechnol. Prog., 1998, Vol. 14, No. 5

tion of the coating liquid into the biological specimen


(Hershko et al., 1996). The second immersion of the gum
coated bulb (to practically accomplish the cross-linking
of the alginate or the gellan in our study) takes between
30 s and 2 min and depends on the concentration and
temperature of the cross-linking agent and the alginate
or gellan solution, the thickness of the coating gum
solution, and the geometric complexity of the coated
object. The third stage of coating, namely the continuous
strengthening of the gel coating layer, is usually accomplished at a high relative humidity. This is done to
avoid dehydration and to achieve different levels of gel
strengths, depending on duration. This stage can last
between 20 min and 2 h and also depends on the
temperature and the concentrations of hydrocolloids and
other compounds involved. The fourth stage, namely
drying, could result in different dry-film textures and
structures, depending on the duration of drying. When
the coated object is subjected to drying, after a short or
long gelation process, texture and structure vary according to time required for the gelled film layer to lose its
inherent moisture. The properties of the dried films also
depend on the properties of the drying equipment, the
thickness of the coating film and its composition, the Tg
of the polymer, and the final mechanical properties of
the wet film, obtained before the drying process took
place.
The coating process involves wetting of the produce to
be coated by the coating gum solution, possible penetration of the solution into the skin (Hershko et al., 1996),
followed by a possible adhesion between these two
commodities. The wetting stage (spreadability) is, of
course, the shortest and most important one because, if
the suitability of the compound used for spreading and
the object to be coated is ideal, the time interval necessary for such an operation is minimal, or, in other words,
spreadability is spontaneous (Mittal, 1977). Since it is
almost impossible to find hydrocolloid solutions or their
combinations that tend to be absolutely suitable for the
surface properties of the object such as surface tension
and polarity, the user should seek the nearest possible
combination for the achievement of such compitability.
To achieve a successful tailored coating that adheres to
a fruit or vegetable skin, the interfacial tension (SL),
between the coating solution and the vegetable surface
should be estimated. The interfacial tension (SL) depends on the surface tension of the solid skin (SV), the
surface tension of the adherent (e.g., the coating solution)
(LV), and the contact angle () of a specific coating
solution on a solid surface (Adamsom, 1976) according
to the Young equation

LV cos ) SV - SL

(2)

in which denotes surface tension and subscripts L, V,


and S denote liquid, vapor, and solid, respectively (see
Figure 1).
Critical Surface Tension of Garlic Skin. To estimate solid surface tension SV, critical surface tension
should first be calculated. To comply with this requirement, the critical surface tension of the garlic was derived
from Zisman plots followed by extrapolation (Figure 2).
Zisman plots are obtained by calculating the cosin of each
of the measured contact angles of the above listed liquids
(see Materials and Methods) on the garlic skin and
plotting it against the already-known surface tension
values of the solvents and binary mixtures used for this
study (Dann, 1970; Barton, 1983). The combination of
liquids used in this work for the Zisman approach were

chosen after preliminary testing of their ability to produce


drops on garlic skin. Only drops of polar liquids were
not absorbed immediately into the skin and as such were
used for contact angle measurements.
Contact angle measurements were conducted for not
more than 60 s to avoid changes in the tested surface
due to tissue drying.
The critical surface tension of garlic skin is 18.3 ( 2.1
dyn/cm and was extrapolated from Figure 2. The critical
surface tension value is the mean of the extrapolation
product obtained from three independent plots. Correlation coefficients in the range 0.903-0.985 were determined.
It should be noted that critical surface-tension values
had been reported to be lower than the surface tension
values of the same tested surfaces (Dann, 1970). An
example of this common situation is the fact that the
critical surface tension of polyethylene films is 23.3, and
their surface tension has been found to be 27.8 dyn/cm,
a difference of 19.3% (Erbil and Meric, 1988).
Since there is no information on a study of the surface
tension (free surface energy) of vegetative skins, we
decided to estimate those solid surface-tension values by
another method, based on visual observation of the
spreading of liquids with known surface tension and with
partial components of the surface tension, i.e. dispersion
and polarity, upon solid surfaces. Thus, an approximate
value for c, the critical surface tension of a solid can also
be obtained and compared with our results derived from
Zisman plots.
The results of the spreading test are listed in Table 1,
and the critical points marked in the table were defined
in terms of the specific concentration of the polarless
liquid used or complete spreading concentration (CSC)
(Marmur et al., 1987), at which continuous spreading was
first observed. The liquids that were used in the spreading test can be divided into five groups. The first group
contains pure liquids, four of them binary mixtures:
ethanol/water, 2-ethoxyethanol/ethylene glycol, 2-ethoxyethanol/formamide, and n-octane/ethanol. Each of the
binary mixtures mentioned above is based on one polar
compound (water, ethylene glycol, formamide, and ethanol, respectively) and a second less polar compound.
Surface tension is composed of dispersive and polar
components according to eq 3 (Wu, 1974), in which d

