Professional Documents
Culture Documents
Beeswax Tensile Properties and Water Vapor Permeability of Sodium PDF
Beeswax Tensile Properties and Water Vapor Permeability of Sodium PDF
www.elsevier.com/locate/foodres
Abstract
Beeswax or a 1:1 blend of stearic±palmitic acids (S±P) were incorporated into gellan ®lms through emulsi®cation to form gellan/
lipid composite ®lms. The ®lms, containing 0±25% lipid (dry ®lm basis) were examined for mechanical properties, water vapor
permeability (WVP) and opacity. Addition of the lipids to gellan ®lms signi®cantly improved the WVP (P<0.05), but lowered the
mechanical properties and caused the ®lms to become opaque. Beeswax was more eective than S±P acids in reducing the WVP,
and ®lms with beeswax showed better mechanical properties overall than those with S±P acids. The tensile properties of gellan ®lms
containing 14.3% beeswax were evaluated as a function of water activity (aw ) of the ®lm. Increasing the aw decreased the tensile
strength (TS) and elastic modulus but tensile elongation was not aected. The extent of the decreases in TS for the composite ®lm
was less pronounced than that for a similar ®lm without lipids, suggesting that lipids help to alleviate moisture sensitivity of gellan
®lms. # 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Gellan; Edible ®lm; Water vapor permeability; Beeswax; Stearic acid; Palmitic acid; Tensile properties; Puncture properties
& Fennema, 1989; Koelsch & Labuza, 1992; Shellham- testing. The thickness of conditioned composite ®lms
mer & Krochta, 1997). Among the lipid materials ranged from 0.07 to 0.09 mm. All treatments were made
investigated, waxes and long-chain saturated fatty acids in duplicate.
and fatty alcohols were most able to eectively improve
the moisture barrier properties of hydrophilic ®lms. 2.3. Tensile tests
However, it has also been reported that incorporation
of certain lipid materials into hydrophilic ®lms has an Tensile strength (TS), percentage tensile elongation
adverse eect on the mechanical and optical properties (TE) at break and elastic modulus (EM) of the ®lm were
of the ®lms. determined at 211 C using an Instron Universal Test-
Gellan, a polysaccharide secreted by the microorganism ing Machine (Model 4502, Instron Corp., Canton, MA)
Sphingomonas elodea (formerly referred to as Pseudo- according to ASTM standard method D882-91 (ASTM
monas elodea), forms an elastic gel in the presence of D882-91, 1991). Seven ®lm specimens, 82.5 cm strips,
cations, and with an appropriate plasticizer the gel can be were cut from each preconditioned (54% RH) ®lm and
dried to form a ®lm. In a previous study, biodegradable/ mounted between the tensile grips. The initial grip
edible gellan ®lms with good clarity and mechanical separation and cross-head speed were set to 50 mm and
properties were been developed, and their basic 300 mm/min, respectively. A microcomputer was used
mechanical and moisture barrier properties were eval- to record the stress±strain curves. Elastic modulus is
uated (Yang & Paulson, 2000). de®ned as the ratio of stress to strain in the initial linear
The major objectives of this study were to develop part of the stress±strain curve, and is a fundamental
gellan/lipid composite ®lms through emulsi®cation and measurement of ®lm stiness.
to determine the eect of the lipids (beeswax and 1:1
blend of stearic±palmitic acids) on the moisture barrier, 2.4. Puncture tests
mechanical and optical properties of the ®lms.
Puncture strength (PS) and deformation (PD) of the
®lm at rupture were determined using a TA.XT2 Tex-
2. Materials and methods ture Analyzer (Stable Micro Systems, Surrey, UK) as
described by Gontard, Guilbert and Cuq (1992). Three
2.1. Materials specimens (4 cm diameter discs), were cut from each
preconditioned ®lm. Each specimen was mounted on
Food grade deacylated gellan gum was donated by top of a cup and a smooth edged cylindrical probe (0.8
Nutrasweet Kelco, Monsanto Co., San Diego, CA. cm i.d.) was moved perpendicularly on the ®lm surface
Glycerol, white beeswax, stearic and palmitic acids were at a constant speed (1 mm/s) until the ®lm broke. A
purchased from Sigma Chemical Co., St. Louis, MO. force±deformation curve was recorded with a micro-
Magnesium nitrate and CaSO4 desiccant (Drierite1, computer for determining force and deformation at
indicating, 8 mesh) were purchased from BHD Inc., rupture.
