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Synthesis and characterization of silver nanoparticles impregnated into

bacterial cellulose

Article  in  Materials Letters · April 2009

DOI: 10.1016/j.matlet.2009.01.007

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 Materials Letters 63 (2009) 797–799

Contents lists available at ScienceDirect

Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Synthesis and characterization of silver nanoparticles impregnated into

bacterial cellulose
Luiz Claudio de Santa Maria a,⁎, Ana L.C. Santos a, Philippe C. Oliveira a, Hernane S. Barud b,
Younés Messaddeq b, Sidney J.L. Ribeiro b
a
Departamento de Química Orgânica, Instituto de Química, Universidade do Estado do Rio de Janeiro, Rua São Francisco Xavier, 524, CEP 20550-900, Rio de Janeiro/RJ, Brazil
b
Instituto de Química, Universidade Estadual Paulista — UNESP, CEP 14800-900 Araraquara/SP, Brazil

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

Article history: This article presents a study about the synthesis of colloidal silver (Ag)/biopolymer where Ag submicron
Received 12 July 2008 particles were prepared in situ on bacterial cellulose (BC) produced by Gluconacetobacter xylinus. Different
Accepted 6 January 2009 reducing agents were compared (hydrazine, hydroxylamine or ascorbic acid) together with the influence of
Available online 10 January 2009
gelatin or polyvinylpyrrolidone (PVP) employed as colloid protectors. Particle size distribution and
morphology were investigated by scanning electron microscope (SEM). SEM images show silver
Keywords:
nanoparticles (40–100 nm) size range attached on (BC) microfibrils. XRD analyses confirmed the Ag cubic
Bacterial cellulose
Silver nanoparticles
phase deposited on to BC fibrils. The ash contents determined by thermogravimetric analyses have indicated
Nanocomposites high level of silver loading on the obtained composites.
Electron microscopy © 2009 Elsevier B.V. All rights reserved.

1. Introduction In this work, silver nanoparticles were impregnated into bacterial

Cellulose produced by Gluconacetobacter xylinus is markedly
different from cellulose obtained from trees and cotton. Bacterial
cellulose (BC) is obtained free of lignin and hemicellulose, in a 3-D
network composed of a bundle of much finer microfibrils of
nanometric size. BC is an interesting material for using as a wound
dressing since it provides moist environment to a wound resulting in a
better wound healing [1,2]. However, bacterial cellulose itself has no
antimicrobial activity to prevent wound infection [3].
Silver powders having ultrafine and uniformly distributed sizes are
of large current use in chemical industry, electronics, medicine due to
singular properties such as high electrical and thermal conductivity,
high resistance to oxidation, and also bactericidal action (colloidal
silver). Silver is a durable (persistent) biocide with high temperature
stability and very low volatility compared to other usual biocide
agents, such as iodine [4]. Polymer nanocomposites containing metal
nanoparticles can be prepared by different methods: mechanical
mixing of a polymer with metal nanoparticles; the in situ polymer-
ization of a monomer in the presence of metal nanoparticles; or the in
situ reduction of metal salts or complexes in a polymer [5,6]. The
literature describes out many methods to prepare ultrafine silver
powders [7–10], including the formation of Ag nanoparticles attached
on bacterial cellulose [3]. Barud et al. have produced spherical metallic
silver particles with mean diameter of 8 nm well adsorbed onto the BC
fibrils utilizing triethanolamine (TEA) as chelating-reducing agent [6].
⁎ Corresponding author. Tel.: +55 21 2587 7631.
E-mail address: santamaria@pesquisador.cnpq.br (L.C. de Santa Maria).
cellulose through the chemical reduction by immersing bacterial
cellulose in the silver nitrate solution. In situ Ag+ reduction by different
reducing agents in the presence of colloid protective agent is investigated.
2. Experimental
2.1. Materials
BC membranes were supplied by Fibrocel — Produtos Biotecnológicos
Ltda. (Ibiporã, Brazil). Others reagents were used as received.
2.2. Ion anchorage and Ag+ reduction
BC membranes were previously treated with AgNO3 0.06 M
aqueous solution at room temperature during 24 h. BC/Ag+ mem-
branes were then treated with different reducing agents in aqueous
solutions containing 0.2% wt/v of PVP or gelatin. Aqueous solution
(0.06 M) of NH2NH2, NH2OH or ascorbic acid (C6H8O6) containing 0.2%
wt/v of PVP or gelatin were slowly added to the BC/Ag+ immersed in
PVP or gelatin aqueous solution at pH 13–14. Resulting membranes
were dried in air at 100 °C. The membranes (BC/Ag0) were named
according to the reductant used as shown on Table 1.
2.3. WAXD characterization
X-ray diffraction patterns (XRD) were obtained in a Siemens
Kristalloflex diffractometer using nickel filtered CuKα radiation from
4 to 70° (2θ angle).

