Cellulose-Based Bio - and Nanocomposites: A Review

Hindawi Publishing Corporation International Journal of Polymer Science Volume 2011, Article ID 837875, 35 pages doi:10.
1155/2011/837875
Review Article Cellulose-Based Bio- and Nanocomposites: A Review

Susheel Kalia,1 Alain Dufresne,2 Bibin Mathew Cherian,3 B. S. Kaith,4 Luc Av rous,5 e 6 and Elias Nassiopoulos6 James Njuguna,
1 Department
of Chemistry, Shoolini University of Biotechnology and Management Sciences, Bajhol-173 229, District Solan (Himachal Pradesh), India 2 Grenoble Institute of Technology, The International School of Paper, Print Media and Biomaterials (Pagora), Grenoble Institute of Technology, BP 65-38402 Saint Martin dH`res, Grenolde, France e 3 Department of Natural Resources, Sao Paulo State University (UNESP), Botucatu 18610-307, SP, Brazil 4 Department of Chemistry, Dr. B.R. Ambedkar National Institute of Technology, Punjab, Jalandhar 144011, India 5 LIPHT-ECPM, EAC (CNRS) 4375, University of Strasbourg, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France 6 School of Applied Sciences, Craneld University, Bedfordshire MK43 0AL, UK Correspondence should be addressed to Susheel Kalia, susheel [email protected] Received 16 June 2011; Accepted 1 August 2011 Academic Editor: Jose Ramon Leiza Copyright 2011 Susheel Kalia et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Cellulose macro- and nanobers have gained increasing attention due to the high strength and stiness, biodegradability and renewability, and their production and application in development of composites. Application of cellulose nanobers for the development of composites is a relatively new research area. Cellulose macro- and nanobers can be used as reinforcement in composite materials because of enhanced mechanical, thermal, and biodegradation properties of composites. Cellulose bers are hydrophilic in nature, so it becomes necessary to increase their surface roughness for the development of composites with enhanced properties. In the present paper, we have reviewed the surface modication of cellulose bers by various methods. Processing methods, properties, and various applications of nanocellulose and cellulosic composites are also discussed in this paper.
1. Introduction
Cellulose-ber-reinforced polymer composites have received much attention because of their low density, nonabrasive, combustible, nontoxic, low cost, and biodegradable properties. A lot of research works have been performed all over the world on the use of cellulose bers as a reinforcing material for the preparation of various types of composites. However, lack of good interfacial adhesion, low melting point, and water sensitivity make the use of cellulose-berreinforced composites less attractive. Pretreatments of the cellulose bers can modify the ber surface, such as chemical functionalization stop the moisture absorption process and increase the surface roughness [1]. The production of nanoscale cellulose bers and their application in composite materials have gained increasing attention due to their high strength and stiness combined with low weight, biodegradability, and renewability. Application of cellulose nanobers in polymer reinforcement is a relatively new research eld [2]. The main reason
to utilize cellulose nanobers in composite materials is because one can potentially exploit the high stiness of the cellulose crystal for reinforcement. This can be done by breaking down the hierarchical structure of the plant into individualized nanobers of high crystallinity, with a reduction of amorphous parts [3]. In this paper we describe various approaches to the synthesis of nanobers from plant resources. Potential use of macro- and nanobers as reinforcing material for the development of polymers composites with enhanced properties and application of these composites in various elds are also discussed.
2. Cellulose Fibers
Cellulose bers are being used as potential reinforcing materials because of so many advantages such as abundantly available, low weight, biodegradable, cheaper, renewable, low abrasive nature, interesting specic properties, since these are waste biomass, and exhibit good mechanical properties
2 [46]. Cellulose bers also have some disadvantages such as moisture absorption, quality variations, low thermal stability, and poor compatibility with the hydrophobic polymer matrix [7, 8]. 2.1. Chemistry of Cellulose. Cellulose is the most abundant form of living terrestrial biomass [9] and nds applications in many spheres of modern industry. Existence of cellulose as the common material of plant cell walls was rst recognized by Anselm Payen in 1838 [10]. Cellulose has been shown to be a long-chain polymer with repeating units of Dglucose, a simple sugar. It occurs in almost pure form in cotton ber. However, in wood, plant leaves and stalks, it is found in combination with other materials, such as lignin and hemicelluloses. Although, generally considered a plant material, but some bacteria are also found to produce cellulose. Cellulose is a natural polymer, a long chain made by the linking of smaller molecules. The links in the cellulose chain consist of sugar, -D-glucose [11]. The sugar units are linked when water is eliminated by combining the H and OH group. Linking just two of these sugars produces a disaccharide called cellobiose [12]. In the cellulose chain, the glucose units are in 6-membered rings, called pyranoses. They are joined by single oxygen atoms (acetal linkages) between the C-1 of one pyranose ring and the C-4 of the next ring. Since a molecule of water is lost due to the reaction of an alcohol and a hemiacetal to form an acetal, the glucose units in the cellulose polymer are referred to as anhydroglucose units. The spatial arrangement or stereochemistries of these acetal linkages is very important. The pyranose rings of the cellulose molecule have all the groups larger than hydrogen sticking-out from the periphery of the rings (equitorial positions). The stereochemistry at carbons 2, 3, 4 and 5 of the glucose molecule are xed, but in pyranose form, the hydroxyl at C-4 can approach the carbonyl at C-1 from either side, resulting in two dierent stereochemistry at C-1. When the hydroxyl group at C-1 is on the same side of the ring as the C-6 carbon, it is said to be in the conguration. In cellulose, the C-1 oxygen is in the opposite or conguration (i.e., cellulose is poly[-1,4-D-anhydroglucopyranose]). This conguration, with all functional groups in equatorial positions, causes the molecular chain of cellulose to extend in a more or less straight line, making it a good ber-forming polymer [13]. Because of the equatorial positions of the hydroxyls on the cellulose chain, they protrude laterally along the extended molecule and are readily available for hydrogen bonding. These hydrogen bonds cause the chains to group together in a highly ordered structure. Since the chains are usually longer than the crystalline regions, they are thought to pass through several dierent crystalline regions, with areas of disorder in between (fringed-micelle model) [14]. The interchain hydrogen bonds in the crystalline regions are strong, giving the resultant ber good strength and insolubility in most solvents. They also prevent cellulose from melting (nonthermoplastic). In the less-ordered regions, the chains are further apart and more available for hydrogen bonding with other molecules, such as water. Most cellulose structures
International Journal of Polymer Science can absorb large quantities of water (hygroscopic). Thus, cellulose swells but does not dissolve in water [13]. The cellulose molecule contains three dierent kinds of anhydroglucose units, the reducing end with a free hemiacetal (or aldehyde) group at C-1, the nonreducing end with a free hydroxyl at C-4 and the internal rings joined at C1 and C-4. But because of long-chain length, the chemistry of the alcohol groups of the internal units predominates, so long as the chains are not cleaved by the reaction conditions. However, unlike simple alcohols, cellulose reactions are usually controlled by steric factors than would be expected on the basis of the inherent reactivity of the dierent hydroxyl groups. C-2, C-3, and C-6 hydroxyls and C-H groups are active sites in cellulose for the incorporation of polymeric chains through grafting. In grafting, it has been reported that the reactivity of hydroxyl group at C-6 is far less than those at C-2 and C-3 [13]. 2.2. Chemical Composition, Structure, and Properties of Cellulose Fibers. Cellulose bers can be classied according to their origin and grouped into leaf: abaca, cantala, curaua, date palm, henequen, pineapple, sisal, banana; seed: cotton; bast: ax, hemp, jute, ramie; fruit: coir, kapok, oil palm; grass: alfa, bagasse, bamboo; stalk: straw (cereal). The bast and leaf (the hard bers) types are the most commonly used in composite applications [15, 16]. Commonly used plant bers are cotton, jute, hemp, ax, ramie, sisal, coir, henequen, and kapok. The largest producers of sisal in the world are Tanzania and Brazil. Henequen is produced in Mexico whereas abaca and hemp in Philippines. The largest producers of jute are India, China, and Bangladesh [1]. Plant bers are constitutes of cellulose bers, consisting of helically wound cellulose microbrils, bound together by an amorphous lignin matrix. Lignin keeps the water in bers, acts as a protection against biological attack and as a stiener to give stem its resistance against gravity forces and wind. Hemicellulose found in the natural bers is believed to be a compatibilizer between cellulose and lignin [1]. The cell wall in a ber is not a homogenous membrane (Figure 1) [17]. Each ber has a complex, layered structure consisting of a thin primary wall which is the rst layer deposited during cell growth encircling a secondary wall. The secondary wall is made up of three layers and the thick middle layer determines the mechanical properties of the ber. The middle layer consists of a series of helically wound cellular microbrils formed from long-chain cellulose molecules. The angle between the ber axis and the microbrils is called the microbrillar angle. The characteristic value of microbrillar angle varies from one ber to another. These microbrils have typically a diameter of about 1030 nm and are made up of 30100 cellulose molecules in extended chain conformation and provide mechanical strength to the ber. The properties of cellulose bers are aected by many factors such as variety, climate, harvest, maturity, retting degree, decortications, disintegration (mechanical, steam explosion treatment), ber modication, textile, and technical processes (spinning and carding) [18]. In order to understand the properties of natural ber-reinforced composite materials, it becomes necessary to know the mechanical,
International Journal of Polymer Science

Secondary wall S3 Lumen Secondary wall S2 Helically arranged crystalline microbrils of cellulose Spiral angle Secondary wall S1
Primary wall Amorphous region mainly consisting of lignin and hemicellulose
Disorderly arranged crystalline cellulose microbrils networks
Figure 1: Structural constitution of natural ber cell [17].
physical, and chemical properties of natural bers. Flax bers are relatively strong bers as compared to other natural bers. The tensile strength of elementary bers is in the region of 1500 MPa and for technical bers a value of circa 800 MPa was observed at 3 mm clamp length [19]. Baley [20] and Lamy and Baley [21] investigated the modulus of ax bers. The modulus of elementary bers is dependent on the diameter of ber and it ranges from 39 GPa for bers having diameter approximately 35 m to 78 GPa for bers having 5 m diameter. This variation is related to the variation in relative lumen size between bers having dierent diameter. An average Youngs modulus of 54 GPa was observed after numerous tensile tests on single ax bers and the results are within the range of moduli measured on technical bers. The mechanical, chemical, and physical properties of plant bers are strongly harvest dependent, inuenced by climate, location, weather conditions, and soil characteristics. These properties are also aected during the processing of ber such as retting, scotching, bleaching, and spinning [22]. Cellulose bers have relatively high strength, high stiness, and low density [23]. The characteristic value for soft-wood-Kraft-bers and ax has been found close to the value for E-glass bers. Dierent mechanical properties can be incorporated in natural bers during processing period. The ber properties and structure are inuenced by several conditions and varies with area of growth, its climate and age of the plant [24]. Technical digestion of the ber is another important factor which determines the structure as well as characteristic value of ber. The elastic modulus of the bulk natural bers such as wood is about 10 GPa. Cellulose bers with moduli up to 40 GPa can be separated from wood by chemical-pulping process. Such bers can be further subdivided into microbrils within elastic modulus of 70 GPa. Theoretical calculations of elastic moduli of cellulose chain have been given values up to 250 GPa. However, no technology is available to separate these from microbrils [25]. The tensile strength of natural bers depends upon the test length of the specimen which is of main importance with respect to reinforcing eciency.
Mieck et al. [26] and Mukherjee and Satyanarayana [27] reported that tensile strength of ax ber is signicantly more dependent on the length of the ber. In comparison to this, the tensile strength of pineapple ber is less dependent on the length, while the scatter of the measured values for both is located mainly in the range of the standard deviation. The properties of ax ber are controlled by the molecular ne structure of the ber which is aected by growing conditions and the ber processing techniques used. Flax bers possess moderately high-specic strength and stiness. Quality and other properties of bers depend on factors such as size, maturity, and processing methods adopted for the extraction of bers. Properties such as density, electrical resistivity, ultimate tensile strength, and initial modulus are related to the internal structure and chemical composition of bers [23]. Desirable properties for bers include excellent tensile strength and modulus, high durability, low bulk density, good moldability, and recyclability.