LV ) LVd + LVp

(3)

refers to the nonpolar component (dispersion) and p to


the polar one. Dispersive forces are apolar, weak attractions that operate at a relatively long range, in excess of
100 (Owens and Wendt, 1969). Polar interactions are
much stronger than dispersive interactions, can act over
ranges as short as 5 , and require an intimate contact
between the liquid and the solid surface.
Table 1 also includes values of dispersive and polar
components of the surface tension of the above-mentioned
solutions. These values were adapted from manuscripts
written by Dann (1970), Barton (1983), and Panzer
(1973). No information has been found on the polar and
dispersive components of n-octane/ethanol combinations.
The surface tension of all the liquids mentioned in Table
1 (pure or binary mixtures) ranged between 72.8 dyn/cm
for water and 21.8 dyn/cm for n-octane. The spreadability tests indicated that three combinations out of 23
compositions had better spreadability on the garlic skin.
These combinations included a binary mixture of ethanol/
water (98.5:1.5), 2-ethoxyethanol/formamide (97.5:2.5),
and n-octane/ethanol (5:95), respectively.

Biotechnol. Prog., 1998, Vol. 14, No. 5

In the cases of the ethanol/water and ethoxyethanol/


formamide combinations, the surface tension ranged
between 24.9 and 28.8 dyn/cm and the polar components
of the surface tension were between <6.0 and 4.8 dyn/
cm, respectively. The binary mixtures of 2-ethoxyethanol/ethylene glycol did not spread at all on the garlic skin
perhaps due to their relatively high surface tensions.
They ranged between 30.4 and 39.6 dyn/cm, and the polar
component ranged between 6.0 and 12.6 dyn/cm, respectively. These values are higher than the critical surface
tension values derived from the Zisman plot found for
garlic skin.
The fluids of which the third mixture was composed,
namely n-octane and ethanol, were found to have very
close values of surface tension, 21.8 and 22.7 dyn/cm,
respectively, but are totally different in their polarity.
n-Octane is apolar LVp ) 0, and ethanol is polar LVp )
6.9 dyn/cm, comparatively (Marmur et al., 1987).
The mixture of 5:95% n-octane/ethanol spread spontaneously on the surface of the garlic skin, better than
its two pure separate components. The polarity of
ethanol improves the spreadability of the ethanol mixtures with other apolar components, such as n-octane,
due to polar interaction between the surface and the
spreaded liquid.
As a result of the spreading tests, it can be estimated
that the magnitude of the surface tension of garlic skin
ranged between 24.9 and 28.8 dyn/cm and its polar
component is 5.0 dyn/cm. In other words, 17-20% of
the surface tension is due to polarity of the skin (polarity
defined as sp/s). In comparison to commercial polymers
that were defined as polar, poly(vinyl acetate) is as
much as 33% polar and poly(methyl methacrylate) has a
polar component of 28%; poly(dimethylsiloxane) is also
defined as polar, but its polarity is only 4% (Wu, 1973).
To conclude the issue of garlic surface-tension characterization, two experimental methods of estimating solid
surface tension were used. The lower values were
obtained using Zismans approach to critical surface
tensions (namely 16-20 dyn/cm); values of 24.9-28.8
dyn/cm were obtained using the other method (spreading). Since it is widely accepted (Wu, 1979) that Zismans
approach gives lower critical surface tensions, and since
spreadability is influenced by surface tension and polarity
and is considered to be more sensitive than contact angle
measurements (Marmur et al., 1980), the higher ranged
values derived from the spreadability test can be used
for further calculation. Therefore the lowest and highest
extremes from the spreadability test, i.e. 24.9 and 28.8
dyn/cm, were considered.
In general, the spreading results of different liquids
tested on solid surfaces differ in terms of their polar and
dispersive components. Since it is very difficult to find
complete compatibility between the components of the
surface tension of liquid solutions and solid surfaces, the
long list of above-mentioned compounds (see Materials
and Methods) enabled us to define the surface properties
of the solid films (garlic skin or hydrocolloid dry films)
more precisely. Thus, spreading results can give an
estimation of the solid surface-tension ranges but do not
provide exact values of the surface tension and its
components.
Surface Tension of Coating Solutions. Since coating solutions are water-based and contain about 98%
water with surface tension of 72.8 dyn/cm, and taking
into account the low surface-tension value found for garlic
skin, the detection of a suitable water-based coating gum
solution can be very complicated.