0167-577X/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2009.01.007
798 L.C. de Santa Maria et al. / Materials Letters 63 (2009) 797–799

Table 1
Identification of the BC/Ag0 Composites; silver contents and particle average sizes of the
BC/Ag0 composites

BC/Ag0 composites Ag (%)a Range of particle average size (nm)b

C0AA (C6H8O6 without colloid protector) 25.0 70–100
C0HZ (NH2NH2 without colloid protector) 22.4 N 100
C0HX (NH2OH without colloid protector) 11.3 N 100
CGAA (C6H8O6 and gelatin) 19.6 50–70
CGHZ (NH2NH2 and gelatin) 4.9 40–60
CGHX (NH2OH and gelatin) 7.8 30–50
CPAA (C6H8O6 and polyvinylpyrrolidone) 6.0 20–50
CPHZ (NH2NH2 and polyvinylpyrrolidone) 4.9 80–100
CPHX (NH2OH and polyvinylpyrrolidone) 8.0 70–100
a
Estimated from the residue of thermogravimetry.
b
Determined by microscopy analysis.

2.4. Thermogravimetric analyses

Thermogravimetry (TG) was conducted using dried samples in a

SDT 2960 equipment from TA Instruments. Samples were heated in
open alumina pans from 40 to 600 °C, under static air atmosphere,
50 mL min− 1, at heating rate of 10 °C min− 1. The silver content of the
BC/Ag composites was estimated from the residue.

2.5. SEM characterization of the samples

Scanning electron microscopy images were obtained with a FEG-

SEM JSM 6330F at the LNLS (Brazilian Synchroton Light Laboratory).
Samples were coated with a 3 nm thick carbon layer.