Toronto, ON, Canada.
2.5. Water vapor permeability
2.2. Preparation of gellan/lipid composite ®lms
Water vapor permeability (WVP) of ®lm was deter-
Gellan ®lm-forming solutions (2%, w/v) were pre- mined gravimetrically at 212 C using the ASTM
pared by dissolving 3.0 g gellan gum in 150 ml distilled standard method E96-93 (ASTM E96-93, 1993), and the
water with constant stirring, followed by heating to 95± WVP values were calculated using the WVP Correction
100 C on a hot plate. 6.0 g glycerol (plasticizer) and an Method described by Gennadios, Weller and Gooding
appropriate amount of lipid were added to the solution (1994). Two specimens, 4 cm diameter discs, were cut
during heating and stirring. After the lipid melted, the from each ®lm. Each specimen was sealed, with the smooth
hot solution was immediately emulsi®ed with a high and shiny side facing up, by a rubber O-ring to the test
speed Polytron Homogenizer (Model PT10/35, Kine- cup (Plexiglas) containing a 10 ml saturated magnesium
matica GmbH, CHE) for 3 min at 27,000 rpm. The nitrate solution (54% RH) leaving a 17.95 mm air gap
emulsion (above 70 C) was then poured onto leveled beneath the ®lm, and placed in an air-tight plastic
and pre-warmed glass plates framed by four glass bars desiccator containing CaSO4 desiccant (0% RH). The cups
(1.55 mm thick) and spread evenly with a glass rod. The were 4.50 cm (i.d.), 5.00 cm (o.d.) and 2.65 cm (depth) with
glass bars were removed after the gel set, and the plates an exposed ®lm area of 15.90 cm2. The water vapour
were then dried in an oven at 40 C for 48 h. The ®nished transmission rate through the test ®lms was determined
intact ®lms were peeled from the glass plates, and all from weight loss of the cups over time. The cups were
®lm samples were conditioned in an environmental weighed to the nearest 0.1 mg at 5 h intervals. The
chamber at 221 C and 54% RH for 3 days prior to steady state of weight loss was reached after 5 h.
L. Yang, A.T. Paulson / Food Research International 33 (2000) 571±578 573
2.6. Film opacity cracking and pinhole formation during oven drying (e.g.
Kamper & Fennema, 1984a,b; Vojdani & Torres, 1990),
Opacity of the ®lms was determined using a spectro- were not observed for gellan/lipid composite ®lms.
photometer (Model PU 8800 UV/VIS, Pye Unicam The appearance of the two composite ®lms with and
Ltd., Cambridge, UK) according to the procedure without vacuum application during ®lm formation was
described by Gontard et al. (1994). Three ®lm specimens compared in preliminary experiments. It was noticed
(14 cm strips) were taken from each ®lm sample and that deaeration of the emulsi®ed ®lm-forming solutions
placed on the inner side of a transparent plastic cuvette. deteriorated, to some extent, stability of the emulsion
The absorption spectrum of the sample was obtained systems, leading to an uneven distribution of the lipids
from 400 to 800 nm. Film opacity was de®ned as the in the ®lm matrix, hence an inconsistent appearance.
area under the recorded curve which was obtained Therefore, deaeration should be avoided during formation
through an integration procedure, and was expressed as of gellan/lipid ``emulsion'' ®lms. Nonetheless, without
Absorbance unitswavelength product (Anm). deaeration, small pores could be present within the ®lm,
which may result in an elevated WVP (McHugh, Aujard
2.7. Film thickness & Krochta, 1994).
A micrometer (Model CD-600 BS, Mitutoyo Co., Japan) 3.2. Water vapor permeability (WVP)
was used to measure the thickness of the conditioned
®lms and the gap depth in the WVP test to 0.001 mm. WVP of the gellan/lipid composite ®lms at various
Six random measurements for each ®lm and gap depth lipid concentrations was evaluated at 0/54% RH. As
were taken and averaged. shown in Fig. 1, addition of the two lipids to gellan ®lms
caused an essentially linear reduction in ®lm WVP.