3. Cellulose Nanobers
Cellulose nanobers have a high potential to be used in many dierent area particularly as reinforcement in development of nanocomposites. Many studies have been done on isolation and characterization of cellulose nanobers from various sources. Cellulose nanobers can be extracted from the cell walls by simple mechanical methods or a combination of both chemical and mechanical methods. 3.1. Synthesis of Cellulose Nanobers. Alemdar and Sain [28] have extracted cellulose nanobers from wheat straw by a chemical treatment, resulting to puried cellulose. To individualize the nanobers from the cell walls a mechanical treatment (cryocrushing, disintegration, and debrillation steps) was applied to the chemically treated bers. Cellulose nanobers were extracted from the agricultural residues, wheat straw and soy hulls, by a chemomechanical technique [29]. The wheat straw nanobers were determined to have diameters in the range of 1080 nm and lengths of a few
International Journal of Polymer Science can provide information about widths of cellulose nanober but it is very dicult to nd out the lengths of nanober because of entanglements and diculties in identifying both ends of individual nanobers. It is often reported that MFC suspensions are not homogeneous and that they consist of cellulose nanobers and nanober bundles [2]. Teixeira et al. [34] obtained the suspensions of white and colored nanobers by the acid hydrolysis of white and naturally colored cotton bers. Possible dierences among them in morphology and other characteristics were investigated. Morphological study of cotton nanobers showed a length of 85225 nm and diameter of 618 nm. It was found that there were no signicant morphological dierences among the nanostructures from dierent cotton bers. The main dierences found were the slightly higher yield, sulfonation eectiveness, and thermal stability under dynamic temperature conditions of the white nanober. On the other hand, the colored nanobers showed a better thermal stability than the white in isothermal conditions at 180 C. The structure of the cellulose nanobers from agricultural residues was investigated by Alemdar and Sain [29]. FTIR spectroscopic analysis demonstrated that chemical treatment also led to partial removal of hemicelluloses and lignin from the structure of the bers. PXRD results revealed that this resulted in improved crystallinity of the bers. Thermal properties of the nanobers were studied by the TGA technique and were found to increase dramatically. Stelte and Sanadi [35] have studied the mechanical brillation process for the preparation of cellulose nanobers from two commercial hard- and softwood cellulose pulps. The degree of brillation was studied using light microscopy (LM), scanning electron microscopy (SEM), and atomic force microscopy (AFM). LM and SEM images (Figure 3) of hard- and softwood bers showed that the hardwood bers that were brillated only on the surface during the rening step are now disintegrated into a network of small bers. AFM images (Figure 4) of the nal products after highpressure homogenization showed that the size distribution of the hard- and softwood nanobers is in the range of 10 25 nm in diameter. Wang and Sain [31] synthesized soybean stock-based nanobers having a diameter in the range 50100 nm by chemomechanical isolation. X-ray crystallography (Figure 5) was carried out to investigate the percentage crystallinity after various stages of the chemomechanical treatment. It has been found that crystallinity of the samples increased after each stage of nanober development. Figure 6 shows the network of cellulose nanobers. The nanober suspension obtained after the high pressure debrillation was analyzed to determine diameters using AFM. The AFM image (Figure 6) shows the surface of airdried soybean stock nanober. It is seen that the bers are indeed nanosized and the diameter of nanobers is within the range 50100 nm.
Raw material (soybean stock)
Pretreatment (17.5% w/w NaOH, 2h)
Acid hydrolysis (1M HCl, 7080 C, 2h)
Alkaline treatment (2% w/w NaOH, 2h, 7080 C)
Cryocrushing in liquid nitrogen
High pressure debrillation
Figure 2: Isolation of nanobers by chemomechanical treatment [31].
thousand nanometers. By comparison, the soy hull nanobers had diameter 20120 nm and shorter lengths than the wheat straw nanobers. Zimmermann et al. [30] separated nanobrillated cellulose (NFC) at the greatest possible lengths and diameters below 100 nm from dierent starting cellulose materials by mechanical dispersion and high pressure (up to 1500 bar) homogenization processes. The treatment resulted in nanoscaled bril networks. Two commercial brous celluloses showed bigger cellulose aggregates with micrometer dimensions and a less homogeneous network structure. The cellulose nanobers were extracted by Wang and Sain [31] from soybean stock by chemomechanical treatments (Figure 2). These are bundles of cellulose nanobers with a diameter ranging between 50 and 100 nm and lengths of thousands of nanometers. The cellulose nanobrils were extracted from wheat straw using steam explosion, acidic treatment, and high shear mechanical treatment. Alkaline-treated pulp was soaked in 8% solution of H2 O2 (v/v) overnight. Bleached pulp was then rinsed with abundant distilled water. Bleached pulp was then treated with 10% HCl (1 N) solution and mixed using ultrasonicator at temperature around 60 1 C for 5 h. Finally, the bers were taken out and washed several times with distilled water in order to neutralize the nal pH and then dried. Fibers were suspended in water and continuously stirred with a high shear homogenizer for 15 min. Highshearing action breaks down the ber agglomerates and result in nanobrils [32]. 3.2.Structure and Properties of Cellulose Nanobers. Transmission electron microscopy (TEM), scanning electron microscopy (SEM), eld-emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), wide-angle Xray scattering (WAXS), and NMR spectroscopy have been used to study the structure of cellulose nanobers [33]. A combination of microscopic techniques with image analysis
4. Surface Modication of Cellulose Fibers

In order to develop composites with better mechanical properties and environmental performance, it becomes necessary
Figure 3: Scanning electron micrographs of hard- and softwood cellulose bers, before and after 10 passes through the homogenizer [35].
1 m
(a) (b)
1 m
Figure 4: AFM images (a) hard- and (b) softwood cellulose nanobers at process equilibrium [35].
to increase the hydrophobicity of the cellulose bers and to improve the interface between matrix and bers. Lack of good interfacial adhesion, low melting point, and poor resistance towards moisture make the use of plant cellulose berreinforced composites less attractive. Pretreatments of the cellulose ber can clean the ber surface, chemically modify the surface, stop the moisture absorption process, and increase the surface roughness [1, 36]. Among the various pretreatment techniques, silylation, mercerization, peroxide, benzoylation, graft copolymerization, and bacterial cellulose
treatment are the best methods for surface modication of natural bers. 4.1. Silylation, Mercerization, and Other Surface Chemical Modications. Silane-coupling agents usually improve the degree of cross-linking in the interface region and oer a perfect bonding. Among the various coupling agents, silanecoupling agents were found to be eective in modifying the natural ber-matrix interface. Eciency of silane treatment was high for the alkaline-treated ber than for the untreated
82.648
15
20
25
30 80 75 70 65 60 55 50 45 40 35 30
29.586
Intensity
12
2 (degrees)
30
Figure 5: X-ray pattern to demonstrate the crystallinity of soybean stock nanobers [31].
500 m
Figure 6: Atomic force micrograph of soybean stock nanobers [31].
ber because more reactive site can be generated for silane reaction. Therefore, bers were pretreated with NaOH for about half an hour prior to its coupling with silane. Fibers were then washed many times in distilled water and nally dried. Silane-coupling agents may reduce the number of cellulose hydroxyl groups in the bermatrix interface. In the presence of moisture, hydrolyzable alkoxy group leads to the formation of silanols. The silanol then reacts with the hydroxyl group of the ber, forming stable covalent bonds to the cell wall that are chemisorbed onto the ber surface [37]. Therefore, the hydrocarbon chains provided by the application of silane restrain the swelling of the ber by creating a crosslinked network due to covalent bonding between the matrix and the ber [1]. Silanes were eective in improving the interface properties [3841]. Alkoxy silanes are able to form bonds with hydroxyl groups. Fiber treatment with toluene dissocyanate
and triethoxyvinyl silane could improve the interfacial properties. Silanes after hydrolysis undergo condensation and bond formation stage and can form polysiloxane structures by reaction with hydroxyl group of the bers. The reactions are given in Schemes 1 and 2 [1, 42]. In the presence of moisture, hydrolysable alkoxy group leads to the formation of silanols. Hydrogen and covalentbonding mechanisms could be found in the natural bersilane system. It is understood that the hydrocarbon chains provided by the silane application inuenced the wetability of the bers, thus improving the chemical anity to polyethylene. 1% solution of three aminopropyl trimethoxy silane in a solution of acetone and water (50/50 by volume) for 2 h was reportedly used to modify the ax surface [43]. Rong et al. [17] soaked sisal ber in a solution of 2% aminosilane in 95% alcohol for 5 min at a pH value of 4.55.5 followed by 30 min air drying for hydrolyzing the coupling agent. Silane solution in water and ethanol mixture with concentration of 0.033% and 1% was also carried by ValadezGonzalez et al. [44] and Agrawal et al. [37] to treat henequen and oil-palm bers. They modied the short henequ n bers e with a silane coupling agent in order to nd out its deposition mechanism on the ber surface and the inuence of this chemical treatment on the mechanical properties of the composite. It was shown that the partial removal of lignin and other alkali soluble compounds from the ber surface increases the adsorption of the silane coupling-agent whereas the formation of polysiloxanes inhibits this process. Mercerization is the common method to produce highquality bers [45]. Scheme 3 shows the probable mechanism of mercerization of cellulose bers. Mercerization leads to brillation which causes the breaking down of the composite ber bundle into smaller bers. Mercerization reduces ber

OC2 H5 Si OC2 H5 OC2 H5 H2 O OH Si OH OH + 3 C2 H5 OH
H2 C
H2 C
Scheme 1
O Cellulose Fibers Hemicellulose Lignin O O O H H + CH2 H CH Si O O H H H
O Cellulose O Si O O Fiber Hemicellulose O Si O O Lignin O Si O
H CH H H CH H H CH H CH2 CH2 CH2
Scheme 2
diameter, thereby increases the aspect ratio which leads to the development of a rough surface topography that results in better ber-matrix interface adhesion and an increase in mechanical properties [46]. Moreover, mercerization increases the number of possible reactive sites and allows better ber wetting. Mercerization has an eect on the chemical composition of the ax bers, degree of polymerization, and molecular orientation of the cellulose crystallites due to cementing substances like lignin and hemicellulose which were removed during the mercerization process. As a result, mercerization had a long-lasting eect on the mechanical properties of ax bers, mainly on ber strength and stiness [47]. Sreekala et al. [42] indicated that a 1030% sodium hydroxide solution produced the best eects on natural ber properties. Flax bers were soaked into 2.5, 5, 10, 13, 15, 18, 20, 25, or 30% NaOH solutions, and it was found that 5%, 18%, or 10% of sodium hydroxide solution was the appropriate concentration for mercerization. Jute bers were treated with 5% alkali solution for 0, 2, 4, 6, and 8 h at 30 C by Ray et al. [45]. The bers were then dried at room temperature for 48 h followed by oven drying at 100 C for 6 h. It has been reported by Garcia-Jaldon et al. [48] that 2% alkali solution at 200 C and 1.5 MPa pressure for 90 s was suitable for degumming and debrillation to individual bers. Several workers have carried out work on
alkali treatment and reported that mercerization leads to an increase in the amount of amorphous cellulose at the cost of crystalline cellulose and the removal of hydrogen bonding in the network structure [42, 46]. The jute bers were washed with detergent (2 vol.% in aqueous solution, 15% active matter) and then immersed in beakers with a solution of 5 wt. % NaOH for 24 h at room temperature. After that, the bers were washed thoroughly with distilled water to remove the excess of NaOH and dried at 70 C for 24 h under vacuum [49]. The banana bers were cleaned and reuxed in 0.25% solution of NaOH for 1 h and then washed in very dilute acid to remove the nonreacted alkali. Washing was continued until the bers were alkali free. The washed bers were then dried in an oven at 70 C for 3 h [50]. Peroxide treatment of cellulose ber has attracted the attention of various researchers due to easy processability and improvement in mechanical properties. Organic peroxides tend to decompose easily to free radicals (RO), which further react with the hydrogen group of the matrix and cellulose bers. Schemes 4 and 5 show the peroxide treatment reaction onto cellulose bers [42]. In peroxide treatment, bers are treated with 6% benzoyl peroxide or dicumyl peroxide in acetone solution for about 30 min after alkali pretreatment [42, 51, 52]. Flax bers were coated with dicumyl peroxide from acetone solution