761

The surface tension of the coating solutions (LV) plays


a key role in the interfacial tension and is the component
of fruit and vegetables coatings that can be adjusted to
special requirements. The values of the surface tension
of the specific combinations of solutions used for coating
are listed in Table 2. The surface tensions of alginate
solutions in two predetermined concentrations (1 and 2%
w/w) which can be considered as potential coating solutions were measured at a temperature of 21.5 C. The
dissolution of gum in distilled water usually decreases
the surface tension of the water. A decrease of 15.9%
was found for 1.0% alginate solution and of 14.7% for
2.0% alginate solution. Not surprisingly, hydrocolloids
have the potential to lower the surface tension of solutions designated for use as coating agents (Gaonkar,
1991). Many synthetic surface-active agents are more
effective for commercial use than the natural ones at the
same concentrations. As mentioned above, the dissolution of alginate in distilled water led to a decrease in its
surface and interfacial tensions. The same tendency of
lowering surface tension was observed in xanthan gum
solution when surfactants were added to the solution and
the same procedure was followed (Prudhomme and Long,
1983). The surface tension of 1.0% xanthan solution had
been 42.3 dyn/cm and was reduced to 24.3 dyn/cm after
addition of 0.6% sodium lauryl sulfate
Interfacial Tension between Coating and Coated
Surface. Since efficient coating involves good compatibility between liquid and solid surface tensions, (Wu,
1973), our aim was to reduce the surface tension of the
coating solutions to adjust it to the lower surface tension
of the fruit or vegetable skin and to lower the interfacial
tension in order to improve adhesion (Wu, 1973). Among
the tested additives (-sitosterol, lecithin, ethanol, SDS,
and Tween 80), Tween 80 (1000 ppm) was found to be
the most effective in reducing the surface tension of 1.0%
alginate solution from 60.9 to 36.9 dyn/cm, an apparent
reduction of 40%.
The addition of 200 ppm sitosterol and the same
concentration of Tween 80 to 1% alginate solution
decreased its surface tension from 60.9 to 58.9 and 43.9
dyn/cm, respectively. In other words, a small reduction
of only 3.2% was observed for the sitosterol and 27.9%
for Tween (Table 3).
Since the reliability of the common methods for the
estimation of surface tensions of viscous hydrocolloid
solutions has been questioned (Adamson, 1976), an
examination of the results using the pendent drop
method (Adamson, 1976) designed especially for viscous
solutions was inevitable.
In such cases, L is calculated according to eq 4, in
which F is the difference in density between air and the
tested solution, g is the acceleration constant, and 1/H

L )

Fgde2
H

(4)

is quantity achieved from numerical tabulation of S


against 1/H, which was first obtained by Niederhauser
and Bartell (1950). S is equal to ds/de (see Figure 4). We
used this procedure to evaluate the surface tension of
1.0% and 2.0% alginate solutions with and without the
addition of 0.2% -sitosterol. The results were found to
be similar to those obtained using the tensiometer: 62.5
and 65.1 dyn/cm for the 1% and 2% alginate solutions,
respectively, and 52.3 and 49.5 dyn/cm, respectively, after
the addition of the -sitosterol.
In our previous studies (Nussinovitch and Hershko,
1996), it was observed that the addition of -sitosterol

762

Biotechnol. Prog., 1998, Vol. 14, No. 5

Table 3. Calculation of Interfacial Tension between Garlic Skin and Coating Solutions

solution dialyzed
alginate (1%)
alginate (2%)
alginate (1%) + 2000
ppm -sitosterol
alginate (2%) + 2000
ppm -sitosterol
alginate (1%) + 2000
ppm -sitosterol +
Tween (0.25 mL)
alginate (2%) + 2000
ppm -sitosterol +
Tween (0.25 mL)
a

surface
tension
(dyn/cm)

contact
angle
(deg)

interfacial tension
SL (dyn/cm)
(S ) 24.9, r ) 1.05)a

interfacial tension
SL (dyn/cm)
(S ) 28.8, r ) 1.05)a

interfacial tension
SL (dyn/cm)
(S ) 24.9, r ) 1.18)a

interfacial tension
SL (dyn/cm)
(S ) 28.8, r ) 1.18)a

45.15
51.5
32.70

60
81
56

1.19
16.44
5.70

5.09
20.30
9.60

-1.73
15.39
3.32

2.16
19.29
7.22

33.0

51

3.09

6.99

0.39

4.29

29.59

37

0.08

3.98

-2.98

0.91

31.1

62

9.56

13.46

7.67

11.57

SL was calculated from the S and r in parantheses.