2.8. Scanning electron microscopy WVP of the ®lms containing 20% S±P acids or 20%
beeswax was decreased by 20 and 53%, respectively, as
Film samples were examined for surface character- compared with that of gellan ®lm without lipid. At the
istics using a Jeol 35C scanning electron microscope same lipid level, WVP of ®lms with beeswax was sig-
(SEM) (Jeol Ltd., Tokyo, Japan) operated at 10 kV. ni®cantly (P<0.05) lower than that of ®lms with S±P
Film samples were axed to aluminum stubs with double- acids.
sided cellophane tape and left at high vacuum overnight. In general, WVP of composite ®lms comprised of
The samples were then sputter-coated with a layer of biopolymers and lipids strongly depend on the type,
gold prior to imaging. structure and quantity of the lipids. For ®lms containing
fatty acids or fatty alcohols, the WVP decreased with
2.9. Statistical analysis increased chain-length and degree of saturation of the
lipids (Hagenmaier & Shaw, 1990; Kamper & Fennema,
Systat (SPSS Inc., Chicago, IL) was used for all sta- 1984a,b; Koelsch & Labuza, 1992; McHugh & Krochta,
tistical analyses. Analysis of variance and Bonferroni
multiple comparisons were performed to detect sig-
ni®cant dierences in ®lm properties at the 5% con-
®dence level.
1994a). Kamper and Fennema (1984a,b) examined the side facing toward the lower RH environment (Avena-
eect of fatty acids on the WVP of hydroxypropyl Bustillos & Krochta, 1993; McHugh & Krochta, 1994a).
methylcellulose (HPMC) ®lm, and indicated that stearic In this study, lipid-enriched sides of the composite ®lms
acid and a 1:1 blend of stearic±palmitic acids were the were faced down to the high RH during the WVP mea-
most eective fatty acids in reducing WVP of the ®lms. surements.
They observed no signi®cant dierence in barrier e-
ciency between the two composite ®lms at the same lipid 3.3. Mechanical properties
concentration. Therefore, S±P acids was recommended
for use in hydrophilic ®lms since these composite ®lms Adequate mechanical strength and extensibility are
are easier to prepare in a laboratory situation (low generally required for a packaging ®lm to withstand
melting point) and have a more consistent appearance external stress and maintain its integrity as well as barrier
than other lipids. properties during applications in packaging. Research
Beeswax was also reported to be an excellent moisture on lipid/hydrocolloid composite ®lms has focused
barrier for wheat gluten ®lms, whey protein ®lms, and mainly on their moisture barrier properties. The in¯uence
cellulose-based ®lms (Avena-Bustillos & Krochta, 1993; of lipid incorporation on the mechanical properties of
Fennema et al., 1994; Gontard et al., 1994; McHugh & hydrocolloid ®lms has not been extensively investigated.