OR O Na+ + NaOH RO O OR Cellulose Mercerized cellulose
+ Na O
OR OH RO O OR O HO O O OH
O O O Na+
+ H2 O
Scheme 3
O O O O Benzoyl peroxide 2
O O
Scheme 4
after alkali pretreatments. Saturated solution of the peroxide in acetone was used. Soaking of the bers in the solution was conducted at a temperature of 70 C for 30 min. High temperatures were favored for decomposition with the peroxide. The chemically treated bers were washed with distilled water and placed in an oven at 80 C for 24 h [53]. In benzoylation treatment, benzoyl chloride is most often used in ber pretreatment and inclusion of benzoyl (C6 H5 C=O) group in the ber is responsible for the decreased hydrophilic nature of the treated ber [46]. A known amount of washed bers (35 g) were soaked in 18% NaOH solution for 30 minutes followed by ltration and washing with water. The treated ber was suspended in 10% NaOH solution and agitated with 50 mL benzoyl chloride. The reaction between the cellulosic OH group of sisal ber and benzoyl chloride is shown in Scheme 6 [46, 54]. Joseph et al. [46] and Kalia et al. [54] used NaOH and benzoyl chloride (C6 H5 COCl) solution for surface treatment of sisal bers. The ber was initially alkaline pretreated in order to activate the hydroxyl groups of the cellulose and lignin in the ber; then the ber was suspended in 10% NaOH and benzoyl chloride solution for 15 min. The isolated bers were then soaked in ethanol for 1 h to remove the benzoyl chloride and nally was washed with water and dried in the oven at 80 C for 24 h [55]. 4.2. Polymer Grafting. Desirable and targeted properties can be imparted to the cellulose bers through graft copolymerization in order to meet out the requirement of specialized applications. Graft copolymerization is one of the best methods for modifying the properties of cellulose bers. Dierent binary vinyl monomers and their mixtures have been graftcopolymerized onto cellulosic material for modifying the properties of numerous polymer backbones [1, 56]. During last decades, several methods have been suggested for the preparation of graft copolymers by conventional chemical techniques. Creation of an active site on the
preexisting polymeric backbone is the common feature of most methods for the synthesis of graft copolymers. The active site may be either a free-radical or a chemical group which may get involved in an ionic polymerization or in a condensation process. Polymerization of an appropriate monomer onto this activated backbone polymer leads to the formation of a graft copolymer. Ionic polymerization has to be carried-out in presence of anhydrous medium and/or in the presence of considerable quantity of alkali metal hydroxide. Another disadvantage with the ionic grafting is that low molecular weight graft copolymers are obtained while in case of free radical grafting high molecular weight polymers can be prepared. C2 , C3 , and C6 hydroxyls and C-H groups are the active cites for grafting in cellulosics (Figure 7) [57]. The conventional technique of grafting and chemical modication of natural bers requires signicant time and energy. The use of MWR technique to modify the properties of natural bers within the textile industry, although somewhat slow and still rather limited, is nding its way into numerous uses in production plants. Microwave radiation technique reduces the extent of physicochemical stresses to which the bers are exposed during the conventional techniques. Microwave technology uses electromagnetic waves, which passes through material and causes its molecules to oscillate. Microwave energy is not observed by nonpolar materials to any degree while polar water molecules held within a polymer matrix do absorb energy very prociently, thus becoming heated [58, 59]. Graft copolymerization of methyl methacrylate onto ax ber was carried out under three dierent reaction methods, in air, under pressure, and under the inuence of microwave radiations. Grafting through microwave-radiation technique is an eective method in terms of time consumption and cost eectiveness. Maximum percentage grafting has been observed in case of grafting carried out in air followed by grafting under pressure and under the inuence

OR OH RO O OR Cellulose O HO O O + O RO O OR O OR O H O OH O O + OH OR O
OH
Scheme 5
OH
+ Na O
O HO OH Cellulose ber n + NaOH

+ Na O
O + H2 O O Na+ n
+ Na O
C O
+ Na O
O + COCl O C
O O n O C + NaCl
O Na+ Mercerized ber
n Benzoyl chloride O
Benzoylated ber
Scheme 6
OR RO O O HO C4
OR C6 C5 C3 C2 OH O O C1
ization and thermal stability has been found to be increased. Microwave radiation-induced grafting showed a diminutive eect on the crystalline behavior of the sunn hemp bers as optimum time to get maximum grafting is very less (40 minutes) in comparison to conventional grafting [60]. 4.3. Bacterial Modication. The coating of bacterial cellulose onto cellulose bers provides new means of controlling the interaction between bers and polymer matrices. Coating of bers with bacterial cellulose does not only facilitate good distribution of bacterial cellulose within the matrix, but also results in an improved interfacial adhesion between the bers and the matrix. This enhances the interaction between the bers and the polymer matrix through mechanical interlocking [3, 61]. Surface modication of cellulose bers using bacterial cellulose is one of the best methods for greener surface treatment of bers. Bacterial Cellulose has
OR
Figure 7: Structure of cellulose [57].
of microwave radiations. Flax ber faces less surface deformations during grafting process under the inuence of microwave radiations as compared to grafting in air and under pressure, thereby retaining better crystalline structure. Morphological and thermal studies showed that surface of sunn hemp bers becomes rough through graft copolymer-
10 gained attention in the research area for the encouraging properties it possesses; such as its signicant mechanical properties in both dry and wet states, porosity, water absorbency, moldability, biodegradability, and excellent biological anity [62]. Because of these properties, BC has a wide range of potential applications. Acetobacter xylinum (or Gluconacetobacter xylinus) is the most ecient producer of bacterial cellulose. BC is secreted as a ribbon-shaped bril, less than 100 nm wide, which is composed of much ner 24 nm nanobrils. In comparison to the methods for obtaining nanocellulose through mechanical or chemomechanical processes, it is produced by bacteria through cellulose biosynthesis and the building up of bundles of microbrils [6365]. The cultivation of the cellulose producing bacteria in the presence of natural bers, such as sisal and hemp, results in the coating of natural ber surfaces by bacterial nanocellulose (Figure 8) [61]. Strong and highly crystalline nanocellulosic brils preferentially attached to the surface of natural bers thereby creating hairy bers (Figure 9), leading to a nanostructured natural ber surface. Simply weighing the bers before and after the BC fermentation process conrmed that between 5 and 6 wt% of bacterial cellulose adhered to the bers after the surface modication. The strength of attachment of the nanocellulose coating to the bers can be attributed to strong hydrogen bonding between the hydroxyl groups present in bacterial cellulose and the lignocellulose in natural bers [66]. The modication process did not aect the mechanical properties of sisal bers but it signicantly reduced the mechanical properties of hemp bers. Figure 10 shows the coating of bacterial nanocellulose onto hemp bers [61]. To improve the compatibility between natural bers and hydrophobic polymer matrices, various greener methods have been explored such as fungi, enzymes and bacterial treatments. Kalia and Sheoran [67] have reported cellulase enzyme assisted biopolishing of ramie bers using bacteria Streptomyces albaduncus. Biopolishing of ramie bers by utilizing cellulase from bacteria Streptomyces albaduncus was observed for 5 days, at the pH 7.4 and 2.0 g glucose, which results in enhanced brightness due to the removal of gum materials and small brils protruding from the ber surface. Bacterial treatment has diminutive eect on thermal stability and crystalline structure of ramie bers.
Figure 8: Photographs of sisal bers before and after bacterial culture [61].
1 m
(a)
1 m
(b)
Figure 9: SEM micrographs (a) sisal ber and (b) bacterial cellulose-coated sisal ber [61].
5. Cellulose-Fiber-Reinforced Biocomposites
5.1. Processing Method. Natural ber composites are prepared using various composites manufacturing methods such as compression molding, injection molding, resin transfer molding (RTM), and vacuum bagging. The preforms are mostly bers, fabrics, or nonwovens. Prepregs are also widely used to prepare composites [68]. Equation (1) is commonly used in the preparation of composites Vf = W f / f W f / f + Wm /m
(1)
where V f is the ber-volume fraction, W f is the weight of ber, and Wm is the weight of matrix. r f and rm are the densities of the ber and matrix, respectively. The production of the composites is optimized in relation to temperature, pressure, and molding time. It is often necessary to preheat the natural bers to reduce the moisture before processing the composites. High temperatures degrade the cellulose; thus, negatively aecting the mechanical properties of the composites. Inecient ber dispersion in the matrix causes ber agglomeration which decreases the tensile strength [68]. Most of the previous research on natural ber composites has focused on reinforcements such as ax, hemp, sisal and jute, and thermoplastic and thermoset matrices. Some of these composites have been produced using matrices made of derivatives from cellulose, starch, and lactic acid to develop fully biodegradable composites or biocomposites [69]. The emerging diversity of applications of natural ber composites has seen the production of sandwich structures based on natural-ber composite skins. In some cases, these sandwich composites have been produced from paper honeycomb and natural ber-reinforced thermoplastic or thermoset skins, depending on the applications.
11 An alternative variant of this process is the vacuum injection or vacuum-assisted resin transfer molding (VARTM), where a single solid mould and a foil (polymeric lm) are used. The VARTM process is a very clean and low cost manufacturing method: resin is processed into a dry reinforcement on a vacuum-bagged tool, using only the partial vacuum to drive the resin. As one of the tool faces is exible, the moulded laminate thickness depends partially on the compressibility of the ber-resin composite before curing and the vacuum negative pressure. 5.1.3. Compression Molding. Compression molding is another major technique for the construction of ber-reinforced polymers, which involves a seminished composite sheet widely known as sheet molding compound (SMC) that is later moulded into the nal parts by compression. For the SMC the process consists of a rolling lm of resin on which bers are added. A second lm of resin is then added, so as to later be compressed in a composite sheet that may be stored for few days. To get the nal product the reinforced sheet is then placed into a press to take its desired shape. Advantages of compression molding are the very high volume production ability, the excellent part reproducibility and the short cycle times. Processing times of <2 min are reached during the compression molding of three-dimensional components with a high forming degree. It has also been shown that the adhesion of natural bers and matrix resin is important in order to obtain good mechanical properties of natural ber composites, and the mechanical properties were improved by the molding condition, the molding pressure and temperature. A big concern with compression molding that needs always to be considered is the maximum pressure before the damage of the bers and the structure. 5.1.4. Injection Molding. Injection molding process is suitable to form complex shapes and ne details with excellent surface nish and good dimensional accuracy for high production rate and low labour cost. In the injection molding resin granules and short bers are mixed into a heated barrel and transported to the mould cavity by a spindle. Injection molding is another process among the most important for the manufacturing of plastics/composites and can produce from very small products such as bottle tops to very large car body parts. 5.1.5. Pultrusion. Pultrusion is a continuous process to manufacture composite proles at any length. The impregnated bers are pulled through a die, which is shaped according to the desired cross-section of the product. The resulting prole is shaped until the resin is dry. Advantages of this process are the ability to build thin wall structures, the large variety of cross-sectional shapes and the possibility for high degree of automation. 5.2. Interfacial Interactions. All natural bers are (in dierent extent) hydrophilic in nature. This is attributed mainly to the lignocellulose into their structure, which contain strongly polarized hydroxyl groups [68]. These bers, therefore, are inherently incompatible with many well known and popular
Mag = 50.00 kX
1 m
EHT = 5.00 kV WD = 8 mm
Signal A = Inlens Date: 1 Feb 2006 Photo no. = 9173 Time: 11:24:10
Figure 10: Hemp ber after bacterial cellulose modication [61].