was more effective in obtaining better adhesion between


garlic skin and coating films due to better compatibility
in the hydrophobicity of the two adhered surfaces.
The contact angles of hydrocolloid solutions on garlic
skin or any other produce to be coated are critical for the
calculation of interfacial tension between the solid surface
and the coating solution. Therefore the contact angles
were determined using the Bikerman method (Adamson,
1976) and goniometeric measurements. Using the Bikerman method, the contact angles of 1.0% and 2.0%
alginate gum solutions on garlic skin were 82.5 and
83.5, respectively. The results of goniometric measurements for the same solutions were 80.0 and 81.0,
respectively. The addition of sitosterol to the alginate
solutions changed the contact angles as determined by
the goniometeric equipment. Values of 51 for 2.0%
alginate-sitosterol solution and a contact angle of 62
for an addition of Tween 80 were observed. From
preliminaty unpublished data, it can be concluded that
2% alginate solution yields in most cases a more successful coating than 1%; therefore, further details were
verified regarding the former concentration.
Surface Roughness and Its Affect on Spreadability and Interfacial Tension. Spreading is enhanced
by rough surfaces for liquids that have contact angles
smaller than 90 (Oliver and Mason, 1977) and inhibited
by rough surfaces for liquids with contact angles greater
than 90. In the case of 1% and 2% alginate solutions,
the two measurements were <90, so that spreading was
enhanced on the rough surfaces of garlic skin. We found
that garlic is rougher than other fruit or vegetable
surfaces that we have tested in a recently published
manuscripts (Ward and Nussinovitch, 1996; Hershko and
Nussinovitch, 1998a).
Roughness was observed to influence the wettability
of alginate coating solutions; therefore, it was important
to estimate its magnitude. This was performed according
to eq 5, where roughness (r), is defined by

r ) (true surface area/apparent plane area) (5)


Surface roughness has been defined as the ratio of the
true area of the solid to the apparent area. Wenzel (1936)
was the first to propose the relations cos r ) r cos ,
which related the contact angle of a liquid on a rough
surface (r) to the contact angle () of an ideally smooth
surface.
Since garlic skin is far from being an ideally smooth
solid surface, its roughness influences the contact angle.
We have managed to calculate these values by using
AFM data (Hershko et al., 1998) and found the r to range
between 1.05 for the small smoother areas located

Figure 4. Schematic representation of the hanging drop for


the pendent drop method; ds is the diameter measured at a
distance equal to de from the bottom of the drop upward.

between the delicate vascular tubing on garlic skin and


1.18 for rougher areas.
The results of garlic skin surface tensions of 24.9 and
28.8 dyn/cm were used to calculate the interfacial tension
SL according to Youngs equation. The value of the
calculated interfacial tension was found to range between
1.19 and 5.09 for 1.0% alginate and 16.44 and 20.30 dyn/
cm for 2.0% alginate, respectively (Table 3). When
sitosterol was incorporated into the 1 and 2% alginate
solutions, the calculated values of interfacial tension for
both surface tensions of garlic skin were 5.70 and 9.60
for 1% alginate solutions and 3.09 and 6.99 for 2%
alginate, respectively. Addition of Tween 80 to 2%
alginate-sitosterol solution yielded interfacial tension of
9.56 and 13.46 dyn/cm, respectively, for the same solid
surface tensions.
If surface roughness is considered as 1.18 and the
cosine of the contact angle is multiplied by the r value
as proposed by the Wenzel equation (see above), then the
resulting interfacial tension of 1.0 and 2.0% alginate after
dialysis becomes -1.73 and 15.39 dyn/cm, respectively,
for solid surface tension of 24.9 dyn/cm. Although, there
is considerable evidence that zero is the lower limit of
all solid-liquid interfacial tensions (Spelt et al., 1992).
Such small deviations toward negative values were
experimentally reported for much more homogeneous
systems (Schoff, 1992). For S ) 28.8, the calculated
interfacial tension was found to be 2.16 and 19.29 dyn/
cm for 1 and 2% alginate solutions (Table 3). Considering
the r value, the addition of sitosterol to 2% alginate
solution yields an interfacial tension value of 0.39 dyn/
cm. Incorporation of Tween 80 increases the interfacial
tension to 7.67 dyn/cm for S ) 24 and 11.57 dyn/cm for
S ) 28.8 dyn/cm.
It can be concluded from Table 3 that roughness
decreases the calculated interfacial tension due to improvement of spreadability (Oliver and Mason, 1977).
Furthermore, the use of Tween as an emulsifier, although
it increases emulsion stability and contributes to wetta-

