Food Biophysics (2011) 6:106​–​114 DOI 10.

1007/s11483-010-9181-0
ORIGINAL ARTICLE

Thermal, Mechanical and Microstructures Properties of

Cellulose Derivatives Films: A Comparative Study
Norma Espinoza-Herrera ​& R
​ uth Pedroza-Islas ​& E
​ duardo San Martín-Martinez ​& A
​ lfredo Cruz-Orea ​&
Sergio Armando Tomás
Received: 6 December 2009 /Accepted: 12 October 2010 /Published online: 21 October 2010 ​© ​Springer Science+Business Media, LLC
2010
Abstract ​The proposal in this study was to evaluate the physical properties of different biopolymers films. The
materials used were: pectin, carboxyl methylcellulose, methylcellulose, hydroxyl propylcellulose, hydroxypropyl-
methylcellulose, and corn waxy starch; from these poly- saccharides aqueous dispersions were prepared to 3% (​w​/​v​)
for obtained films. In these biopolymer films, the thermal diffusivities (​α​) was evaluated by the Open Photoacoustic
Cell method; also, their mechanical properties as tensile strength, elongation, and Young​’​s modulus were measured,
their crystallinity percentage was evaluated by X-ray diffraction and microstructure through atomic force micros-
copy in contact mode. From the polysaccharide films, it was observed that most of them were flexible and
transparent. In the case of the films, mechanical properties were found that the highest value of tensile strength and
Young​’​s modulus corresponded to carboxyl methylcellulose with 69.17 and 1,912.20 MPa values, respectively. Also,
Open Photoacoustic Cell method and X-ray diffraction measurements showed that there exist a correlation between
the thermal diffusivity values and the crystallinity measured in the biopolymer films. It was also observed that ​α
values of cellulose derived was affected by the substitution group in the molecule, reaching the highest ​α ​value, the
films of carboxyl methylcellulose. Regarding the microstructural of the films, starch showed the highest roughness
value (88.6 nm) whereas hydroxypropyl-methylcellulose resulted with the lowest roughness value (7.67 nm).
N. Espinoza-Herrera Facultad de Química,
.​ .​ .​
Keywords ​Photoacoustic ​ Carboxyl methylcellulose ​ Hydroxyl propylcellulose ​ Hydroxypropyl ​Universidad
Autónoma del Estado de México, Paseo Colon esq. Paseo Tollocan s/n,
.​ .​
methylcellulose ​ Pectin ​ Starch
50120 Toluca, Estado de México
R. Pedroza-Islas
Introduction ​Departamento de Ingeniería y Ciencias Químicas, Universidad Iberoamericana, Prolongación Paseo de la Reforma 880,
Mexico CP 01210 DF, Mexico
A considerable interest exists to use natural polymers, generally used in the daily diet, for preparing active principles
of specific action in the colon, since they are ​E. San Martín-Martinez (​*​) Centro de Investigación en Ciencia Aplicada y
Tecnología Avanzada del Instituto Politécnico Nacional, Calzada Legaria 694, Col. Irrigación CP 11500 DF, Mexico
safer materials and also more available than the synthetic ones,​1 ​they also possess cost-effectiveness and broad
regulatory acceptance. Delivery of sensitive bioactive ingredients to the colon is a common practice in the ​e-mail:
esanmartin@ipn.mx
.​
pharmaceutical industry and is drawing growing attention ​A. Cruz-Orea​ S. A. Tomás Departamento de Física, Cinvestav-IPN
apartado postal 14-740, 07360 Mexico, DF, Mexico
in the food ingredients industries.​2 ​An enteric cover should protect from the effect of severe conditions in the
gastrointestinal tract, including the acid nature of the
stomach (pH 1​–​2), the pH of 6.1​–​8 of the intestine and theembedding in biodegradable matrices in which the matrices of
presence of bile and pancreatic enzymes.​2​,​3 ​The pharma-polysaccharides are assumed to remain intact in the
ceutical industry used various approaches for the develop- mentphysiological environment of stomach and small intestine but
of colon-targeted drug delivery systems, one of them is:once they reach in the colon, they are acted upon by the
bacterial polysaccharidases and results in the degradation of the bacteria with optionally modified resistant starch as a carrier
matrices.​4 and growth medium to alter the gastrointestinal tract microbial
In this sense, the use of diverse polysaccharides aspopulations has resulted in a number of signifi- cant
advantages, such as protection of probiotics, and as a carrier to
pectin and their salts, also amylosa,​4 ​dextrin, guar,​5
delivery economically and efficiently to specific sites.​13
hydroxylpropylmethylcellulose ftalato, hydroxylmethyl-
cellulose,​6 ​quitosano,​7 ​shellac,​8 ​carboxylmethylcellulose,​9 However, the information on other physical character-
10 ​
acetate of cellulose ftalato,​ inulina and cyclodextrins, among istics as the thermal and structural properties is scarce. The
others, it has been investigated exploring their potential to be materials used to elaborate coverings should be able to form
21 ​
used in the liberation of drugs in the colon​11​–​13 ​and also theuniform films,​ where the selections of the components during
design of functional ingredients that should be present in thethe formation of the film, plays a fundamental role in the
colon in enough quantity in order to exercise their beneficialdetermination of its properties.