The main criteria for the selection of the appropriate process technology for natural-ber composite manufacture include the desired product geometry, the performance needed, and the cost and the ease of manufacture. The fabrication methods for natural ber composites are similar to those used for glass bers. The most commonly used manufacturing processes are introduced in the following. Although many variants on these techniques exist, this overview gives a good indication of the production possibilities. 5.1.1. Hand Laminating. The bers are placed in a mould and the resin is later applied by rollers. One option is to cure using a vacuum bag, as then excess air is removed and the atmospheric pressure exerts pressure to compact the part. The simplicity, low cost of tooling, and exibility of design are the main advantages of the procedure. On the other end, the long production time, intensive labour, and low automation potential, consist some of the disadvantages. 5.1.2. Resin Transfer Molding (RTM). The resin transfer molding technique requires the bers to be placed inside a mould consisting of two solid parts (close mould technique). A tube connects the mould with a supply of liquid resin, which is injected at low pressure through the mould, impregnating the bers. The resulting part is cured at room temperature or above until the end of the curing reaction, when the mould is opened and the product removed. Parameters such as injection pressure, ber content, and mould temperature have a great inuence on the development of the temperature proles and the thermal boundary layers, especially for thin cavities. This technique has the advantage of rapid manufacturing of large, complex, and high performance parts. Several types of resins (epoxy, polyester, phenolic, and acrylic) can be used for RTM as long as their viscosity is low enough to ensure a proper wetting of the bers. Parameters such as injection pressure, ber content, and mould temperature have a great inuence on the development of the temperature proles and the thermal boundary layers, especially for thin cavities. Good knowledge of all the operating steps is very important to obtain high-quality parts [68].
12 in composite manufacturing resins. Only some thermosets such as the phenol-formaldehyde and related polymers are less hydrophilic and thus less problematic. This discrepancy leads often to the formation of ineective interface between the bers and the matrix. The major limitations of using these bers as reinforcements in such matrices include poor interfacial adhesion between polarhydrophilic bers and nonpolar-hydrophobic matrix, and diculties in mixing due to poor wetting of the bers with the matrix. The role of the matrix in a ber-reinforced composite is to transfer the load to the sti bers through shear stresses at the interface. This process requires a good bond between the polymeric matrix and the bers [70]. Poor adhesion at the interface means that the full capabilities of the composite cannot be exploited and leaves it vulnerable to environmental attacks that may weaken it, thus reducing its life span. Insucient adhesion between the polymer and the bers results in poor mechanical properties of the natural ber-reinforced polymer composites. Pretreatments of the bers can clean the ber surface, chemically modify the surface, stop the moisture absorption process, and increase the surface roughness [71, 72]. These properties may be improved by both physical treatments like cold plasma treatment or corona treatment, and chemical treatment such as maleic anhydride, organosilanes, isocyanates, sodium hydroxide, permanganate, and peroxide. 5.2.1. Physical Treatment. Physical treatments change the structural and surface properties of the bers and thereby inuence the mechanical bonding to polymers. Corona treatment is one of the most popular techniques for surface oxidation activation through electric discharge that changes the surface energy of the cellulose bers. Cold plasma treatment is another electric discharge technique and can have the same surface eects and increase the ber matrix adhesion [72]. A traditional physical method is mercerization. In this process, the bers are treated with an aqueous solution of a strong base (alkali treatment) so as to produce great swelling that results in changes of their structure, dimensions, morphology, and mechanical properties [72]. 5.2.2. Chemical Treatment. Among the most eective methods of chemical treatment is graft copolymerization [68, 72]. The cellulose is treated with an aqueous solution with selected ions and is exposed to a high energy radiation. Under the radiation, the cellulose molecule cracks and radicals are formed. Using then a suitable (compatible with the matrix) solution it is possible to create a copolymer with properties and characteristics of both the bers and the matrix. Graft copolymers of natural bers with vinyl monomers provide better adhesion between matrix and ber. Gauthier et al. [73] reported that adhesion may be improved by using coupling agents like maleic anhydride to incorporate hydroxyl groups on the matrix through hydrophilization and consequently enhancing the wetting eect of the resin on the bers. The hydroxyl groups then interact with OH molecules on the lignocellulosic bers via hydrogen bonding, thus producing stronger bond. George et al. [74] reviewed the physical and chemical treatments that may improve the
International Journal of Polymer Science ber-matrix adhesion and manufactured biocomposites by applying an alkaline solution to the bers. Natural bers are mainly composed of cellulose, whose elementary unit, anhydro d-glucose, contains three hydroxyl (OH) groups. These hydroxyl groups form intra- and intermolecular bonds, causing all vegetable bers to be hydrophilic. The alkaline solution regenerated the lost cellulose and dissolved unwanted microscopic pits or cracks on the bers resulting in better ber-matrix adhesion. Coupling agents are based on the concept that when two materials are incompatible, a third material with intermediate properties can bring the compatibility to the mixture [72]. The coupling agents have two functions: to react with OH groups of the cellulose and to react with the functional groups of the matrix with the goal of facilitating stress transfer between the bers and the matrix. Numerous studies [68, 72] have been conducted on the use of coupling agents including organosilanes, triazine, and maleicanhydride (MAH). For instance, Xie et al. [75] used silanecoupling agents in natural ber/polymer composites and concluded that proper treatment of bers with silanes can increase the interfacial adhesion and improve the mechanical performance of the resulting composites. Gassan and Bledzki [76] improved the tensile and exural strength and stiness of jute/epoxy composites by treating the bers with silane. Acetylation, isocyanate treatment, and treatment with stearic acid are some more chemical methods for modication and preparation of the ber/matrix adhesion. 5.3. Characterization. Plant bers are basically composite materials designed by nature and consist of a collection of long and thin cells made up of hollow cellulose brils held together by a lignin and hemicellulose matrix [77]. The strength and stiness of the bers are provided by hydrogen bonds and other linkages. The overall properties of the bers depend on the individual properties of each of its components. Hemicellulose is responsible for the biodegradation, moisture absorption, and thermal degradation of the ber. On the other hand, lignin (or pectin) is thermally stable but is responsible for UV degradation of the ber. On average, natural bers contain 6080% cellulose, 520% lignin (or pectin), and up to 20% moisture. On a composite, the properties of the bers are combined with those of the matrix, which is responsible to transfer the external loads to the sti bers through shear stresses at the interface as well as keep the bers together in a specic structural form. Thus, the properties of the composite are a combination of the properties of the ingredients and their prediction and estimation becomes a dicult job. 5.3.1. Stiness and Strength. The mechanical properties of natural ber composites are much lower than those of glass bers. However, their specic properties, especially stiness, are comparable to the stated values of glass bers. Moreover, natural bers are about 50% lighter than glass, and in general cheaper. It is widely acknowledged that natural ber composites combine good mechanical properties with a low specic mass and oer an alternative material to glass ber-reinforced plastics in some technical applications.
International Journal of Polymer Science For example, Bledzki and Gassan [72] observed that the characteristic values of natural bers are comparable to those of glass bers. Experimental data giving the tensile strength, exural strength, modulus, impact force, and compressive force are available in the literature for dierent types of natural-ber composites. The ultimate strength of any composite depends on several factors, most important of which are the properties of the components and the volume fraction. Wambua et al. [70] studied the importance and eect of the volume fraction on the tensile strength of natural ber composites. They reported that an increase in the ber weight fraction produces an increase in the tensile strength. Testing dierent ber reinforcement, they also found that hemp/polypropylene (PP) composites with a 30% volume fraction displayed a tensile strength of 52 MPa, higher than equivalent glass-reinforced composites with the same volume fraction. Further, hemp and kenaf-polypropylene composites registered a high tensile modulus of 6.8 GPa compared to 6.2 GPa of equivalent glass composites. The increase of the modulus and the tensile strength with increase of the volume or weight fraction was also showed by Bos et al. [78, 79] on ax/PP composites with maleic-anhydride grafted polypropylene for improved adhesion. Studies and results of tensile tests on ax-ber-reinforced PP composites were conducted by Garkhail et al. [80] which concluded that ber length aect the strength and modulus of the composites for small ber lengths whilst after a specic value for the length the two parameters are constant. The stiness of a ax/PP composite was shown to be comparable to E-glass-based composite, especially when the specic properties are concerned due to the very low density of ax. However, the results also depicted a relatively low tensile strength. Nishino [81] studied the mechanical properties of kenaf/ poly-L-lactide (PLLA) composites. He concluded that the modulus of the composites increases with the increase of the volume fraction, but only up to a certain level. When this threshold is achieved, further increase of the ber fraction leads to a dramatic reduction of the composite properties. Water content has also a dramatic eect on the properties of natural-ber composites. Espert et al. [82] showed this eect on cellulose/PP composites by submerging samples into distilled water under dierent temperatures. The samples were removed from the water at certain times and the water absorption was measured. The results of tensile tests showed a signicant eect of the water content to the youngs modulus of the samples, and an even bigger eect on the tensile strength. The studies also concluded that the eect of the water to the properties is highly inuenced by the ber content, the matrix and mainly the temperature. Thwe and Liao [83] investigated the same eect on bamboo-ber composites and resulted that both the tensile strength and modulus have decreased after aging in water at 25 and 75 C for prolonged period. The extent of strength and stiness loss depends upon aging time and temperature. They also concluded that tensile strength and stiness are enhanced by inclusion of a coupling agent, maleic anhydride polypropylene (MAPP),
13 in matrix material as a result of improved interfacial bonding.
5.3.2. Impact Performance. There are only few studies known about the impact behaviour of natural-ber reinforcedcomposites. The impact performance of several natural ber composites was compared and reviewed by Wambua et al. [70]. Using kenaf-, coir-, sisal-, hemp-, and jutereinforced polypropylene the study concluded that natural ber composites display low impact strengths compared to glass composites, whereas their specic impact strength can be comparable with those of glass mat composites. Among the materials studied, sisal and hemp showed the higher impact strength. Pavithran et al. [84] determined the fracture energies for sisal, pineapple, banana, and coconut ber-polyester composites in a Charpy impact test. They concluded that increased ber toughness results in increased fracture energy and found that bers with higher bril angles have higher fracture-toughness than those with small spiral angle. Fiber content and ber length have also a contribution to the impact performance of the composite. Tobias [85] examined this inuence with banana-ber composites and concluded that smaller ber lengths have higher impact strength which also increases for higher ber content. Contradictorily, the ber length was also studied by Garkhail et al. [80] on ax/PP composites. The results showed that (as in glass ber composites) the impact strength increases with increasing ber length until a plateau level is reached. After that level, the impact performance drops depending on the pretreatment of the bers and the adhesion of the ber/matrix interface. Mueller [86] investigated the eect of several material parameters on the impact strength of compression-molding components of hemp-, ax- and kenaf-polypropylene composites. The studies showed a strong inuence of the thermal process conditions during the molding. He concluded that for every material studied there is an optimum temperature that results to a peak of the impact strength. Higher and lower processing temperature resulted in lower mechanical values that could be explained by a thermal decomposition of the bers. Strong impact of the ber neness was also proved, with the impact performance getting higher from composites with ber of higher neness. The eect of temperature and water on the impact properties of natural-ber thermoplastics were reviewed by De Bruijn [87] and showed not signicant eect on the impact properties of the composites. However, the results showed that the impact strength was 20 to 25% to that of glass-reinforced thermoplastics. A signicant contribution of coupling agents on the impact strength has also been reported. When the composites have no coupling agent, a part of the energy is lost in the interface, by for example debonding and friction eects. Maleic-anhydride-treated jute composites showed higher impact strength than untreated samples made out of the same process.