Biotechnol. Prog., 1998, Vol. 14, No. 5

763

bility did not reduce the interfacial tension for the 2%


alginate solution. The lowest value of the interfacial
tension was achieved when -sitosterol and Tween 80
were added to 1% alginate solution.
The importance of the magnitude of the interfacial
tension has already been recognized in the polymer
coating industry. For example, polymers such as poly(methyl methacrylate) (PMMA) with a surface tension
of 32.0 dyn/cm and polystyrene (PS) with a surface
tension of 32.1 dyn/cm, both at 140 C, will never spread
on each other because the interfacial tension 1.7 dyn/cm
is greater than the difference between the two surface
tensions, i.e. 0.1 dyn/cm (Wu, 1973).
The interfacial tension SL is an important factor in
wettability. If it is greater than the difference between
the surface tension of the solid and the surface tension
of the solution, no wetting will occur. In other words,
the spreading coefficient G has to be positive to obtain
complete or optimum wettability.

GSL ) S - L - SL

(6)

The greater the positive G value, the greater the free


energy loss when a specific liquid spreads on a specific
solid and the more stable the combination of the two
components to be adhered (Gans, 1966). In the literature
G values range from 50.4 to -26.45 for 88 organic liquids
on water, and no zero value has been found (Harkins,
1952).
We calculated the interfacial tension for all the pure
hydrocolloid solutions tested and their combinations. The
interfacial tension has values higher than the difference
between the surface tension of the solid and that of the
solution (S - L). Therefore, at least from a theoretical
point of view, no optimal wetting of the surface of the
garlic skin can be obtained. In our coating procedure,
which includes immersion of the object to be coated in
the coating solution, wettability is not the most important
criterion; however, avoiding dewetting is of much importance and is a more realistic goal for performance than
wetting. Most coatings will not dewet from a surface once
they have been applied, even though they may not spread
spontaneously if applied as a drop (Schoff, 1992).
The spreading coefficients of the 2% alginate solutions
with and without the 2000 ppm -sitosterol were -43.0
and -11.19 dyn/cm, respectively. It has been reported
previously that such compatibility increased the peeling
force required to separate the coating from the garlic
skin. In other words, addition of 2000 ppm sitosterol can
enhance the adhesion of the film to the object. The
addition of sitosterol also improved the compatibility
toward proven decrease in interfacial tension, resulting
an improvement in adhesion (Nussinovitch and Hershko,
1996; Mittal, 1977).
We are not familiar with previous reports of values of
spreading coefficients on natural organic surfaces determined for hydrcolloid solutions and their combinations
with surfactants or emulsifiers. The literature concentrates on the fields of the paint and polymer industries.
For example, it has been reported that when n-alcohols
or different chlorinated biphenyls (Aroclors) were spread
on -CF2H or silica surface, respectively, the calculated
values of spreading coefficients for the alcohols were
positive when their molecular weight was smaller and
decreased parallel to an increase in their molecular
weight (Gans, 1969). In our case, since ethyl alcohol was
added for the solubilization of sitosterol, to permit its fine
dispersibility in the hydrophilic alginate medium, we
assume that the ethyl alcohol influenced the system not