effect, as the case of probiotic microorganisms.​14 The homogeneity of films constituted by biopolymers should
be closely monitored. This can be done by atomic force
Pectins belong to a group of substances generally
microscopy (AFM) in order to obtain images of the coating
termed dietary fibers, which are the essential part of the plant
surfaces.​2 ​It is desirable that the films have good mechanical
and have numerous beneficial effects on human health.​15
properties to assure their integrity and their resistance during
Pectins, as other dietary fibers, are not digestible by
the handling, and also they should be transparent.​22 ​Other
endogenous enzymes, but they are fermented total or partially
by colon microflora and act as prebiotics, thus modifying the important film characteristics are in function of the materials to
cover, for example, when the active principle is sensitive to the
composition of colon microflora.​16 ​In vitro experiments
heat, it would be desirable that the cover has low thermal
demonstrate that high methoxy pectin, when applied as a
diffusivity​23​; mainly in the case when the cover process involve
compression coat, proved capable of protecting a core table
during conditions simulating gastrointestinal environment and heating. The crystallinity, measured by X-ray diffraction, indi-
was susceptible to enzymatic attack. However, in the in vivo cates the proportion of orderly regions where the chains of
conditions, a coat of considerable thickness was required to polysaccharides form the first clusters, after they increase their
24
protect the drug core. Due to its water solubility, pectin needs size, giving the formation of crystalline regions as a result.​
structural modifications for its utility in targeted delivery.​13 The polymeric films must be capable of resisting considerable
stress without fractures, and appropriate elongation during the
Cellulose derivatives have promising applications in
microencapsulation process by dried aspersion.​25 ​Tensile
food industry, pharmaceutics and other technological
strength, elongation, and elastic mod- ulus (Young​’​s modulus)
applications by the fact that they are low-cost biodegrad- able
can be used to describe how the mechanical properties of films
materials and their films are flexible, resistant, and transparent.
are related to their chemical structure.
However, the mechanical and moisture barrier properties can be
improved; studies performed in hydrox- ypropyl Each polymer used as enteric cover has specific
methylcellulose (HPMC) films when they were cross-linkedphysical properties, and often it is difficult that a single
with acid citric improved the hygroscopic, mechanical, and polymer posse the profile required by the material to cover
hydrophilic properties, also when they were loaded with (drugs, microorganisms, and functional ingredients) as well as
nisin-acquired antimicrobial properties.​17 ​Other studies withfor the specific liberation mechanism. Then, frequently they
HPMC improved their mechanical properties by reinforcing theshould be elaborated by combinations of biopolymers to
films with microcrystalline cellulose, at nano-scale level, whengenerate a cover with the desirable physicochemical
characteristics. Due to this fact, it is necessary to determine the
compared with those elaborated with only HPMC.​18 ​Films
properties of each biopolymer, to select the appropriate
formed with methyl- cellulose MC, which is derived from less
material, and also to propose mixtures of the same
hydrophilic cellulose, when added cellulose nanoparticles at
biopolymers. In the present investigation, films made mainly
0.25%, improved the mechanical and water vapor barrier
from cellulose derivatives were studied because it is
properties.​19
biodegradable, has safer materials, and also more available; in
Starch has been evaluated for colon-targeted delivery as
those materials, the mechanical and thermal (thermal
enteric-coated capsules.​20 ​The administration of probiotic
diffusivity) properties as well as the crystallinity grade and
microstructural topography of the films were evaluated.
