Materials Letters 246 (2019) 67–70

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Materials Letters
journal homepage: www.elsevier.com/locate/mlblue

Stiff all-bacterial cellulose nanopaper with enhanced mechanical and

barrier properties
Leire Urbina, María Ángeles Corcuera, Arantxa Eceiza, Aloña Retegi ⇑
‘Materials + Technology’ Group, Engineering School of Gipuzkoa. Department of Chemical and Environmental Engineering, University of the Basque Country (UPV/EHU), Pza. Europa
1, 20018 Donostia – San Sebastián, Spain

a r t i c l e i n f o a b s t r a c t

Article history: This work reports on the development of fully bacterial cellulose-derived stiff nanopapers by the infiltra-
Received 30 January 2019 tion of bacterial cellulose nanocrystals (BCNCs) into bacterial cellulose (BC) membranes. The incorpora-
Received in revised form 28 February 2019 tion of the nanocrystals into BC membranes led to a more dense and compacted structure with smoother
Accepted 2 March 2019
surface, improving both, the oxygen barrier properties due to the tortuous path created by the BCNCs, and
Available online 5 March 2019
the mechanical performance. This simple and practical method provides a new approach to make stiff
nanopapers fully derived from BC with potential applications in eco-friendly packaging.
Keywords:
Ó 2019 Elsevier B.V. All rights reserved.
Bacterial cellulose nanocrystals
Stiff
Infiltration
Nanopapers
AFM
Nanocrystalline materials

1. Introduction aspect ratio, low cost, renewability and biodegradability. BCNCs

have been used as reinforcing fillers for hybrid nanocomposites
In recent years, the use of biobased polymers and composites in with potential applications in eco-friendly food packaging [7,8].
packaging materials as an alternative to materials produced from In the present work a completely renewable BC-based nanopa-
non-renewable resources has become a recurring practise. In this per with improved oxygen barrier properties to be used as a stiff
way, cellulose and its derivatives are considered promising packaging layer has been developed. To the best of our knowledge,
biopolymers for food packaging applications [1]. Paper and paper- it is the first work which produces a fully BC-based nanopaper
board are one of the most common packaging materials used, since obtained from agricultural wastes by the infiltration of nanocrys-
can be considered renewable, provide mechanical strength and tals into the BC structure. For this, BCNCs were isolated from pre-
have good printability [2], however, are less durable than plastic viously biosynthesized BC membranes and infiltrated into BC
and present poor barrier properties [3]. The application of nan- membranes. The effective improvement of the quality of the
otechnology in the papermaking science offers the possibility to nanopaper in terms of mechanical strength and oxygen permeabil-
optimizing the paper quality in terms of mechanical strength ity was analyzed.
together with gas barrier properties and processing that would
not be achieved using the traditional microsized pulp papers [4].
Nanocellulose can be obtained from different sources, and con- 2. Material and methods
cretely there is a type of nanocellulose named bacterial cellulose
(BC) which is produced by some bacteria and it is attracting special 2.1. Preparation of bacterial cellulose nanopapers
attention [5]. BC forms characteristic ribbon-like fibrils during
biosynthesis which result in a 3D nano-network conformation Firstly, BC membranes were obtained according to a published
with interesting properties, especially outstanding mechanical protocol using agroindustrial apple residues [9]. Then, these were
properties [6]. Moreover, BC nanocrystals (BCNCs) have attracted mechanically disintegrated in a blender and the gel-like material
a great deal of interest, due to the highly crystalline nature, high was vacuum filtered to remove most of the adsorbed water. The
cellulosic material was treated with sulphuric acid 64 wt% (cellu-
lose/acid ratio: 4.5 g L 1), at 45 °C with stirring for 90 min. After
⇑ Corresponding author. the hydrolysis, the obtained suspensions were diluted with deion-
E-mail address: alona.retegui@ehu.es (A. Retegi). ized water and washed using 4 centrifuge cycles at 4500 rpm for

https://doi.org/10.1016/j.matlet.2019.03.005
0167-577X/Ó 2019 Elsevier B.V. All rights reserved.
68 L. Urbina et al. / Materials Letters 246 (2019) 67–70