14 5.3.3. Fatigue Behaviour. The cyclic loading of natural ber composites is still poorly investigated. Gassan [88] investigated the fatigue behaviour of ax and jute epoxy resin composites. Fiber type, textile architecture, interphase properties, and ber properties and content were found to aect the fatigue behaviour strongly. It was also found that natural ber-reinforced plastics with higher ber strength and modulus, stronger ber-matrix adhesion, or higher ber fractions possess higher critical loads for damage initiation and higher failure loads. In addition, damage propagation rates were reduced. Furthermore, unidirectional composites were less sensitive to fatigue-induced damage than woven reinforced ones. Savastano et al. [89] presented the results of experimental studies of resistance-curve behaviour and fatigue crack growth in cementitious matrices reinforced with natural bers such as sisal, banana, and bleached eucalyptus pulp. Fatigue crack growth was observed to occur in three stages: an initial decelerated growth, a steady-state growth, and a nal catastrophic crack growth. In the case of the composites reinforced with sisal and banana bers, most of fatigue life was spent in the second stage of steady-state crack growth. The results showed that fatigue crack growth in the composites occurred via matrix cracking, crack deection around bers, and crack-bridging by uncracked bers and ligaments, whilst ber pullout was also observed. The fatigue performance of sisal/epoxy composites was also studied by Towo and Ansell [90, 91] which looked into the eect of surface modication on the fatigue performance of the composite. The results show that an NaOH surface treatment has a signicant eect on the tensile modulus and strength of the material, but the fatigue life is not highly inuenced, especially in low stress levels. Their conclusion states that the behaviour of sisal ber composites is similar to that of conventional synthetic ber composites and static and fatigue strengths are suitably high for many commercial applications. Towo et al. also studied the fatigue properties of ax/polyester with alkali-treated and untreated bers. In this case they observed a high inuence of the treatment on the fatigue life of the components and they also underlined that the polyester matrix samples had lower life than the epoxy samples. A comparison between hemp- and ax-reinforced polyester composites with focus on the fatigue behaviour was conducted by Yuanjian and Isaac [92]. A steeper gradient of the S-N curve for the hemp-ber composite was indicative of a higher rate of reduction in fatigue strength. However, the fatigue performance levels of this hemp mat composite were comparable and slightly greater than those of the glass ber composite.
International Journal of Polymer Science Owing to the hierarchical structure and semicrystalline nature of cellulose, nanoparticles can be extracted from this naturally occurring polymer. Native cellulose bers are built up by smaller and mechanically stronger long thin laments, the microbrils consisting of alternating crystalline and noncrystalline domains. Multiple mechanical shearing actions can be used to release more or less individually these microbrils. This material is usually called microbrillated cellulose (MFC). Figure 11 [9396] shows transmission electron micrographs from dilute suspensions of MFC obtained from dierent sources. Longitudinal cutting of these microbrils can be performed by submitting the biomass to a strong acid hydrolysis treatment, allowing dissolution of amorphous domains. The ensuing nanoparticles occur as rod-like nanocrystals or whiskers with dimensions depending on the source of cellulose and preparation procedure. Examples are shown in Figure 12 [97104]. The typical geometrical characteristics for nanocrystals derived from dierent species and reported in the literature are collected in Table 1 [105139]. Impressive mechanical properties and reinforcing capability, abundance, low weight, and biodegradability of cellulose nanocrystals make them ideal candidates for the processing of polymer nanocomposites [140143]. With a Youngs modulus around 150 GPa and a surface area of several hundred m2 g1 [144], they have the potential to signicantly reinforce polymers at low ller loadings. A broad range of applications of nanocellulose exists even if a high number of unknown remains at date. Tens of scientic publications and experts show its potential even if most of the studies focus on their mechanical properties as reinforcing phase and their liquid crystal self-ordering properties. However, as for any nanoparticle, the main challenge is related to their homogeneous dispersion within a polymeric matrix. 6.1. Nanocomposite Processing. Cellulose nanoparticles are obtained as stable aqueous suspensions and most investigations focused on hydrosoluble (or at least hydrodispersible) or latex-form polymers. The main advantage is that the dispersion state of the nanoparticles is kept when using an aqueous medium for the processing. After dissolution of the hydrosoluble or hydrodispersible polymer, the aqueous solution can be mixed with the aqueous suspension of cellulosic nanoparticles. The ensuing mixture is generally cast and evaporated to obtain a solid nanocomposite lm. It can also be freeze-dried and hot-pressed. The preparation of cellulose nanober reinforced starch [145150], silk broin [151], poly(oxyethylene) (POE) [152156], polyvinyl alcohol (PVA) [157161], hydroxypropyl cellulose (HPC) [157, 158], carboxymethyl cellulose (CMC) [162], or soy protein isolate (SPI) [163] has been reported in the literature. The rst publication reporting the preparation of cellulose nanocrystals-reinforced polymer nanocomposites was carried out using a latex obtained by the copolymerization of styrene and butyl acrylate (poly(S-co-BuA)) and tunicin (the cellulose extracted from tunicatea sea animal) whiskers [137]. The same copolymer was used in association
6. Cellulose Nanober-Reinforced Nanocomposites

The potential of nanocomposites in various sectors of research and application is promising and attracting increasing investments. In the nanocomposite industry, a reinforcing particle is usually considered as a nanoparticle when at least one of its linear dimensions is smaller than 100 nm.
15
200 nm
100 nm
(b)
(a)
1 m
(c) (d)
Figure 11: Transmission electron micrographs from dilute suspension of MFC obtained from wood bers by mechanical processing combined to (a) enzymatic [93], (b) TEMPO-mediated oxidation [94], (c) carboxylmethylation pretreatment [95], and (d) extracted from Opuntia cus-indica [96].
with wheat straw [103, 164] or sugar beet [101] cellulose nanocrystals. Other latexes such as poly(-hydroxyoctanoate) (PHO) [165167], polyvinylchloride (PVC) [168171], waterborne epoxy [172], natural rubber (NR) [122, 173, 174], and polyvinyl acetate (PVAc) [99] were also used as matrix. Recently, stable aqueous nanocomposite dispersionscontaining cellulose whiskers and a poly(styrene-co-hexylacrylate) matrix were prepared via miniemulsion polymerization [106]. Addition of a reactive silane was used to stabilize the dispersion. Solid nanocomposite lms can be obtained by mixing and casting the two aqueous suspensions followed by water evaporation. The possibility of dispersing cellulosic nanobers in nonaqueous media has been investigated using surfactants or chemical grafting and it opens other possibilities for nanocomposites processing. Cellulose nanoparticles possess a reactive surface covered with hydroxyl groups, providing the possibility to extensive chemical modication. Although this strategy decreases the surface energy and polar character of the nanoparticles, improving by the way the adhesion with nonpolar polymeric matrix, a detrimental eect is generally reported for the mechanical performances of the composite. This unusual behavior is ascribed to the originality of the reinforcing phenomenon of polysaccharide nanocrystals resulting from the formation of a percolating network thanks
to hydrogen bonding forces. Therefore, grafting of long chains instead of small molecules can be used to preserve the mechanical properties of the material. Very few studies have been reported concerning the processing of cellulose nanobers-reinforced nanocomposites by extrusion methods. The hydrophilic nature of cellulose causes irreversible agglomeration during drying and aggregation in nonpolar matrices because of the formation of additional hydrogen bonds between amorphous parts of the nanoparticles. Therefore, the preparation of cellulose whiskers-reinforced PLA nanocomposites by melt extrusion was carried out by pumping the suspension of nanocrystals into the polymer melt during the extrusion process [175]. An attempt to use PVA as a compatibilizer to promote the dispersion of cellulose whiskers within the PLA matrix was reported [176]. Organic acid chlorides-grafted cellulose whiskers were extruded with LDPE [177]. The homogeneity of the ensuing nanocomposite was found to increase with the length of the grafted chains. Polycaprolactone-grafted cellulose nanocrystals obtained by ring-opening polymerization (ROP) of the corresponding lactone were also used as masterbatches by melt blending with a PCL matrix [178]. An attempt to use a recently patented concept (Dispersed nanoobjects protective encapsulationDOPE process) intended to disperse carbon nanotubes in polymeric
16
200 nm
(a) (b)
200 nm
200 nm
(c)
150 nm
(d)
0.5 m
200 nm
(e) (f)
250 nm
(g) (h)
200 nm
Figure 12: Transmission electron micrographs from dilute suspension of cellulose nanocrystals from: (a) ramie [97], (b) bacterial [98], (c) sisal [99], (d) microcrystalline cellulose [100], (e) sugar beet pulp [101], (f) tunicin [102], (g) wheat straw [103], and (h) cotton [104].
matrices was reported. Physically cross-linked alginate capsules were successfully formed in the presence of either cellulose whiskers or microbrillated cellulose [179]. The ensuing capsules have been extruded with a thermoplastic material. 6.2. Interfacial Interactions. Strong interactions between cellulose nanobers prepared from cottonseed linters and
between the ller and the glycerol-plasticized starch matrix were reported to play a key role in reinforcing properties [120]. In nonpercolating systems, for instance for materials processed from freeze-dried cellulose nanocrystals, strong matrix/ller interactions enhance the reinforcing eect of the ller. This observation was reported using EVA matrices with dierent vinyl acetate contents and then dierent
17
Table 1: Geometrical characteristics of cellulose nanocrystals from various sources: length (L), cross section (D), and aspect ratio (L/d). Source Acacia pulp Alfa Algal (Valonia) Bacterial Banana rachis Bioresidue from wood bioethanol production Capim dourado Cassava bagasse Cladophora Coconut husk bers Cotton Cottonseed linter Curaua Date palm tree (rachis/leaets) Eucalyptus wood pulp Flax Grass Zoysia Hemp Lua cylindrica MCC Mulberry Pea hull Ramie Recycled pulp Sisal Sugar beet pulp Sugarcane bagasse Tunicin Wheat straw Wood L (nm) 100250 200 >1,000 100several 1,000 5001,000 several 100 300 3601,700 80500 100300 170490 80170 260/180 145 100500 200700 several 1,000 242 150-300 400500 240400 350700 150250 1001,800 100500 215 210 200310 100several 1,000 150300 100300 D (nm) 515 10 1020 510 3050 5 1020 4.5 211 20 20 6 515 4060 610 6.1 6 1030 1060 30100 5.2 37 2040 712 70120 68 3080 35 5 5 26 1020 5 35 L/D 20
67 39 10 13-17 43/30 24 15 47 34 [97, 131, 132] 60/43 42 64 67 45 50
Reference [105] [106] [107, 108] [98, 109, 110] [111] [112] [113] [114] [115] [116] [117119] [120] [121] [122] [123] [124] [125, 126] [127] [128] [100] [129] [130]
[133] [99, 134, 135] [101] [136] [137] [103] [115, 138, 139]
polarities [180]. Improvement of matrix/ller interactions by using cellulose whiskers coated with a surfactant was shown to play a major role on the nonlinear mechanical properties, especially on the elongation at break [181]. Grunert and Winter [98] founded a higher reinforcing eect for unmodied cellulose whiskers than for trimethylsilylated whiskers. Apart from the fact that 18% of the weight of the silylated crystals was due to the silyl groups, they attributed this dierence to restricted ller/ller interactions. 6.3. Mechanical Performance. The rst demonstration of the reinforcing eect of cellulose nanocrystals in a poly(Sco-BuA) matrix was reported by Favier et al. [137]. The authors measured by DMA in the shear mode a spectacular improvement in the storage modulus after adding tunicin whiskers even at low content into the host polymer. This increase was especially signicant above the glass-rubber transition temperature of the thermoplastic matrix because
of its poor mechanical properties in this temperature range. Figure 13 shows the isochronal evolution of the logarithm of the relative storage shear modulus (log GT /G200 , where G200 corresponds to the experimental value measured at 200 K) at 1 Hz as a function of temperature for such composites prepared by water evaporation. In the rubbery state of the thermoplastic matrix, the modulus of the composite with a loading level as low as 6 wt% is more than two orders of magnitude higher than the one of the unlled matrix. Moreover, the introduction of 3 wt% or more cellulosic whiskers provides an outstanding thermal stability of the matrix modulus up to the temperature at which cellulose starts to degrade (500 K). The macroscopic behavior of cellulose nanobers-based nanocomposites depends as for any heterogeneous materials, on the specic behavior of each phase, the composition (volume fraction of each phase), the morphology (spatial arrangement of the phases) and the interfacial properties.