only by lowering its surface tension but also by achieving


better spreadability as a result of a possible increase in
the spreading coefficient.
The critical surface tension of our dry coating films
derived from a Zisman plot and a spreading technique
was determined similarly to what was performed with
the garlic skin. For 2.0% alginate films and alginate-sitosterol films, values of 44.8 ( 2.9 and 31.8 ( 1.8 dyn/
cm were obtained, respectively (Figure 3). Similar tests
and calculations were repeated for 2% gellan, which was
recognized to have potential use as a coater because as
a dry film it is transparent and strong and has a nice
appearance and gloss (Nussinovitch and Hershko, 1996;
Nussinovitch, 1997). Its critical surface tension, derived
from a Zisman plot, was 32.1 ( 3.1 dyn/cm. When
-sitosterol was incorporated into the 2% gellan solution
before dehydration, to change the surface tension and the
polarity of the films, critical surface tensions of 27.5 (
2.8 dyn/cm were detected for these solid surfaces.
From our study of spreading of 14 different fluids and
binary mixtures (Table 1) on 2.0% dry alginate films, two
mixtures were observed to spread out spontaneously over
the solid. Thus, the ethanol/water mixture at concentrations of 90:10 and a binary mixture of 2-ethoxyethanol/
ethyleneglycol at concentrations of 80:20 were identified
as CSC (Marmur et al., 1987). For an ethanol/water
mixture, surface tension values of 24.0 dyn/cm and the
dispersive and polar component of 17.2 and 6.0 dyn/cm,
respectively, have been previously evaluated by Dann
(1970). For ethylenglycol/2-ethoxyethanol, a surface tension of 30.4 and polar and dispersive components of 6.0
and 24.4 dyn/cm, respectively, have been evaluated
(Dann, 1970). The critical surface tension of alginate film
determined by the Zisman approach and the spreading
tests ranged between 24 and 44.8 dyn/cm. Such a wide
range is maybe the result of the qualitative appreciation.
When these values are compared with the critical surface
tension of the garlic skin derived from the spreadability
test (24.9-28.8), a partial compatibility between the film
and the object to be coated can be concluded. After the
addition of sitosterol, the critical solid surface tension of
the dry alginate films was 31.8 dyn/cm (Figure 3) and a
better compatibility was achieved between the garlic skin
and its coating film.
It is rare to find solid surface tension values of natural
dried hydrocolloid films in the literature. Chitosan films
found to have surface tension of 24.8 dyn/cm and addition
of lauric acid yielded a increase in surface tension to 28.9
dyn/cm (Wong et al., 1992). Synthetic films such as
polystyrene and L-polyethylene have surface tensions of
40.7 and 35.7 dyn/cm, respectively, at 20 C. Natural
films composed of amylopectin, amylose, starch, and
casein were found to have surface tensions of 35.0, 37.0,
40.0, and 43.0 dyn/cm, respectively (Barton, 1983). Gray
(in Gans (1969)) attributed a critical surface tension of
40-45 dyn/cm to wood surfaces, high enough to command
the spontaneous spreading of nearly all organic liquids.
It is interesting to note that our hydrocolloid films,
although different in their nature and properties, had the
same range of solid surface tension.

References and Notes


Adamson, A. W. Physical Chemistry of Surfaces, 3rd ed.; John
Wiley and Sons: New York, 1976; pp 1-43.
Allan, A. J. G. The spreading of liquids on polyethylene film.
The effect of preprinting treatments. J. Polym. Sci. 1959, 37,
297-306.

764
Allen, L.; Nelson, A. L.; Steinberg, M. P.; McGill, J. N. Edible
corn-carbohydrate food coatings. 1. Development and physical
testing of a starch-algin coating. Food Technol. 1963, 17,
1442-1446.
Baldwin, E. A. Edible coatings for fresh fruits and vegetables:
past, present and future. In Edible Coatings and Films to
Improve Food Quality; Krochta, J., Baldwin, E., NisperosCarriedo, M., Eds.; Technomic Publ. Co.: Basel, Switzerland,
1994; pp 25-65.
Banks, N. H. Some effects of Tal Pro-long coating on ripening
bananas. J. Exp. Bot. 1984a, 35, 127-137.
Banks, N. H. Studies of the banana fruit surface in relation to
the effects of Tal Pro-long coating on gaseous exchange. Sci.
Hort. 1984b, 24, 279-286.
Barkai-Golan, R. Postharvest disease suppression by atmospheric modifications. In Food Preservation by Modified
Atmospheres; Calderon, M., Barkai-Golan, R., Eds.; CRC
Press: Boca Raton, FL, 1990; pp 238-265.
Barton, A. F. M. CRC Handbook of Solubility Parameters and
Other Cohesion Parameters; CRC Press Inc.: Boca Raton, FL,
1983; pp 427, 441.
Bikerman, J. J. A method of measuring contact angles. Anal.
Chem.1941, 13 (6), 443-444.
Bikerman, J. J. Physical Surface; Academic Press Inc.: New
York, 1970; pp 1-33.
de Bruyne, N. A. The nature of adhesion. The Aircraft Engineer
XVII; 1939, Vol. 12, p 53.
Dann, J. R. Forces involved in the adhesive process 1. Critical
surface tensions of polymeric solids as determined with polar
liquids. J. Colloid Interface Sci. 1970, 32 (2), 302-319.
Debeaufort, F.; Martin-Polo, M.; Voilley. Polarity homogeneity
and structure affect water vapor permeability of model edible
films. J. Food Sci. 1993, 58 (2), 426-434.
Drake, S. R.; Fellman, J. K.; Nelson, J. W. Postharvest use of
sucrose polyesters for extending the shelf-life of stored Golden
Delicious apples. J. Food Sci. 1987, 52, 1283-1285.
Earle, R. D. Method of preserving food by coating same. U.S.
Patent No. 3,395.024, 1968.
Erbil, H. Y.; Meric, R. A. Determination of surface free energy
components of polymers from contact angle data using
nonlinear programming methods. Colloids Surf. 1988, 33,
85-97.
Gans, D. M. Wetting, spreading and contact angles. J. Paint
Technol. 1966, 38 (497), 322-326.
Gans, D. M. The measurement of equilibrium spreading coefficients of liquids on solids and liquids. J. Paint Technol. 1969,
41 (536), 515-522.
Garti, N.; Reichman, D. Surface properties and emulsification
activirt of galactomannans. Food Hydrocolloids 1994, 9 (2);
155-173.
Gaonkar, A. G. Surface and interfacial activities and emulsion
characteristic of some food hydrocolloids. Food Hydrocolloids
1991, 5 (4), 329-337.
Greener, I. K.; Fennema, O. Barrier properties and surface
characteristics of edible bilayer films. J. Food Sci. 1989, 54
(6), 1393-1399.
Hagenmaier R. D.; Baker, R. A. Reduction in gas exchange of
citrus fruit by wax coating. J. Agric. Food Sci. 1993, 41, 283287.
Hall, D. M. A study of surface wax deposits on apple fruit. Aust.
Biol. Sci. 1966, 19, 1017-1025.
Hardenburg, R. E. Wax and related coatings for horticultural
products. A bibliography. Agric. Res. Bull. 15-51; U.S. Department of Agriculture, Washington, DC, 1967.
Harkins, W. D. The Physical Chemistry of Surface Films;
Reinhold Publishing Co.: New York, 1952.
Hershko, V.; Nussinovitch, A. Physical properties of alginate
coated onion (Allium cepa) skin. Food Hydrocolloids 1998a,
in press.
Hershko, V.; Nussinovitch, A. Relationships between hydrocolloid coating and mushroom structure. J. Agric. Food Chem.
1998b, in press.
Hershko, V.; Klein, E.; Nussinovitch, A. Relationships between
edible coating and garlic skin. J. Food Sci. 1996, 61 (4), 769777.