Food Biophysics (2011) 6:106​–​114 107
Experimental
Materials
HPMC (Pharmacoat 606G 2910, USP/NF Shin-Etsu Chemical Co., Ltd. Tokyo, Japón), was kindly provided (by
Nutrer S.A. de C.V., México); carboxymethyl cellulose sodium (CMC; CMC-7LF PH, DS: 0.65​–​0.95.
Aqualon®Cellulose gum) and hydroxypropyl cellulose (HPC; Klucel-LS®Hydroxypropylcellulose) were kindly
provided by Hércules de México S.A. de C.V. México; pectin citrus of high methoxyl, rapid set (P) was acquired
from Central de Drogas S.A. de C.V., México; waxy corn starch (S; Thermflo) was provided by Tecnovam, S.A. de
C.V.; MC (Methocel A15) was provided by Colorcon de México S. de R.L. de C.V.
Films Preparation
Single-component aqueous dispersions (3% ​w/​ ​v​) of biopolymer materials were prepared with a mixer (IKA
Labortechnik RW 20.nS1, IKA Works Malaysia) at 3,000 rpm, at different conditions as showed in Table ​1​. The
dispersions were then degassed by vacuum to remove bubbles that could eventually form pinholes during film
drying. Finally, 20 ml of each dispersion was spread onto plates of Teflon with 11 cm internal diameter, which were
placed horizontally at room temperature (20 °C) during 24 h or until they were completely dried.​20 ​The obtained
films were kept in polyethylene bags.
Film Thickness
The film thickness was measured by a digital micrometer (model IDC-112CB, Mitutoya Corp., Tokio Japan) at five
different positions of the sample and the average thickness was taken for each film.
Mechanical Properties
The film mechanical properties were determined by tensile test, through a texturometer TA.TX Plus (Stable Micro
108 Food Biophysics (2011) 6:106​–​114
Systems, Godalming, UK), using ten replicates for each material. The film mechanical resistance, including tensile
strength (TS) and elongation percentage (E) at breakpoint, was measured uniaxially by stretching the specimen (60×
20 mm), in one direction, at 5 mm/min. Also the tensile modulus (Young​’​s modulus, YM) was calculated. The films
were maintained at room temperature (20 °C) and 53% of relative humidity (by using saturated salt solutions of
magnesium nitrate) during 36 h before the measurements.
X-ray Diffraction and Crystallinity
The X-ray diffraction patterns were taken by a Siemens D5000 diffractometer operating at 35 kV with CuK​α ​(​λ​=
1.5418Å) radiation, at 25 mA. The diffractograms were recorded from 5° to 50° on the 2​θ ​scale at 2.0°/min speed.
The crystallinity percentage was defined as the ratio of the area under the crystalline diffraction peaks to the non-
coherent diffracted intensity. The non-coherent intensity was obtained by subtracting the sharp diffraction peaks
from the total diffraction intensity.​21
Thermal Diffusivity (​α​) Measurements
The Open Photoacoustic Cell (OPC) technique​22 ​was used to obtain the ​α ​values of the films. The OPC experimental
set-up consisted of a 100 mW Ar-ion laser whose light beam was modulated by a mechanical chopper and directed
onto the sample. Since the films are optically transparent, it was necessary to attach 14-​μ​m aluminum foil to them by
using thermal silicon paste. Then the film sample, with the attached aluminum foil, was fixed on the electret micro-
phone by using vacuum grease. The microphone output signal was amplified with a lock-in amplifier, and the
photoacoustic (PA) signal amplitude and phase were measured as a function of chopper frequency (​f)​ . The PA signal
was generated either by thermal diffusion or the thermoelastic bending effect depending of the sample
characteristics. In the case of thermal diffusion and thermally thick sample, i.e., when the sample thickness (​l)​ is
larger than the thermal diffusion length (​α​/(​π​f​))​1/2​, the thermal diffusivity can be obtained by fitting the PA signal
()
​ Þ​exp ​À​af 1​​ /​2 ​
​ ⁄4 ​A​/​f ð
amplitude to the expression (​1​): ​S 1
ð​1​Þ
Here, ​A d​ epends on the light beam intensity, room temperature, geometric constants, and thermal parameters. The