20 min. The resulting suspensions were then dialyzed (Spectra/ 40 N m 1. A drop of BCNC/water suspension was deposited onto
PorR 6 MWCO 8000 dialysis membranes) against ultrapure water mica and prepared by spin coating. In the case of BC and BC/BCNC
for 5 days to neutral pH. Finally, BCNC suspensions were freeze- nanopapers, samples were cut in 5  5 mm2 and stuck in mica.
dried. Aqueous suspensions of 0.25 wt% of freeze-dried BCNCs Light transmittance (LT600) at 600 nm was measured using a UV–
were prepared by ultrasonication for infiltration. Subsequently, vis spectrophotometer Shimadzu (UV-3600). The density (q) was
BC wet membranes were vacuum filtered with these suspensions calculated in an Archimedes balance using benzene as solvent
in a Büchner funnel four consecutive times until the filtered BCNC (qbenzene = 0.870 g mL 1). The oxygen transmission rate of the sam-
suspensions became clear. Finally, BC/BCNC nanopapers were dried ples was determined at 50% relative humidity, 23 °C and 760 mm
at 60 °C for three days and then compressed at 10 Ton for 2 min at Hg using an OX-TRAN 2/21 equipment of Mocon following the
room temperature. The approximate BCNCs content in the nanopa- ASTM 3985-10. Oxygen permeability (OP) was calculated consider-
pers was approximately 34 wt%. The weight ratio of BCNCs ing film thickness and gas partial pressure. Mechanical behavior
retained in the nanopapers to the weight of BCNCs added by the (tensile strength (rmax), Young’s modulus (E) and elongation at
infiltration method was 0.76 ± 0.03. break (eb)) was determined at room temperature by tensile tests
in an Instron 5967 with a load cell of 500 N (crosshead rate of
1 mm min 1; 30  5 mm2 rectangular specimens following ASTM
2.2. Characterization
D1708-93 standard procedure). At least five samples were tested,
being the average values reported.
X-ray diffraction was performed by a PHILIPS X’Pert Pro diffrac-
tometer, in theta-theta configuration secondary monochromator
with CuKa (k = 0.154 nm) and a solid state pixel detector, operat- 3. Results and discussion
ing at 40 kV with a filament of 40 mA. The diffractrograms were
collected in the region 2h = 5°–50°, where h is the angle of inci- BCNCs were obtained by acid hydrolysis of BC membranes to
dence of the X-ray beam on the sample. The crystallinity index obtain a high crystalline material with high aspect ratio to produce
(CI) was calculated using the empirical method described by Segal stiff nanopapers (Fig. 1(a)). It was observed that the hydrolysis
et al. [10]. AFM measurements were performed using a Veeco Mul- treatment led to an increase of the crystallinity of the initial BC
timode scanning probe microscope equipped with Nanoscope IIIa membrane, being the crystallinity indexes 0.80 and 0.86 for neat
Controler in peak force mode in the case of the BCNCs and in tap- BC and BCNCs, respectively (Fig. 1(b)). In addition, the morphology
ping mode in the case of the nanopapers. All measurements were of isolated BCNCs was studied by AFM (Fig. 2(a)). BCNCs with
recorded using TESP type silicon tips having a resonance frequency 17.0 ± 3.1 aspect ratio (L/D) were obtained (length of
of approximately 340 kHz and a cantilever spring constant about 741 ± 269 nm).

Fig. 1. (a) Production process of stiff nanopapers and (b) XRD patterns and CI of BC and BCNCs.
 L. Urbina et al. / Materials Letters 246 (2019) 67–70 69

Fig. 2. AFM height, phase and 3D height topographic images of (a) BCNCs, (b) BC and (c) BC/BCNC nanopaper.

Table 1
Density, light transmittance, oxygen permeability and mechanical properties of neat BC and BC/BCNC nanopapers.

Sample q (g mL 1) LT600 (%) OP (cm3 mm m 2

day 1
atm 1
) E (MPa) rmax (MPa) eb (%)
BC 1.24 ± 0.07 33.4 ± 2.7 25.0 ± 2.0 7151.5 ± 215.3 116.9 ± 17.0 2.5 ± 0.3
BC/BCNC 1.35 ± 0.18 20.1 ± 2.4 1.4 ± 0.5 8067.7 ± 913.5 159.6 ± 53.4 3.6 ± 1.1

AFM was used to analyze the morphology of the surface, and nanopapers are better than the ones reported in the literature for
images and average roughness values are shown in Fig. 2(b) and other biopolymers usually employed in food packaging applica-
(c). As it can be observed, the incorporation of BCNCs resulted in tions: PLA 15–25, PHB 2–10 and PHBV 5–14 cm3 mm m 2 day 1-
a more dense structure as BCNCs occupied the spaces between atm 1 [14]. This suggests that the nanopaper could be used as a
large nanofibers of BC, suggesting that the surface was covered base material for the development of multilayer structures for
by BCNCs (Fig. 2(c)). This fact was confirmed by the densimetry packaging applications.
results, which indicate that the nanopapers exhibit higher density From the mechanical point of view, the incorporation of BCNCs
values than the neat BC (Table 1). Therefore, it seems that the BC led to an improvement of 11% of the modulus and 37% of the
sheet showed a more continuous structure with the incorporation tensile strength (Table 1). The improvement of the tensile proper-
of BCNCs. Lower roughness value was obtained for the nanopaper ties depends on the affinity between the matrix and the nanorein-
sample being the half of the one of neat BC sheet (Fig. 2). This fact forcement and the homogeneous dispersion of the last. In this
is important when thinking of applying coatings, since the struc- work, BC membranes with 34 wt% of BCNCs were obtained and
ture of a base paper is crucial to obtain homogenous composites the improvement of the tensile properties was probably the result
[11]. Additionally, the incorporation of BCNCs to the BC membrane of: (1) the suitable filling of the interstices between the nanofibers
led to a loss of transparency (Table 1, LT600 values), which was of the 3D network of the BC membrane by the BCNCs and (2) the
probably related to both, increase of crystallinity and density. strong hydrogen bonding formation between the hydroxyl groups
The barrier properties of nanopapers were analyzed through gas of the nanofiber matrix and the BCNCs. These results suggest that
permeation measurements with O2 and the results are presented the infiltration method used in this work was appropriate to obtain
in Table 1. As it can be observed, the OP of the nanopaper was stiffer BC nanopapers.
18 times lower than the one of the neat BC. This result suggests
that the incorporation of the BCNCs into the BC nanonetwork hin-
ders the passage of oxygen molecules through it, as it has been 4. Conclusions
observed in AFM images that the nanopapers’ structure is denser
and more compacted. Usually, the decrease of OP is ascribed to In this work BC-derived stiff nanopapers with proper oxygen
the increase in the tortuous path of oxygen and reduced porosity barrier properties which could be used as base materials for mul-
created by the nanoentities [12,13]. OP values obtained for the tilayer packages have been developed. The vacuum infiltration of
70 L. Urbina et al. / Materials Letters 246 (2019) 67–70

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