Biotechnol. Prog., 1998, Vol. 14, No. 5


Hershko, V.; Weisman, D.; Nussinovitch, A. Predetermined
surface topography of fruits and vegetables: a necessary step
for high quality coatings. J. Food Sci. 1998, 63 (2), 317-321.
Kamper, S. L.; Fennema, O. Water vapor permeability of edible
bilayer films. J. Food Sci. 1984, 49 (6), 1478-1481.
Kampf, N.; Nussinovitch, A. Hydrocolloid Coating of Cheeses.
Polymer Networks Program and Abstracts Book. June 28July 3, 1998, Trondheim, Norway, p 61.
Kaplan, H. J. Washing, waxing and color adding. In Fresh Citrus
Fruits; Wardowski, W. F., Nagy, S., Grierson, W., Eds.; AVI
Publishing Co.: Westport, CT, 1986; pp 379-393.
Kester, J. J.; Fennema, O. R. Edible films and coatings: a
review. Food Technol. 1986, 42, 47-59.
Koelsch, C. M.; Labuza, T. P. Functional, physical and morphological properties of methyl cellulose and fatty acid-based
edible barriers. Lebebsm.-Wiss. Technol. 1992, 25, 404-411.
Krochta, J. M.; De Mulder-Johnston, C. Edible and biodegradable polymer films: challenges and opportunities. Food
Technol. 1997, 51 (2), 61-74.
Labuza, T. P.; Acott, K.; Tatini, S. R.; Lee, R. Y. Water activity
determination: a collaborative study of different methods. J.
Food Sci. 1976, 41, 910-917.
Mack, G. L. The determination of contact angles from measurements of the dimensions of small bubbles and drops. 1. The
spheroidal segment method for acute angles. J. Phys. Chem.
1935, 40 (2), 159-167.
Marmur, A.; Narkis, M.; Woogen, W. Characterization of treated
polyolfin surfaces by liquid mixture spreading technique. J.
Appl. Polym. Sci. 1980, 25, 1253-1256.
Marmur, A.; Dodiuk, H.; Pesach, D. The effect of contamination
on adhesive strength: wettability characterization by CSC
method. J. Adhes. 1987, 24, 139-153.
Mellenthin, W. M.; Chen, P. M.; Borgic, D. M. In line application
of porous wax coating materials to reduce friction discoloration of Bartlett and dAnjou pears. Hortic. Sci. 1982, 17,
215-217.
Mittal, K. L. The role of the interface in adhesion phenomena.
Polym. Eng. Sci. 1977, 17 (7), 467-473.
Niederhauser, D. O.; Bartell, F. E. Report of Progress-Fundamental Research on the Occurrence and Recovery of Petroleum;
American Petroleum Institute, The Lord Baltimore Press:
Baltimore, MD, 1950; pp 114.
Nisperos-Carriedo, M. O.; Shaw, P. E.; Baldwin, E. A. Changes
in volatile flavour components of pineapple orange juice as
influenced by application of lipid and composite film. J. Agric.
Food Chem. 1990, 38, 1382-1387.
Nussinovitch, A. Hydrocolloid Applications: Gum Technology
in the Food and Other Industries; Chapman & Hall: London,
1997; pp 176-184.
Nussinovitch, A.; Hershko, V. Gellan and alginate vegetable
coatings Carbohydr. Polym. 1996, 30, 185-192.
Nussinovitch, A.; Kampf, N. Shelf life extension and conserved
texture of alginate coated mushrooms (Agaricus bisporous).
Lebensm.-Wiss. Technol. 1993, 26, 469-475.
Nussinovitch, A.; Lurie, S. Edible coating for fruits and vegetables. a review article. Postharvest News Info. 1995, 6 (4),
53N-57N.
Nussinovitch, A.; Hershko, V.; Rabinowitch, H. D. Protective
Coatings for Food and Agricultural Products. Israel Patent
Application No. 111,495 PCT/US95/14252, 1994.
Oliver, J. F.; Mason, S. G. Microspreading studies of rougj
surface by scanning electron microscopy. J. Colloid Interface
Sci. 1977, 60 (3), 480-487.
Owens, D. K.; Wendt, R. C. Estimation of the surface free energy
of polymers. J. Appl. Polym. Sci. 1969, 13, 1741-1747.
Panzer, J. Components of solids surface free energy from wetting
measurements. J. Colloid Interface Sci. 1973, 44 (1), 142161.
Prudhomme, R. K.; Long, R. E. Surface tensions of concentrated
xanthan and polyacrylamide solutions with added surfacants.
J. Colloid Interface Sci. 1983, 93 (1), 274-276.
Schoff, C. K. Wettability phenomena and coatings. In Modern
Approaches to wettability; Schrader, E. M., Loeb, G. I., Eds.;
Plenum Press: New York and London, 1992; pp 375-397.