 coefficient ​a i​ s related to the thermal diffusivity according to ​a​=​l(​ ​π​/​α​)1/2​
​ , indicating that ​α ​can be obtained from the
frequency dependence of the PA signal amplitude. When the PA signal is generated in high-modulation frequencies
by the thermoelastic bending effect becomes to
Table 1 ​Conditions to prepare the dispersions
Material Solution temperature (°C) Time of heating (min)
A 83 50 MC 50 35 HPC 38 20 HPMC 20 5 CMC 50 10 P 50 10
be the main contribution in the PA signal. In the OPC configuration, the thermoelastic bending mechanism pre- dicts
a ​1/f f​ requency dependence on PA signal amplitude,​23 ​which was observed also in these measurements. In the
thermally thick regime, ​l>>(​α​/​πf​ )​1/2​, the expression of the PA signal phase (​8​) for the thermoelastic bending signal is
p​ þ ​arctan ​ 1
​ ,​24 ​8 ​1⁄4 ​ 2 ​
shown in Eq. ​2​.17​ ( ​z ​À ​
1
)
ð​2​Þ
​ ​, indicating that ​α ​can be also obtained from the frequency dependence of the PA signal phase.​24
where, ​z=l (​π​f/​α​)1/2
Surface Characterization by AFM
The surface microstructure of the carbohydrate films was analyzed by AFM (digital version, model CPR) in contact
mode. For this measurement, central and outlying sections of each film were taken. A tip of silicon nitride, 11 ​μ​m
lengths and a bend radius of 5 nm, was used. The scan frequency was 1 Hz. The force applied between the sample
and the tip was 10 nN. The used cantilever had a spring constant of 0.06 Nm​−​1​.
Statistical Analysis
All treatments were performed randomly. Analysis of variance and Tukey​’​s test were performed using Minitab
version 14 statistical software.
Results and Discussion
Film Mechanical Properties
The films, elaborated with derived of cellulose, showed desirable physical characteristics as transparency, brilliancy,
and flexibility although not all showed the same mechanical characteristics (see Figures ​1​, ​2​, ​3​). The mechanical
properties commonly reported to characterize films are TS and YM.
The results showed that the highest value for TS corresponded to CMC with 69.17 MPa, followed by HPMC and MC
with 40.81 and 30.16 MPa, respectively and the lowest value corresponded to pectin with 9.26 MPa (Figure ​1​).
Significant statistical differences (​p< ​ 0.05), for TS, were observed among films derived of cellulose (CMC, MC, and
HPMC films), while were not observed significant differ- ences in this parameter for films of starch, pectin, and
HPC. The observed differences among the cellulose derivatives films could be due to the type and the degree of
substitution (DS) in the biopolymer. The ether group confers certain mechanical resistance and elasticity to the films
derived of
Food Biophysics (2011) 6:106​–​114 109
80 70605040302010​
0​ Starch HPMC CMC Pectina HPC MC
Fig. 1 ​Tensile strength for each polysaccharide film
cellulose when this group interacts with the solvent. Higher values of DS weaken the film structure. This fact agrees
with the TS results for CMC and MC films in which the degrees of substitution were 0.7 and 1.2​–​2.2, respectively.
The Figure ​2 ​shows the ​E r​ esults for the different polysaccharides films. The film with the smallest ​E ​value was
elaborated with S base by other hand the HPC film had the highest ​E ​value. The ​E ​values obtained from S, HPMC,
P, and MC films did not show significant statistical differences (​p< ​ 0.05); however, statistical differences were
observed with respect to CMC and HPC films. The CMC and HPC films did not show significant differences (​p< ​
0.05) between them. The obtained ​E ​results are in agreement with those reported by Debeaufort and Voilley,​16 ​where
they indicate that the elongation is increased mainly when the films become rubbery. The CMC and HPC films
maintained their rubbery characteristics after drying in comparison with S and P films which showed a rigid
structure. HPMC and MC films maintained an intermediate structure between rubbery and rigid.