Krochta, 1994b; Shellhammer & Krochta, 1997). In this The TS of the composite ®lms decreased sharply as
study, a 1:1 blend of stearic±palmitic acids as well as concentration of the lipids increased (Fig. 2). For
beeswax were chosen to evaluate the eect of lipids on example, TS of the ®lms with 14.3% S±P or beeswax
the properties of gellan/lipid composite ®lms because of was decreased by 34% as compared with that of the ®lm
their reported high moisture barrier eciency, edibility without lipid. No signi®cant dierence (P<0.05) in TS
and ease in preparation as well as low cost. The results occurred between the two composite ®lms at lipid con-
revealed that both beeswax and S±P acids, at appro- centrations below 14.3%. However, at lipid concentra-
priate concentrations, can eectively reduce the WVP of tions above 14.3%, the ®lms with beeswax had slightly
gellan ®lms, but beeswax was more eective. This higher TS than the ®lms with S±P acids. Tensile elonga-
agreed with the study of Avena-Bustillos and Krochta tion (TE) of the composite ®lms with S±P acids
(1993) for caseinate±lipid composite ®lms. Similar decreased as the concentration of S±P increased,
results have also been reported by Kester and Fennema whereas TE of the ®lms with beeswax changed little as
(1989) and Fennema et al. (1994) who compared the the concentration of beeswax increased (Fig. 3). Addi-
permeance of various lipid ®lms to moisture, and found tion of the two lipids also resulted in marked decreases
that beeswax ®lm had a signi®cantly (P<0.05) lower in both puncture strength (PS) and puncture deforma-
permeance to moisture than stearic acid ®lm at 0/100% tion (PD) of the ®lms as shown in Figs. 4 and 5. As with
RH. According to their hypothesis, the dierence in TS, at lipid concentrations below 14.3%, no signi®cant
barrier eciency between S±P acids and beeswax could dierences in PS and PD were observed between the two
be attributed to their dierent polarity. Although fatty
acids are considered to be hydrophobic substances, their
molecules contain highly polar carboxyl groups that
may interact with water molecules and consequently
facilitate moisture transfer through the ®lm. Beeswax is
a blend of lipid molecules with desirable non-polar
properties. Esters of long-chain fatty alcohols and acids
are the major components, and long-chain hydro-
carbons, free fatty acids and fatty alcohols are the minor
components. Even though polar groups (carbonyl groups
of esters, carboxyl groups of fatty acids and hydroxyl
groups of fatty alcohols) are also present in beeswax,
they are essentially buried within the matrix of long
hydrocarbon chains, and thereby contribute little
polarity (Fennema et al., 1994).
It has previously been reported that ®lm orientation
in the permeability tester has a signi®cant eect on
WVP of composite ®lms resulting from partial emulsion
separation (lipid creaming) during ®lm formation.
Emulsion ®lm oriented with the lipid-enriched side Fig. 2. Tensile strength of gellan/lipid composite ®lms as a function of
facing toward the higher RH environment exhibited a lipid concentration (error bars are standard error of the mean of seven
lower WVP than ®lm oriented with the lipid-enriched measurements from two separate ®lms).
L. Yang, A.T. Paulson / Food Research International 33 (2000) 571±578 575
chains and hence weakening mechanical strength of the highly irregular surface which may have resulted from
®lm. In consideration of both mechanical and moisture greater creaming of S±P acids in the ®lm-forming solution
barrier properties, 14.3% (w/v) beeswax in ®lm-forming prior to setting of the gellan gel. It is unlikely that the
solution is recommended for production of gellan/lipid irregular features were due to entrapped air bubbles
composite ®lms. since each type of ®lm was made by the same procedure.
The dierences in surface structure may have con-
3.4. Opacity tributed to some extent to the dierences in WVP of the
Fig. 6. Opacity of gellan/lipid composite ®lms as a function of lipid Fig. 7. Scanning electron micrographs of gellan ®lm and gellan/lipid
concentration (error bars are standard error of the mean of three composite ®lms containing 14.3% lipid: (a) gellan, (b) gellan/beeswax,
measurements from two separate ®lms). (c) gellan/S-P acids (photo width=171 mm).
L. Yang, A.T. Paulson / Food Research International 33 (2000) 571±578 577
two ®lms. The more highly irregular S±P acids ®lm may hydration would be expected to cause some swelling of
have had a relatively greater eective surface area and the ®lm matrix and changes in ®lm functionality.
shorter eective ®lm thickness for water vapour transmis-
sion than the ®lm with beeswax, resulting in higher WVP.
4. Conclusions
3.6. Eect of water activity on the tensile properties of
gellan/beeswax composite ®lm Gellan/lipid composite ®lms with improved WVP rela-
tive to gellan ®lms without lipids can be made through
Tensile properties of the gellan composite ®lms with emulsion technology. However, the ®lm mechanical
14.3% beeswax over a wide range of water activity (aw ) properties are lowered and the ®lms become more opaque.