Biotechnol. Prog., 1998, Vol. 14, No. 5


Smith, S.; Geeson, J.; Browne, K. M.; Genge, P.; Everson, H.
Modified atmosphere retail packaging of discovery apples. J.
Sci. Food Agric. 1987, 40, 165-178.
Spelt, J. K.; Li, D.; Neumann, A. W. The Equation of State
Approach to Interfacial Tensions. In Modern Approaches to
Wettability; Schrader, M. E., Loeb, G. I., Eds.; Plenum
Press: New York and London, 1992; pp 101-142.
Tanaka, T. Gels. Sci. Am. 1981, 245 (1), 110-123.
Torres, J. A.; Motoki, M.; Karel, M. Microbial stabilization of
intermediate moisture food surface. 1. Control of surface
preservative concentration. J. Food Proc. Preserv. 1985, 9,
93-99.
Ward, G.; Nussinovitch, A. Gloss properties and surface morphology relationships of fruits. J. Food Sci. 1996, 61 (5), 973977.
Ward, G.; Nussinovitch, A. Characterising the gloss properties
of hydrocolloid films. Food Hydrocolloids. 1997, 11 (4), 357365.
Wenzel, R. N. Surface roughness and contact angle. Ind. Eng.
Chem. 1936, 28, 988-993.
Williams, S. K.; Oblinger, J. L.; West, R. L. Evaluation of a
calcium alginate film for use on beef cuts. J. Food Sci. 1978,
43, 292-299.

765
Wills, R. H.; Lee, T. H.; Graham D., McGlasson, W. B.; Hall, E.
G. Postharvest, an Introduction to the Physiology and Handling of Fruit and Vegetables; AVI Publishing Co. Inc.:
Westport, CT, 1981; pp 1-2.
Wong, D. W. S.; Gastineau, F. A.; Gregorski, K. S.; Tillin, S. J.;
Pavlath, A. E. Chitosan-lipid films: microstructure and
surface energy. J. Agric. Food Chem. 1992, 40, 540-544.
Wu, S. Polar and nonpolar interactions in adhesion. J. Adhes.
1973, 5, 39-55.
Wu, S. Interfacial and surface tensions of polymers. J. Macromol. Sci.-Rev. Macromol. Chem. 1974, C10 (1), 1-73.
Wu, S. Surface tension of solids: an equation of state analysis.
J. Colloid Interface Sci. 1979, 71 (3, Oct 1).
Young, Th. Philos. Trans. 1805, 1, 65, 84.
Zisman, W. A. Contact Angle Wettability and Adhesion; Advances in Chemistry. Series No. 43; Americam Chemical
Society: Washington DC, 1964; Chapter 1, pp 1-51.

Accepted August 3, 1998.


BP980075V

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