16

14​) %(n oitagnol​ 12108642​

E​ 0S HPMC CMC P HPC MC
Biopolymers
Fig. 2 ​Elongation (E) of each polysaccharide film
2500
2000
A HPMC CMC P HPC MC
Biopolymer
Fig. 3 ​Young​’​s modulus for each film
derivatives in general have polymorphous crystallinity and when they are processed diminish their crystallinity.​27
The CMC, HPMC, and MC have a high proportion of amorphous
1500
structure and also a natural partial crystallinity,​28​–​30 ​like all natural polymers.​31​,​32
1000
Table ​2 ​shows these percentages, where it is observed that CMC film had the highest value among the films ​500
derived of cellulose. The mechanical properties from the derived films of cellulose seem to have some correlation ​0
with the crystallinity because higher crystallinity values correspond to better mechanical properties, as observed in
the TS and YM results.
The pectin film, with high crystallinity, showed a ductile polymer behavior which suggests that substitution groups
Elastic modulus is the ratio of stress to strain over the
play a very important function in the structural organiza- linear range and measures the intrinsic stiffness of the film.
tion. The pectin is able to form a gel; this property is When the number of bonds between molecules has been
determined by intrinsic factors as its molecular weight and increased, the film flexibility decreased.​25 ​Figure ​3 ​shows
its etherification degree. Pectin films were transparent but that the smaller YM values correspond to pectin and HPC
with slight yellowish tone. It is known that the pectin of films, which indicate that these structures are fragile when
high methoxyl degree requires the addition of solids that compared with the other samples, suggesting that these
compete for water in order to favor the interactions between other samples have a bigger intra- and inter-molecular
polysaccharides. In this case, however, there were no solids interaction. The CMC films retain their elastic property,
added; but during the film formation, the colloidal polymer probably because the CMC maintains some interaction
with
particles coalesce into the film, which occurs concurrently the water without losing the intra- and inter-molecular
during the evaporation. interactions between the polymers.
The film crystallinity percentage of waxy starch (6.11%) Figure ​4 ​shows the stress-deformation curves for each
had a similar value to the HPMC film, however, they film. In agreement with Gibson and Ashby​26​, the forms that
showed different mechanical properties; this fact indicates acquire these curves, are correlated directly with structural
that it is necessary to use different parameters in order to characteristics of the polymer. The differences in behavior
characterize the studied samples, since one parameter alone of film mechanical properties are related to the
composition
would not explain the behavior of the films. and chemical structures of the polymers and their interac-
On the other hand, it was observed in the cellulose tion with the water, forming films after drying.
derivates, as MC, HPC, HPMC, and CMC, that an increment in the molecular weight of the substitution group Film
Crystallinity
of the polymer corresponds also to an increment in the film crystallinity percentage. The film crystallinity
percentages were obtained by using
By using the classification proposed by Gibson and X-ray diffraction. The XRD patterns of cellulose and
Ashby,​26 ​the studied films can be classified as indicated in Table ​2​. Group A refers to lineal elastic polymers; they
are
70
 60​) aPM(e croFs sert​ 5040302010​
S​ 00 1 2 3 4 5 6 7 8 9
Distance (mm)
Table 2 ​Film crystallinity percentage and classification ​Pectin Starch HPC
Polysaccharide film Crystallinity (%) Classification
HPMC CMC MC
S MC 6.11 D 4.19 D HPC 2.93 D HPMC 6.74 B CMC 13.64 A P 17.10 C
A f​ ragile fracture, glassy polymer; ​B o​ nset of plasticity, pseudo ductile polymer; ​C ​extensive cold drawing, ductile polymer; ​D u​ niform
Fig. 4 ​Tensile stress distance curves of polysaccharides films
viscous flow, rubbery polymer
110 Food Biophysics (2011) 6:106​–​114
hard, being in a glassy state. Group B contains the polymers90,000 Da, while for the case of
that change from rigid to ductile, characterized by to yield point HPC film, with an average molecular weight of 95,000 Da, the
followed by rapid drop in your load. Group C refers to obtained ​α ​value was ​a 1⁄4 ​0​.​6732 ​Â ​10​À​3 ​cm​2​s​À​1​; for MC
inhomogeneous cold drawing with extensions, which are large.film, whose molecular weight ranges from 40 to 12,000 Da, the
The polymers in group D are homogeneously deformed in aobtained ​α ​value was similar to the HPC film, i.e., ​a 1⁄4 ​0​.​5931
viscous process, living to large extension to failure.​16 Â ​10​À​3 ​cm​2​s​À​1 ​(see Table ​3​), while the HPMC film, whose
molecular weight ranges from 12,000 to 20,000 Da, had a ​α
Thermal Diffusivity value statistically similar to CMC film.