were examined. TE of the ®lms appeared to be relatively Beeswax was more eective than S±P acids in reducing the
independent of aw over the aw range tested. Increasing WVP, and ®lms with beeswax showed better mechanical
aw caused continuous decreases in TS and EM (Fig. 8), properties overall than those with S±P acids. Dierences
which was similar to that found for gellan ®lm without in surface characteristics of the ®lms suggest that sur-
lipids (Yang & Paulson, 2000). However, the extent of face microstructure may be partially responsible for dif-
the decreases in TS and EM for the composite ®lms was ferences in WVP of gellan/lipid composite ®lms. Although
less pronounced than for gellan ®lm without lipids. For increased water activity weakened gellan/beeswax com-
example, TS of the ®lm without lipids decreased by 45% posite ®lms, the eect was less than with gellan ®lms
as the aw increased from 0.11 to 0.54, whereas TS of the without lipids suggesting that lipid incorporation can help
gellan/beeswax composite ®lm decreased by 31%. Thus, alleviate moisture sensitivity of gellan ®lms.
addition of the beeswax helped alleviate the sensitivity
of gellan ®lms to moisture. However, it should also be
stressed that the composite ®lms remained intact and Acknowledgement
functional up to aw 0.9. Above aw 0.90, they will
extensively absorb water, become softer and may lose This research was supported by the Natural Sciences
their integrity, which would consequently result in and Engineering Research Council of Canada.
markedly elevated WVP and reduced mechanical
strength. As previously described, beeswax is a nonpolar
hydrophobic substance, but a small number of polar References
groups, such as the ester groups of the wax, hydroxyl
groups of the fatty alcohols and carboxyl groups of free ASTM D882-91 (1991). In Annual book of ASTM standards. Phila-
fatty acids, are hydrophilic. Although the hydroxyl and delphia, PA: Amer. Soc. for Testing & Materials.
ASTM E96-93 (1993). In Annual book of ASTM standards. Philadel-
carboxyl groups are buried within the aliphatic chains, phia, PA: Amer. Soc. for Testing & Materials.
they may, at very high RH, still be able to absorb a Avena-Bustillos, R. J., & Krochta, J. M. (1993). Water vapor perme-
small number of water molecules and hydrate suciently ability of caseinate based edible ®lms as aected by pH, calcium
to in¯uence the functional properties of the ®lm. This cross-linking and lipid content. Journal of Food Science, 58, 904±907.
Chalupa, W. F., Colegrove, G. T., Sanderson, G. R., & Valli, R. C.
(1994). Simple ®lms and coatings made with gellan gum. Research
Disclosure No. 361, p. 244.
Debeaufort, F., Martin-Polo, M., & Voilley, A. (1993). Polarity,
homogeneity and structure aect water vapor permeability of model
edible ®lms. Journal of Food Science, 58, 426±434.
Donhowe, G., & Fennema, O. (1992). The eect of relative humidity
gradient on water vapor permeance of lipid and lipid±hydrocolloid
bilayer ®lms. JAOCS, 69, 1081±1087.
Fennema, O., Donhowe, I. G., & Kester, J. J. (1994). Lipid type and
location of the relative humidity gradient in¯uence on the barrier
properties of lipid to water vapor. Journal of Food Engineering, 22,
225±239.
Gennadios, A., Weller, C. L., McHugh, T. H., & Krochta, J. M. (1993).
Edible coating and ®lms based on proteins. In Krochta, J. M., Bald-
win, E. A. & Nisperos-Carrie, M. O., Edible coating and ®lms to
improve food quality. Lancaster, PA: Technomic Publishing Co.
Gennadios, A., Weller, C. L., & Gooding, C. H. (1994). Measurement
errors in water vapor permeability of highly permeable, hydrophilic
Fig. 8. Tensile properties of gellan/beeswax composite ®lms with edible ®lms. Journal of Food Engineering, 21, 395±409.
14.3% beeswax as a function of water activity of the ®lm: TS, tensile Gontard, N., & Guilbert, S. (1994). Biopackaging: technology and
strength; TE, tensile elongation. EM, elastic modulus (error bars are properties of edible and/or biodegradable material of agricultural
standard error of the mean of seven measurements from two separate origin. In Mathlouthi, M., Food packaging and preservation. Lon-
®lms). don: Blackie Academic & Professional.