18
0
1
International Journal of Polymer Science lycerin suggesting a close association between the ller and the matrix [162]. The thermal degradation of unlled CMC was observed from its melting point (270 C) and had a very narrow temperature range of degradation. Cellulose nanocrystals were found to degrade at a lower temperature (230 C) than CMC, but shown a very broad degradation temperature range. The degradation of cellulose whiskersreinforced CMC was observed between these two limits, but of interest was the lack of steps. Composites were reported to degrade as a unit.
300 400 500
log GT /G200
2 3 4 5
200
7. Applications of Polymer Composites

7.1. Biocomposites. The charm of the use of synthetic bres in polymer composites is fading, because these are expensive, nonbiodegradable, and pollute the environment. There is an increasing movement of scientists and engineers who are dedicated to minimizing the environmental impact of polymer composite production. Environmental footprints must be diminished at every stage of the life cycle of the polymer composite. Using natural bers with polymers based on renewable resources will allow many environmental issues to be solved. By embedding biobers with renewable resourcebased biopolymers such as cellulosic plastics; polylactides; starch plastics; polyhydroxyalkanoates (bacterial polyesters); soy-based plastics, the so-called green biocomposites could soon be the future. Nowadays, biocomposites have been the subject of extensive research, specically in construction and building industry due to their many advantages such as lower weight, and lower manufacturing costs. Currently, not only builders, but also many home owners are interested in using biocomposites for dierent products such as decking, fencing, and so on. Biocomposites may be classied, with respect to their applications in building industry into two main groups: structural and nonstructural biocomposites [182, 183]. 7.1.1. Structural Application. A structural Biocomposite can be dened as one that is needed to carry a load in use. For instance, building industry, load-bearing walls, stairs, roof systems, and subooring are examples of structural biocomposites. Structural biocomposites can range broadly in performance, from high performance to low performance materials. Biobased composite materials have been tested for suitability in roof structure (Figure 14) [184]. Structural beams have been designed, manufactured, and tested, yielding good results. Soy oil-based resin and cellulose bers, in the form of paper sheets made from recycled cardboard boxes may be used for the manufacture of the composite structures. Figure 15 represents, stay-in-place bridge forms (SIP) are utilized to span the distance between bridge girders. The SIP forms made from biocomposites have many benets in comparison to steel forms. Biocomposite-based SIP forms are porous or breathable. Therefore, this lets water to evaporate through the form and to avoid any rebar corrosion. The form is also biodegradable; a biobased form has the potential to break down in the future, allowing underside inspection of the bridge deck. In addition, the form is
Temperature (K)
Figure 13: Logarithm of the normalized storage shear modulus (log GT /G200 , where G200 corresponds to the experimental value measured at 200 K) versus temperature at 1 Hz for tunicin whiskers reinforced poly(S-co-BuA) nanocomposite lms obtained by water evaporation and lled with 0 ( ), 1 ( ), 3 ( ), 6 ( ) and 14 wt% ( ) of cellulose whiskers [140].
The outstanding properties observed for these systems were ascribed to a mechanical percolation phenomenon [137]. A good agreement between experimental and predicted data was reported when using the series-parallel model of Takayanagi modied to include a percolation approach. Therefore, the mechanical performances of these systems were not only due to the high mechanical properties of the reinforcing nanoparticles. It was suspected that the stiness of the material was due to innite aggregates of cellulose whiskers. Above the percolation threshold, the cellulosic nanoparticles can connect and form a 3D continuous pathway through the nanocomposite lm. For rod-like particles such as tunicin whiskers with an aspect ratio of 67, the percolation threshold is close to 1 vol%. The formation of this cellulose network was supposed to result from strong interactions between nanobers, like hydrogen bonds. This phenomenon is similar to the high mechanical properties observed for a paper sheet, which result from the hydrogenbonding forces that hold the percolating network of bers. This mechanical percolation eect allows explaining both the high reinforcing eect and the thermal stabilization of the composite modulus for evaporated lms. Any factor that aects the formation of the percolating whiskers network or interferes with it changes the mechanical performances of the composite [141]. Three main parameters were reported to aect the mechanical properties of such materials, namely, the morphology and dimensions of the nanoparticles, the processing method, and the microstructure of the matrix and matrix/ller interactions. 6.4. Thermal Stability. Thermogravimetric analysis (TGA) experiments were performed to investigate the thermal stability of tunicin whiskers/POE nanocomposites [152, 153]. No signicant inuence of the cellulosic ller on the degradation temperature of the POE matrix was reported. Cotton cellulose nanocrystals content appeared to have an eect on the thermal behavior of CMC plasticized with
19 particleboard, and mineral-bonded panels. Bagasse bers are used for particleboards, berboards, and composition panel production. Cereal straw is the second most usual agrobased ber in panel production. The high percentages of silica in cereal straw make them naturally re resistant. Also, the low density of straw panels has made them resilient. Results show that houses built by these panels are resistant to earthquake. Straw is also used in particleboards. Rice husks are also brous and need little energy input to make the husks ready for use. Rice husks or their ash are used in ber cement blocks and other cement products. The presence of rice husks in building products helps to increase acoustic and thermal properties. A stress-skin panel-type product has been made by using polyurethane or polyester foam in the core and ply-bamboo in the faces [185]. Figure 16 indicates performance of cellular biocomposite panels against conventional slab and panel systems for commercial and residential construction [186]. 7.2. Nanocomposites. The potential applicability of nanocellulose is widely extended. Applications of nanocellulose are mainly considered to be in paper and packaging products, although construction, automotive, furniture, electronics, pharmacy, and cosmetics are also being considered. For companies producing electroacoustic devices, nanocellulose is used as a membrane for high quality sound. Additionally, nanocellulose is applied in membrane for combustible cells (hydrogen); additives for high quality electronic paper (e-paper); ultraltrating membranes (water purication); membranes used to retrieve mineral and oils [187], and nowadays, nanocellulose has been greatly discussed and researched a huge variety of applications. The high strength and stiness as well as the small dimensions of nanocellulose may well impart useful properties to composite materials reinforced with these bers, which could subsequently be used in wide range of applications. 7.2.1. Electronic Industry Diaphragms. Among various applications studied so far, which has already reached the level of practical use is related to acoustic diaphragms, nanocellulose has been found to bear two essential properties: high sonic velocity and low dynamic loss. In fact, the sonic velocity of pure lm was almost equivalent to those of aluminium and titanium [63]. Jonas and Farah [188] stated that SONY had already been using it in headphones diaphragm (Figure 17). The nanocellulose diaphragms are developed by dehydration and compressed to a thickness of 20 microns in a diaphragm die. The advantage of the ultrathin nanocellulose diaphragm is that it can produce the same sound velocity as an aluminum or titanium diaphragm, along with the warm, delicate sound that a paper diaphragm provides. Trebles are sparkling clear, and bass notes are remarkably deep and rich in these types of headphones. Digital Displays. Cellulose has always been the prime medium for displaying information in our society; nowadays, eorts have been made to nd dynamic display technology, for
Figure 14: Biobased composite roof panels; one of them is mounted on a demonstration house made of timber [184].
Girder
SIP form
Angle
Cross section of SIP form
Figure 15: Stay-in-place bridge form.
lighter compared to a steel form, allowing faster and cheaper installations. 7.1.2. Nonstructural Application. A nonstructural biocomposite can be dened as one that need not carry a load during service. Materials such as thermoplastics, wood particles, and textiles are used to make this kind of Biocomposites. Nonstructural biocomposites are used for products such as ceiling tiles, furniture, windows, and doors. Wood ber plastic composites are made in standard lumber prole cross-section dimensions in exterior construction. These bioproducts are utilized as dock surface boards, deck, picnic tables, landscape timbers, and industrial ooring. Many manufacturers recommend that biocomposites need gaps on both edges and ends for their thermal expansion. Furthermore, wood-based bioproducts are gapped for expansion due to the moisture absorption. Clear ponderosa pine is utilized in clad components. Currently, it is becoming limited and expensive. In addition, ponderosa pine needs broad cutting, edge gluing, and nger jointing to get clear sections for window and door fabrication. Also, the glued up material have to be milled to the accurate cross section to be used in the assembly which results in increasing cost and waste wood. Therefore, manufacturers use wood ber plastic composites as an alternative for solid wood in clad components. Biocomposites are utilized for the construction of composite panels. There are three types of panels: berboard,
20
9 Allowable pressure (kPa) 7 6 5 4 3 2 1 0 Hollow core PS concrete Solid RC slab 1.8 kPa 8.4 kPa 8 Span length = 6.1 m Thickness = 203 mm Width = 1219 mm allow = L/180
6.7 kPa
Insulted structural Cellular biopanel panel
Figure 16: Performance of cellular biocomposite panels against conventional slab and panel systems for commercial and residential construction [186].
Legnani et al. [191] developed biodegradable and biocompatible exible organic light emitting diode (FOLED) (Figure 20) based on nanocellulose (NC) membrane as substrate. Nanocomposite substrates based on nanocellulose (NC) and Boehmite-siloxane systems with improved optical transmittance in the visible region were used as exible substrate for OLED applications. The nanocomposites formations improve the optical transmittance in visible range. Transmittance of 66% at 550 nm was found for the NCnanocomposite/ITO (Indium Tin Oxide) substrate when compared to the 40% value at the same wavelength for the NC/ITO substrate. ITO lm was deposited at room temperature onto membranes and glass using rf magnetron sputtering with a r f power of 60 W and at pressure of 1 mtorr in Ar atmosphere.
Figure 17: Nanocellulose diaphragm used in SONY headphones.
example in electronic paper. Nanocellulose is dimensionally stable and has a paper-like appearance which puts it into the leading role for the electronic papers basic structure [189]. Shah and Brown [189] proved the concept in a device that holds many advantages such as high paper-like reectivity, exibility, contrast, and biodegradability. Figures 18 and 19 show the fabrication process of display device using nanocellulose. Summarizing, the whole idea is to integrate an electronic dye into the nanostructure of the microbial cellulose, and when integrated, a simple pixel can reversibly switch from the ON to the OFF state. The pixel size is controlled by the minimum addressing resolution of backplane drive circuits [189]. Yano et al. [190] have shown nanocellulose extraordinary potential as a reinforcement material in optically transparent plastics, for instance, as a substrate for bendable displays. According to the author, the composite remained optically transparent even at high ber contents.
Other Electronic Usages. Evans et al. [192] found that nanocellulose catalyzed the deposition of metals within its structure, thus a nely divided homogeneous catalyst layer is generated. Experimental data suggested that nanocellulose possessed reducing groups capable of initiating the precipitation of palladium, gold, and silver from aqueous solution. Thus, the structure is suitable for the construction of membrane electrode assemblies. Olson et al. [193] showed that freeze-dried cellulose nanobril aerogels can be used as templates for making lightweight porous magnetic aerogels, which can be compacted into a sti magnetic nanopaper. 7.2.2. Pharmaceutical. Cellulose has a long history of use in the pharmaceutical industry. The material has excellent compaction properties when blended with other pharmaceutical excipients so that drug-loaded tablets form dense matrices suitable for the oral administration of drugs. Polysaccharides, natural polymers, fabricated into hydrophilic matrices remain popular biomaterials for controlled-release dosage forms and uses of a hydrophilic polymer matrix is one of the most popular approaches in formulating an extended
6.4 kPa
21
Nanocellulose paper
Infusing electrochromic material into the paper
Attaching electrode and protecting layer
Figure 18: Fabrication process of the display using nanocellulose.
(a)
(b)
(c)
(d)
Figure 19: (a) The paper made of nanocellulose; (b) display device; (c) and (d) show the result of the chromogenic testing [189].