3. Results and discussion

It is well known that the polymers can act as reducing and/or covering agents, thus,
preventing particle growth in metal colloids preparation [4–6]. In order to investigate Fig. 1. SEM micrographs of dried BC (a) and BC/Ag composites obtained with hydrazine
the influence of the type of colloid protector and the reducing agent on the formation of without colloid protector (b).
silver particle structure and silver incorporation, the reduction reactions were carried
out at the same conditions (reagents concentration, temperature, addition rate of
reducing agent). Grey colored homogenous membranes were obtained in all cases. Fig. 1 hand, dissimilar profile of silver particles was observed on the BC composites prepared
shows SEM images of the dried BC membrane and a typical composite obtained from with PVP as colloid protector with the same reducing agents (Fig. 3a and c). In this case,
the Ag+ reduction without protective agent. the silver particles have agglomerated in clusters larger than 100 nm with no defined
The redox potentials of the three reducing agents are more negative than that of silver morphology. In addition, the inner structures of these composites have also presented
ions [10,11], suggesting easy reduction to Ag0 what was indeed observed under the very small silver particles (around 100 nm). These results could be attributed to the
experimental conditions used. The OH− addition has an important role on the reduction colloid protector efficiency. It is important to note that the Ag+ reduction process has
reaction of metallic ions. It is possible to increase the reducing power of these compounds place in the solution, where are the reductant and colloid protector. Hence, the
under alkaline conditions compared to their standard reducing potentials [10]. It also protector colloid action has an important role during the silver particles formation.
implies that there is an energy barrier to this reduction reaction. However, when OH− is Table 1 shows the values of particle average size measured by microscopy analyses and
present, the silver conversion increases spontaneously and this conversion is proportional silver content estimated from the residue obtained of thermogravimetry. Analyzing the ash
to the quantity of OH− added to the reaction system, leaving to the AgOH precipitation and contents of the composites determined by thermogravimetry, it seems that the ascorbic
consequently produces Ag2O [12]. Huang and co-workers [12] used the term “auto- acid was the most efficient reductant. However, it was also noted that the use of any colloid
catalytic” reaction to describe the reduction of silver in the presence of colloids. It is
possible that the reduction of Ag+ to Ag occurred on the surface of existing colloids in the
system. Thus, for the initiation of the electroless (autocatalytic) metal deposition process
on dielectrics and other non-catalytic materials (e.g. bacterial cellulose), their surface is
modified by metal-catalyst particles forming catalytically active centers. This process is
known as “surface activation” [13]. SEM images for BC-silver nanoparticles without colloid
protectors (Fig. 1) revealed non-spherical and non-homogeneous silver nanoparticles
attached in to BC microfibril. Therefore, theses images confirm that BC is able to stabilize
silver nanoparticles in to 3-D nanostructure [6].
Representative X-ray diffraction for BC–silver nanoparticles with and without
colloid protectors (Fig. 2) confirms silver particles formation on to BC membrane. Ag
cubic phase was clearly identified from diffraction peaks at of 38.1, 44.3, 64.4
[crystallographic planes (111) and (200), (220), respectively], indicating the face
centered cubic (FCC) structure [14].
Fig. 3 depicts the SEM micrographs of some typical silver composites produced on
BC membrane using two different reductants (namely, hydroxylamine or ascorbic acid)
and two different colloid protector agents (namely, gelatin or PVP). These micrographs
evidence the silver nanoparticles presence on the synthesized composite membranes
surface. It is shown by SEM-FEG micrograph (Fig. 3a), that the primary particle size of
silver in the colloid is around 50 nm. As a rule, these particles are clustered with a size
up to 100 nm.
Fig. 3 shows that the Ag particles on the BC composites surface present two
different features. It is possible to see spherical nanoparticles (Fig. 3b and d) randomly
dispersed on the BC surface of composites prepared by the reduction with ascorbic acid
and hydroxylamine, respectively, both in the presence of gelatin. Actually, few clusters
of Ag particles were observed on preferential regions of their surfaces. On the other Fig. 2. XRD analyses of: a) BC/Ag0 prepared without PVP, b) BC/Ag0 prepared with PVP.
 L.C. de Santa Maria et al. / Materials Letters 63 (2009) 797–799
Fig. 3. SEM micrographs of the BC/Ag composites obtained with colloid protector — a, b, c and d (BC/Ag composites obtained with hydroxylamine/PVP, ascorbic acid/gelatin, ascorbic
acid/PVP and hydroxylamine/gelatin, respectively).
protector has diminished the silver content. This result could be explained by the not
anchored fine silver particles produced during the reduction process. In a general way, the
silver particles obtained in the presence of colloid protector (mostly with gelatin) were
smaller than those obtained without it (C0AA, C0HZ and C0HX composites), indicating that
these agents were able to control the silver particle growth. As shown in this table, smaller
silver particle sizes were attained when gelatin was employed compared to PVP, indicating
that the gelatin was better to control the particle size.
The micrographic analyses of inner structures and external surfaces of the BC/Ag
obtained from the Ag+ reduction in the presence of gelatin (CGHX sample) depicted on
Fig. 3d show clearly morphology features of spherical silver particles. This micrograph
shows clearly that the colloid protector has an important role on avoiding the silver
particle coalescence of the CGHX composite compared to the composites prepared
without it (Fig. 1).
4. Conclusions
The silver particle distribution and their sizes on the BC–Ag0
composites depend on the combination of type of reducing and colloid
protector agents used during their syntheses. The ascorbic acid was
the most efficient reductant for Ag+ among the reductants used, and
the colloid protector, particularly gelatin, has an important role on
avoiding the silver particle coalescence and particle size control
anchored on the BC membrane.
Acknowledgments
We would like to thank financial support of Brazilian agencies FAPERJ
(Proc. No. APQ1 E-26/171.289/2006), FAPESP, CAPES and CNPq (Proc.
View publication stats
799
CNPq no. 473687/2008-9). LME/LNLS for technical support during
electron microscopy work and Fibrocel — Produtos Biotecnológicos Ltda.
for the BC membranes supply.
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