The interaction ability with water is other factor that
The obtained results for thermal diffusivities (​α​) of could influence the thermal diffusivity parameter. It is well
polysaccharide films are shown in Table ​3​, being also included known that cellulose is not soluble in water, which is attributed
the film thickness. The thermal diffusivity indi- cates the rate atto the existence of an intra- and intermolecular extensive
which a substance warms or cools down during a thermalcrystalline domains, formed by hydrogen bridges, generating a
treatment, its importance as a physical parameter is due to the heterogeneous structure, with crystalline and amorphous
fact that this value is characteristic for each material, indicatingdomains, where the water can interact with the amorphous
a strong dependence on the chemical composition anddomains and almost excluded from crystalline regions.​35 ​The
structure,​33 ​as well as the sample porosity and density which presence of substitution groups modifies the molecular
have an effect on the crystallinity degree. structure of cellulose, modifying its interaction with water and
It was observed that the thickness of films were similar, also its properties.​36
while the thermal diffusivity showed important variations for Also, the thermal diffusivity differences between the
the studied polysaccharides (​P< ​ 0.05), evaluated throughCMC and MC films could be influenced mostly by the degree
Tukey​’​s tests of average comparisons. It was observed that ​α of substitution that by hydrophobicity of group methyl, since
values corresponding to MC and HPC films were similar, by the used CMC has a smaller DS (0.7) compared with MC
other hand P, CMC, and HPMC films did not present (1.1​–​2.2). This could explain the difference in crystallinity
significant differences in this parameter and finally the thermal values (see Table ​2​) and the relationship with the value of
diffusivity of S film has an intermediate value, being similar to
thermal diffusivity. Mc Crystal et al.​37 ​studying the distribution
HPMC and CMC. A general analyses of the thermal diffusivity
of water in cellulose ethers, found that MC is the cellulose
results indicated that higher thermal diffusivity values
derivative with smaller capacity to absorb water and also they
correspond to higher crystallinity percentage.
indicated that the quantity of water bounded is related with the
Stolik et al.​34 ​found a linear dependence between the ​α degree and the substitution type of the biopolymer chain.
values and the number of carbon atoms for the case of an
The pectin film showed the highest thermal diffusivity
aliphatic chain, however, for samples of cellulose deriva- tives,
of the studied samples ​a 1⁄4 ​1​.​6321 ​Â ​10​À​3 ​cm​2​s​À​1 ​ð Þ ​and the
which in general corresponds to linear molecules constituted by
film of waxy starch, with a ramified molecule that possesses
one homopolysaccharide, it seems to be decisive the effect of
one of the higher molecular weight found in the nature, ranging
substitution groups. For example, one of the bigger obtained ​α
from 10,000,000 to 500,000,000 Da,​38 ​have also one of the
value was observed for CMC film ​a 1⁄4 ​1​.​4728 ​Â ​10​À​3 ​cm​2​s​À​1
À​3 ​ 2​ À​1 ​
ð Þ​, this biopolymer has an aver- age molecular weight of higher obtained ​α ​value ​a 1⁄4​1​.​1224 ​Â ​10​ cm​ s​ ð Þ​. This
type of starch contains amylpectin almost entirety; its structure
consists mostly of crystalline regions, where the heat flux iswhen compared with the other samples.
bigger,​39 ​this could explain its high value of thermal diffusivity
Food Biophysics (2011) 6:106​–​114 111
Topography and Microstructure of Polysaccharides Film
The film topography and microstructure was characterized by
112 Food Biophysics (2011) 6:106​–​114
the average roughness and half height of the films, considering
their central and outlying regions, obtained from AFM images
and presented in Table ​4​. It was observed that higher values of
half height correspond to more roughness, independently of the
biopolymer type. In accordance with Dimantov et al.,​3 ​a higher
roughness corresponds to non-homogeneous structures.