Figure 20: Cellulose Nanocomposite based Flexible Organic Light Emitting Diode (FOLED).
release dosage forms [194196]. This is due to the fact that these formulations are relatively exible, and a well-designed system usually gives reproducible release proles. Drug release is the process by which a drug leaves a drug product and is subjected to absorption, distribution, metabolism, and excretion (ADME), eventually becoming available for phar-
macologic action. Crystalline nanocellulose oers several potential advantages as a drug delivery excipient. Crystalline nanocellulose and other types of cellulose in advanced pelleting systems whereby the rate of tablet disintegration and drug release may be controlled by microparticle inclusion, excipient layering or tablet coating [197, 198]. The very large surface area and negative charge of crystalline nanocellulose suggest that large amounts of drugs might be bound to the surface of this material with the potential for high payloads and optimal control of dosing. Other nanocrystalline materials, such as nanocrystalline clays, have been shown to bind and subsequently release drugs in a controlled manner via ion exchange mechanisms and are being investigated for use in pharmaceutical formulations [199]. The established biocompatibility of cellulose supports the use of nanocellulose for a similar purpose. The abundant surface hydroxyl groups on crystalline nanocellulose provide a site for the surface modication of the material with a range of chemical groups by a variety of methods. Surface modication may be used to modulate the loading and release of drugs that would not normally bind to nanocellulose, such as nonionized and hydrophobic
22
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Figure 21: Biomedical applications of nanocellulose (a) and (b) never dried nanocellulose membrane [203]; (c) and (d) articial blood vessels [205]; (e) dura mater reconstruction [202] (f) covering Stents [204].
drugs. For example, L nnberg et al. suggested that poly(capo rolactone) chains might be conjugated onto nanocrystalline cellulose for such a purpose [200]. Additionally, since crystalline nanocellulose is a low-cost, readily abundant material from a renewable and sustainable resource, its use provides a substantial environmental advantage compared with other nanomaterials. 7.2.3. Medical. Recently, nanocellulose has been called as the eyes of biomaterial highly applicable to biomedical industry which includes skins replacements for burnings and wounds; drugs releasing system; blood vessel growth; nerves, gum and duramater reconstruction; scaolds for tissue engineering; stent covering and bone reconstruction [201 205]. Figure 21 shows some applications for nanocellulose within biomedical eld. Tissue engineering looks for new material and devices which could interact positively with biological tissues [206], either working as an in vitro basis for cell growth or rearranging and developing tissue about to be implanted. They also aim new classes of degradable biopolymers that are biocompatible and whose activities are controllable and specic [207], more likely to be used as cell scaolds [208] or in vitro tissue reconstruction. As described above, a great variety of biomaterials have been developed recently. They have all sorts of properties (physical,chemical, and mechanical) depending mostly in the nal application (tissue regeneration, medication holding and releasing, tissue grafting, or scaolding) [203]. The scaffolds success depends much on the cellular adhesion and
growth onto the surface, thus biopolymers chemical surface can dictates cellular response by interfering in cellular adhesion, proliferation, migration, and functioning. The surface-cell interaction is extremely important in implant eectiveness, including its rejection. Since the interaction is fully understood in a cell level, new biomaterials and products can be easily developed [209]. The problems still arise due to some methods ineciency such as cell seeds and sources, scaolding, ambient, extracellular matrix producing, and analysis and appropriate models [210]. On the other hand, to regenerate tissues, three specic foundations are taken: cells, support, and growth factors. Cells synthesize the matrix for the new tissues, support holds and keeps the ambient proper for the growth, while the growth factors facilitate and promote the cell regeneration [210]. Material used for implants cannot be either rejected or causes inammatory response, in others, it should be biocompatible. Furthermore, it should promote regeneration and if necessary, be absorbed after a while or biodegradable [211]. Studies on support-cell interactions are crucial to implants viability. Many cell responses are observed out of dierent materials, so the cell ability to discriminate and adapt to it whether adhere or not to its surface [212]. This is crucial as it will direct further responses as cell proliferation, migration, and viability. Due to the clinical importance of skin lesions, many laboratories had been aroused to the search for healing products having benets including immediate pain relief, close adhesion to the wound bed, and reduced infection rate. The nanocellulose developed having huge supercial area that
23 composite is a promising material for cardiovascular softtissue replacement applications. Cai and Kim [216] have three dierent methods to prepare nanocellulose/PEG composite. In the method I, PEG was incorporated in nanocellulose hydrogels by adding PEG solution to the culture medium for Gluconacetobacter xylinus. In the method II, suspensions of microbial cellulose nanobers are mixed with PEG solution with mechanical stirring followed by freezing-thawing process. The composite is a hydrogel and can be used for soft tissue replacement devices. In the method III, a previously produced nanocellulose hydrogel was soaked with PEG solution, allowing the PEG molecules to penetrate the nanocellulose [217]. The third method seems simple and eective. It has also been used to prepare other nanocellulose-based composite. For instance, nanocellulose has been soaked into hydroxyapatite to develop a composite scaold for bone regeneration [218]. Nanocellulose has also been augmented by immersion in solutions of polyacrylamide and gelatin, yielding hydrogels with improved toughness [219]. Similarly, immersion of nanocellulose into poly (vinyl alcohol) has yielded hydrogels having a wide range of mechanical properties of interest for cardiovascular implants [215]. In this study, authors reported method III. SEM images showed that PEG molecules were not only coated on the nanocellulose brils surface but also penetrated into the nanocellulose ber networks. The prepared scaold has very well-interconnected porous network structure and large aspect surface. The TGA results prove the improved thermal stability. Tensile test results indicated that Youngs Modulus and tensile strength tended to decrease while the elongation at break had a slight increase. It showed much better biocompatibility compared with the pure nanocellulose. Thus, the prepared Nanocellulose/PEG composite scaolds are suitable for cell adhesion/attachment, suggesting that these scaolds can be used for wound dressing or tissue-engineering applications. Lin et al. [220] used gelatin and its enzymatically modied form (EMG) to prepare nanocellulose nanocomposites in an attempt to enhance the property of rehydration ability of nanocellulose. Referencing SEM photographs of the low gelatin/nanocellulose composites (LG/NC), gelatin is shown to lodge in nanocellulose networks and wrap up parts of cellulose ribbons (Figure 23(a)). As gelatin content in this sample was around 50% (less than in high gelatin/ nanocellulose composites (HG/NC)), a certain quantity of cellulose ribbons emerged. EMG lled up some of the space in the nanocellulose network and some thickened cellulose ribbons could be observed in EMG/NC composites (Figure 23(b)). Film-like structures were observed only less in nonpolar EMG/nanocellulose (NPEMG/NC) and polar (PEMG/NC) composites. Porous networks and thickened cellulose ribbons could be found in these two composites (Figures 23(c) and 23(d)). It appears that NPEMG and PEMG permeated into the network and adsorbed on the cellulose ribbons, allowing the continuance of porous structures in these composites. According to the results, they concluded that gelatin and its hydrolysates in combination with nanocellulose can eectively improve the rehydration properties of composites.
Figure 22: Nanocellulose and propolis-based bandage [213].
gives great water absorption capacity and elasticity. These are characteristics from an ideal healing bandage. On the other hand, it holds no microbial activity. Nanocellulose mats are very eective in promoting autolytic debridement, reducing pain, and accelerating granulation, all of which are important for proper wound healing. These nanobiocellulose membranes can be created in any shape and size, which is benecial for the treatment of large and dicult to cover areas of the body. Barud [213] has developed a biological membrane with bacterial cellulose and standardized extract of propolis. Propolis has many biological properties including antimicrobial and anti-inammatory activities. All the above mentioned characteristics present, which make the membrane (Figure 22) a good treatment for burns and chronic wounds. Odontology is challenged to nd ideal materials to replace the bones in several procedures, as bones malformation, maxillary, and facial deformities. The biggest challenge is the loss of alveolar bone. Nanocellulose having suitable porosity which gives the mat an infection barrier, loss of uids, painkiller eect, allows medicines to be easily applied and it also absorbs the purulent uids during all inammatory stages, expelling it later on in a controlled and painless manner [214]. Polyvinyl alcohol (PVA) is a hydrophilic biocompatible polymer with various characteristics desired for biomedical applications. PVA can be transformed into a solid hydrogel with good mechanical properties by physical crosslinking, using freeze-thaw cycles. Hydrophilic nanocellulose bers of an average diameter of 50 nm are used in combination with PVA to form biocompatible nanocomposites. According to Millon and Wan [215], the resulting nanocomposites possess a broad range of mechanical properties and can be made with mechanical properties similar to that of cardiovascular tissues, such as aorta and heart valve leaets. On their studies, the stress-strain properties for porcine aorta are matched by at least one type of PVA-nanocellulose nanocomposite in both the circumferential and the axial tissue directions. A PVA-nanocellulose nanocomposite with similar properties as heart valve tissue is also developed. Relaxation properties of all samples, which are important for cardiovascular applications, were also studied and found to relax at a faster rate and to a lower residual stress than the tissues they might replace. So, nally the new PVA-nanocellulose
24
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Figure 23: SEM photographs (10000X) of LG/NC (a) Gelatin/NC (b) EMG/NC (c) NPEMG/NC (d) PEMG/NC [220].
The polar functional groups of gelatin and EMG as well as nanocellulose porous networks with lower level of crystallinity contributed to the rehydration ability of composites. Nanocellulose immersed in 0.5% EMG solution was sucient to prepare the desirable composites and may be applied in a rehydratable membrane. In ophthalmologist area, Huia et al. [221] explored the potentiality of nanocellulose applied as the scaold of tissue engineering cornea. They studied the growth of human corneal stromal cells on nanocellulose. The ingrowth of corneal stromal cells into the scaold was veried by laser-scanning confocal microscope. The results suggest the potentiality for this biomaterial as a scaold for tissue engineering of articial cornea. The surface of nanocellulose is lumpy with rills. In Figures 24(a) and 24(b), the red regions are corneal stromal cells immunouorescent stained by Vim and the blue region is the nanocellulose scaold. It is clearly illustrated that corneal stromal cells ingrew into the scaold.
For otorhinolaryngologist, surgery of the lateral wall of the nose is common procedure in the ENT specialty and was recommended for resection of soft lush, removal of tumors, or to promote aeration of the sinuses. The evolution of surgical techniques provided increased safety to patients, drastically reducing the complications and postoperative morbidity. The nasal bleeding, surgical wound infections, local pain, and the presence of adhesions are the major complicating factors related to nasal surgery. Several types of materials have been developed in order to prevent these complications. Nasal packing has been used in these postsurgical procedures and, although eective in preventing bleeding, requires removal causing great discomfort to the patient. Moreover, their presence has been associated with systemic infections graves. The use of a material that, in addition to preventing bleeding, could provide more rapid healing without the formation of crusts and prevent infection without the need
25 shows the untreated segment of carotid artery revealing a homogeneous endothelialization inside the grafts with an almost smooth transition to the artery. Another use of nanocellulose is for nasal reconstruction. The desire for an ideal shape has always been part of mankind. Nose, centrally located in the face, is better susceptible to traumas, deformities, thus social disorders. Even since having a major breathing function, it has a great esthetic function, highlighting faces genetics. Amorim et al. [223] evaluated the tissue response to the presence of nanocellulose in the nose bone (Figure 26). It had been used 22 rabbits, being that, in 20 a cellulose blanket was implanted in the nasal dorsum, 2 were kept as control group. After three and six months, the back bone was extirpated for further histopathological study, parameter, were such as blood vessels clogging, inammation intensity, and presence of purulent uids. Inammation was found to be stable, which is probably due to the surgical procedure itself and not to the cellulosic blanket. For the other parameters, there was no statistical signicance. Nanocellulosic blanket showed good biocompatibility and did not change over time, thus an excellent material to elevate the nose bone. 7.2.4. Veterinary. Hart et al. [224] studied the pellicle and its ability to promote broblast migration and cellular proliferation in diabetic rats. The treatment accelerated the wound healing for the diabetic rats and improved histological outcome. Diabetic rat is a recognized model for chronic wounds, thus sharing some features with the chronic human wound. So they could predict the applicability in humans. Helenius et al. [225] studied for the rst time the in vivo biocompatibility of nanocellulose systematically. Thus, in the development nanocellulose membrane was implanted into the subcutaneous space of rats for 1, 4, and 12 weeks. The implants were evaluated in aspects of chronic inammation, foreign body responses, cell ingrowth, and angiogenesis, using histology, immunohistochemistry, and electron microscopy. There were no macroscopic signs of inammation around the implants (redness, edema or exudates) (Figure 27). There were no microscopic signs of inammation either (i.e., a high number of small cells around the implants or the blood vessels). No brotic capsule or giant cells were present. Fibroblasts inltrated nanocellulose (Figure 28), which was well integrated into the host tissue and did not elicit any chronic inammatory reactions, so the biocompatibility of nanocellulose is proved and the material has potential to be used as a scaold in tissue engineering. Helenius et al. [225] brought up more knowledge on biomaterial and its interaction with the cell. In their study, membranes of nanocellulose had been implanted into rats and the biocompatibility was evaluated in vivo. Implants did not cause foreign body reaction, brosis or encapsulation, and the rats conjunctive tissues were well integrated to nanocellulose. Some weeks after the implantation, the rearrangement kept on happening and broblasts were fully integrated to the cellulosic structure, they had started to synthesize collagen.