578 L. Yang, A.T. Paulson / Food Research International 33 (2000) 571±578
Gontard, N., Guilbert, S., & Cuq, J. L. (1992). Edible wheat gluten Stewart, Water activity: in¯uences on food quality. New York, NY:
®lms: in¯uence of the main process variables on ®lm properties using Academic Press Inc.
response surface methodology. Journal of Food Science, 57, 190±199. Lenovich, L. M. (1987). Survival and death of microorganisms as
Gontard, N., Duchez, C., Cuq, J. L., & Guilbert, S. (1994). Edible in¯uenced by water activity. In L. B., Rockland & L. B., Beuchat,
composite ®lms of wheat gluten and lipids: water vapor permeability Water activity: theory and applications to food. New York, NY:
and other physical properties. International Journal of Food Science Marcel Dekker Inc.
and Technology, 29, 39±50. Leung, H. K. (1987). In¯uence of water activity on chemical reactivity.
Greener, I. K., & Fennema, O. (1989a). Barrier properties and surface In L. B., Rockland & L. R., Beuchat Water activity: theory and
characteristics of edible, bilayer ®lms. Journal of Food Science, 54, applications to food. New York: Marcel Dekker.
1393±1399. McHugh, T. H., & Krochta, J. M. (1994a). Water vapor permeability
Greener, I. K., & Fennema, O. (1989b). Evaluation of edible, bilayer properties of edible whey protein-lipid emulsion ®lms. JAOCS, 71,
®lms for use as moisture barriers for foods. Journal of Food Science, 307±312.
54, 1400±1406. McHugh, T. H., & Krochta, J. M. (1994b). Dispersed phase particle
Hagenmaier, R. D., & Shaw, P. E. (1990). Moisture permeability of size eects on water vapor permeability of whey protein-beeswax
edible ®lms made with fatty acids and hydroxypropyl methylcellu- edible emulsion ®lms. Journal of Food Processing and Preservation,
lose. Journal of Agricultural and Food Chemistry, 38, 1799±1803. 18, 173±188.
Handa, A., Gennadios, A., Hanna, M. A., Weller, C. L., & Kuroda, McHugh, T. H., Aujard, J. F., & Krochta, J. M. (1994). Plasticized
N. (1999). Physical and molecular properties of egg-white lipid whey protein edible ®lms: water vapor permeability properties.
®lms. Journal of Food Science, 64, 860±864. Journal of Food Science, 59, 416±419.
Kamper, L. S., & Fennema, O. (1984a). Water vapor permeability of Park, H. J., Weller, C. L., Vergano, P. J., & Testin, R. F. (1993). Per-
edible bilayer ®lms. Journal of Food Science, 49, 1478±1481. meability and mechanical properties of cellulose-based edible ®lms.
Kamper, L. S., & Fennema, O. (1984b). Water vapor permeability of Journal of Food Science, 58, 1361±1364.
an edible, fatty acid, bilayer ®lm. Journal of Food Science, 49, 1482± Shellhammer, T. H., & Krochta, J. M. (1997). Whey protein emulsion
1485. performance as aected by lipid type and amount. Journal of Food
Kester, J. J., & Fennema, O. (1986). Edible ®lms and coating: a review. Science, 62, 390±394.
Food Technology, 40(12), 47±59. Tulloch, A. P., & Homan, L. L. (1972). Canadian beeswax: analytical
Kester, J. J., & Fennema, O. (1989). Resistance of lipid ®lms to water values and composition of hydrocarbons, free acids, and long chain
vapor transmission. JAOCS, 66(8), 1139±1146. esters. JAOCS, 49, 696.
Koelsch, C. M., & Labuza, T. P. (1992). Functional, physical and mor- Vojdani, F., & Torres, A. (1990). Potassium sorbate permeability of
phological properties of methyl cellulose and fatty acid-based edible methylcellulose and hydroxypropyl methylcellulose coatings: eect
barriers. Lebensmittel-Wissenchaft + Technologie, 25, 404±411. of fatty acids. Journal of Food Science, 55, 841±846.
Labuza, T. P., & Saltmarch, M. (1981). The non-enzymatic browning Yang, L., & Paulson, A. T. (2000). Mechanical and water vapour
reactions as aected by water in foods. In L. B., Rockland & G. F., barrier properties of edible gellan ®lms.