Table 3 ​Film thickness of the studied polysaccharides and their obtained
thermal diffusivity values (​α​)
​ ​(×10​−​3 ​cm​2​s​−​1​)
Material Thickness (​μ​m) α
S 65.80 1.1224​b​±0.042 MC 63.90 0.5931​a​±0.141 HPC 65.25
0.6732​a,b​±0.12 HPMC 70.50 1.4457​b,c​±0.24 CMC 65.80 1.4728​b,c​±0.219
P 65.40 1.6321​c​±0.230
From the film topographies, it was possible to corrob-
orate differences in microstructure in the same sample, due to
the different roughness observed in the film central or outlying
regions. This fact was more evident in pectin films (Figure ​5a,
b​) where it was observed that P film has a rougher structure in
the central region compared with the outlying region. The
superficial microstructure of starch films (Figure ​5c​) shows a
smoother structure with some bigger depressions that form
holes.
From the AFM images of the cellulose-derivative films,
a higher roughness in CMC and HPC films, only in the film
central regions, was observed when compared with MC and
HPMC films. Although the images seemingly denote a bigger
roughness, the average height and the distances between the
peaks and valleys are small, and then a small roughness is
obtained.
In the cellulose-derivative films, the roughness and the
average height seem to be in function of the substituent
Table 4 ​Average roughness and half
height of film samples
on
 Average roughness (nm) Half height (nm) Average Roughness (nm) Half height (nm)

S 88.6 278 48.3 429 CMC 52.1 207 47.2 233 HPC 62.9 230 43.7 216 MC 7.91 30.7 5.48 46.4
HPMC 7.67 17.2 5.14 17.1 P 13.5 38.4 19.9 122

a) b)

c)

Fig. 5 ​Pectin film topography of ​a ​central region and ​b ​outlying region, and ​c ​starch film
type, this is, the MC films have the smallest values of surface characteristics which finally are very important in the
roughness and average height and the films of HPC and CMCfilm properties.​32
have the higher values for these parameters.
It is also evident that the average height values are, in
the most of cases, bigger in the film outlying region than in the Conclusions
central part, while the roughness was smaller in the outlying
region. This rougher structure in the central region is probablyThe cellulose-derivative films showed different physical
due to a smaller transfer of mass and consequently a slower properties which depend on the substituent type. These
speed of drying in the central part when compared with the differences are reflected in their thermal, mechanical, and
external region, then it is probable that polysaccharides filmsmicrostructural properties. From the measured properties, it is
have time to form a more added structure that drives to the possible to select the more suitable film for some application,
formation of more pores and as a consequence more roughness for example to cover medical and nutritious compounds in
in the central part.​40 order to preserve their functional activities. Among the studied
Due to the diverse structures showed by the cellulose- polymers, the CMC film presents the better mechanical
derivative films, it is evident that the substituent type has a properties, higher values of crystallinity, and thermal
great influence in the film structures which can be observed indiffusivity, followed by HPMC film, the other studied
Figure ​6a​–​d​. polymers are not homogeneous which diminish the values of
these properties. The pectin films have poor mechanical
From AFM results, it is possible to observe that the
properties, although higher values of thermal diffusivity and
ordination of polymer chains as well as its chemical structure
crystallinity, finally the starch film is very
will define its internal structure and also the
Food Biophysics (2011) 6:106​–​114 113

a) b)
 c) d)

Fig. 6 ​3D images of film surfaces (20×20 ​μ​m) elaborated with cellulose derivatives: ​a ​MC, ​b ​CMC, ​c ​HPC, and ​d ​HPMC
rigid and fragile with an intermediate thermal diffusivity value, Pharmaceutical University. ​18​, 395​–​397 (2001) 7. Z. Wakerly,
compared with the other polymers. The films elaborated with J.T. Fell, D. Attwood, D. Parkins, Int J Pharm ​153​,
mixtures of polysaccharides and proteins could present better 219​–​224 (1997) 8. N. Pearnchob, J. Siepmann, R. Bodmeir, Drug
mechanical, thermal, and microstructural properties due to the Dev Ind Pharm ​29​,
synergy effect among them. 925​–​938 (2003) 9. B. Arica, M.Y. Arica, H.S. Kas, A.A. Hincal,
V. Hasirci, J
Microencapsul ​13​, 689​–​699 (1996) 10. S.Y. Lin, Y.L. Tzan, C.J.
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