11520 nm 0 nm
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Figure 24: Growth of Vim immune uorescent stained human corneal stromal cells in nanocellulose scaold, observed by LSCM (400X) [221].
for removal would be of great aid in the postoperative period of patients undergoing resection of the lower nasal concha and other nasal surgeries. In 1984, microbiologist Louis Farah Fernando Xavier was able, through the fermentation of bacteria of the genus Acetobacter, to produce bacterial cellulose. The resulting lm of this synthesis, after processing, is endowed with selective permeability, allowing passage of water vapour but preventing the passage of microorganisms. It is semitransparent, homogeneous, with an average thickness of 0.05 mm and visually very similar to human skin. Schumann et al. [222] studied the articial vascular implants from nanocellulose by two studies. In a rst microsurgical study, the nanocellulose implants were attached in an articial defect of the carotid artery of rats for 1 year. These long-term results show the incorporation of the nanocellulose under formation of neointima and ingrowth of active broblasts. In a second study, the grafts were used to replace the carotid arteries of pigs. After 3 months, these grafts were removed and analyzed both macro- and microscopically. Seven grafts (87.5%) were patent whereas one graft was found occluded. These data indicate that the innovative nanocellulose engineering technique results in the production of stable vascular conduits and conrm a highly attractive approach to in vivo tissue-engineered blood vessels as part of programs in cardiovascular surgery. The Figure 25
26
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Figure 25: SEM (magnication 169 to 199): (a) untreated segment of the carotid artery, (b) and (c) good endothelialization of nanocellulose grafts [222].
Cellulose blanket
Nasal septum
Figure 26: Serial cut from the nasal septum and front part of the nose showing the cellulose blanket in the nose bone structure.
(a source of contaminants, Figure 29). Silva found that nanocellulose associated to the HAP promoted faster bone regeneration if compared with the control group. 8 days after procedure and a delay of 30 days, although after 50 days they had tissues alike. Costa and de Souza [227] studied the skin healing in white swines; they underwent thermal abrasion, (metal temperature at 100 C). Comparing Bionext to the daily healing bandage, all the animals had the healing process completed equally. No dierences were seen between the daily bandage and the cellulose pellicle (Bionext ). For dogs whose peritoneum had been replaced, it was observed that 45 days after the implant, broblasts and blood vessels numbers increased. After 90 days, collagen and broblasts penetrated into nanocellulose and 180 days after implantation nanocellulose formed a net along the conjunctive tissue, little evidence of neovascularization was found [228]. 7.2.5. Dental. Nanocellulose was tested in dental tissue regeneration. Microbial cellulose, produced by the Glucanacetobacter xylinus strain, can be used to regenerate dental tissues in humans (Figure 30). Nanocellulose product Gengiex and Gore-Tex has intended applications within the dental industry. It was developed to aid periodontal tissue recovery [229]. A description was given of a complete restoration of an osseus defect around an IMZ implant in association with a Gengiex therapy. The benets included the reestablishment of aesthetics and function of the mouth and that a reduced number of surgical steps were required. The bandage, called Gengiex, consists of two layers: the inner layer is composed of microbial cellulose, which oers rigidity to the membrane, and the outer alkalicellulose layer is chemically modied [230]. Salata et al. [231] compared the biological performance of Gengiex and GoreTex membranes using the in vivo nonhealing bone-defect model proposed by Dahlin et al. [232]. The study showed that Gore-Tex membranes (a composite with polytetrauoroethylene, urethane, and nylon) were associated with signicantly less inammation and both membranes promoted the same amount of bone formation
Figure 27: Explantation of implants after 1 week [225].
Helenius et al. [225] had also shown that the density inuenciates the morphology and cell penetration such as density increased, cell migration lowed. It was observed that nucleus morphology depends on the direction taken by the cellulosic nanober, blood ow was also observed. Fewer cells are present compared to that after 1 and 4 weeks and the broblasts inside the nanocellulose have synthesized collagen (B) high magnication of the interface area at the porous side of nanocellulose after 12 weeks. Arrow heads show collagen synthesized by the broblasts Silva [226] had evaluated the biological behavior of synthetic hydroxyapatite (HAP-91) when implanted in the dental cavities and covered by nanocellulose. Membranes were shaped into triangles fully covering the cavities avoiding the contact between hydroxyapatite and the oral cavity
27
100 m
50 m
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Figure 28: Ladewigs trichrome staining. (a) The compact side after 12 weeks showing the broblasts inside the nanocellulose have synthesized collagen (seen as blue staining; indicated with arrow heads), (b) High magnication of the interface area at the porous side of nanocellulose after 12 weeks (Arrow heads show collagen synthesized by the broblasts) [225].
Figure 29: Cellulosic membranes used as dental cavities covering in cats [226].
Before
After
Figure 30: Nanocellulose used in dental tissue regeneration in 39-year-old female patient.
during the same period of time. A greater amount of bone formation was present in bone defects protected by either Gore-Tex or microbial cellulose membrane, when compared to the control sites. Gore-Tex is better tolerated by the tissues than Gengiex. Recently, in a similar vein, Macedo et al. [233] also compared bacterial cellulose and polytetrauoroethylene (PTFE) as physical barriers used to treat bone defects in guided tissue regeneration. In this study, two osseous defects (8 mm in diameter) were performed in each hind-foot of four adult rabbits, using surgical burs with constant sterile saline solution irrigation. The eects obtained on the right hind-feet were protected with PTFE barriers, while
Gengiex membranes were used over wounds created in the left hind-feet. After 3 months, the histological evaluation of the treatments revealed that the defects covered with PTFE barriers were completely repaired with bone tissue, whereas incomplete lamellar bone formation was detected in defects treated with Gengiex membranes, resulting in voids and lack of continuity of bone deposition. Nanocellulose with its characteristics like nanobers size and distribution, mechanical properties, compatibility, and ability to mold create it has a unique biomaterial indispensable in health area. The nanocellulose composite scaolds are biocompatible with less rejection with cellular contact and
28 blood contact cells interaction to be a promissory biomaterial and may be suitable for cell adhesion/attachment suggesting that these scaolds can be used for wound-dressing or tissueengineering scaolds.

[13] http://www.bersource.com/f-tutor/cellulose.htm. [14] P. M. Visakh and S. Thomas, Preparation of bionanomaterials and their polymer nanocomposites from waste and biomass, Waste and Biomass Valorization, vol. 1, no. 1, pp. 121134, 2010. [15] G. I. Williams and R. P. Wool, Composites from natural bers and soy oil resins, Applied Composite Materials, vol. 7, no. 5-6, pp. 421432, 2000. [16] F. G. Torres and R. M. Diaz, Morphological characterisation of natural bre reinforced thermoplastics (NFRTP) processed by extrusion, compression and rotational moulding, Polymers & Polymer Composites, vol. 12, no. 8, pp. 705718, 2004. [17] M. Z. Rong, M. Q. Zhang, Y. Liu, G. C. Yang, and H. M. Zeng, The eect of ber treatment on the mechanical properties of unidirectional sisal-reinforced epoxy composites, Composites Science and Technology, vol. 61, Article ID 10.1016/S02663538(01)00046-X, pp. 14371447, 2001. [18] K. Van de Velde and P. Kiekens, Thermoplastic pultrusion of natural bre reinforced composites, Composite Structures, vol. 54, no. 2-3, pp. 355360, 2001. [19] H. L. Bos, M. J. A. van den Oever, and O. C. J. J. Peters, Tensile and compressive properties of ax bres for natural bre reinforced composites, Journal of Materials Science, vol. 37, no. 8, pp. 16831692, 2002. [20] C. Baley, Analysis of the ax bres tensile behaviour and analysis of the tensile stiness increase, Composites Part A, vol. 33, no. 7, pp. 939948, 2002. [21] B. Lamy and C. Baley, Stiness prediction of ax bersepoxy composite materials, Journal of Materials Science Letters, vol. 19, no. 11, pp. 979980, 2000. [22] A. J hn, M. W. Schr der, M. F ting, K. Schenzel, and W. a o u Diepenbrock, Characterization of alkali treated ax bres by means of FT Raman spectroscopy and environmental scanning electron microscopy, Spectrochimica Acta Part A, vol. 58, no. 10, pp. 22712279, 2002. [23] J. Gassan and A. K. Bledzki, Einu von haftvermittlern auf das feuchteverhalten naturfaserverst rkter kunststoe, Die a Angewandte Makromolekulare Chemie, vol. 236, pp. 129138, 1996. [24] A. J. Michell, Wood cellulose-organic polymer composites, in Composite Asia Pacic, vol. 89, p. 19, Institute of Australia, Adelaide, Australia, 1989. [25] T. M. Maloney, in International Encyclopedia of Composites, S. M. Lee and R. M. Rowell, Eds., p. 656, VCH Publishers, New York, USA, 1995. [26] K. P. Mieck, A. Nechwatal, and C. Knobelsdorf, Potential applications of natural bres in composite materials, Melliand Textilberichte, vol. 75, no. 11, p. 892, 1994. [27] P. S. Mukherjee and K. G. Satyanarayana, An empirical evaluation of structure-property relationships in natural bres and their fracture behaviour, Journal of Materials Science, vol. 21, no. 12, pp. 41624168, 1986. [28] A. Alemdar and M. Sain, Biocomposites from wheat straw nanobers: morphology, thermal and mechanical properties, Composites Science and Technology, vol. 68, no. 2, pp. 557565, 2008. [29] A. Alemdar and M. Sain, Isolation and characterization of nanobers from agricultural residueswheat straw and soy hulls, Bioresource Technology, vol. 99, no. 6, pp. 16641671, 2008. [30] T. Zimmermann, N. Bordeanu, and E. Strub, Properties of nanobrillated cellulose from dierent raw materials and its
8. Conclusions
The potential applicability of cellulose-based biocomposites and nanocomposites is widely extended. Due to a great number of properties, applications of nanocellulose-based materials are mainly considered to be in a wide range of applications such as paper and packaging products, construction, automotive, furniture, and electronics. Pharmacy, cosmetics, and biomedical applications are also being considered. The mechanical properties such as high strength and stiness, the surface reactivity (with numerous hydroxyl groups), the specic organization as well as the small dimensions of nanocellulose may well impart useful properties to (nano)composite materials reinforced with these bers.
References
[1] S. Kalia, B. S. Kaith, and I. Kaur, Pretreatments of natural bers and their application as reinforcing material in polymer composites-a review, Polymer Engineering and Science, vol. 49, no. 7, pp. 12531272, 2009. [2] I. Siro and D. Plackett, Microbrillated cellulose and new nanocomposite materials: a review, Cellulose, vol. 17, no. 3, pp. 459494, 2010. [3] S. J. Eichhorn, A. Dufresne, M. Aranguren et al., Review: current international research into cellulose nanobres and nanocomposites, Journal of Materials Science, vol. 45, no. 1, pp. 133, 2010. [4] A. K. Bledzki, S. Reihmane, and J. Gassan, Properties and modication methods for vegetable bers for natural ber composites, Journal of Applied Polymer Science, vol. 59, no. 8, pp. 13291336, 1996. [5] P. R. Hornsby, E. Hinrichsen, and K. Tarverdi, Preparation and properties of polypropylene composites reinforced with wheat and ax straw bres: part II analysis of composite microstructure and mechanical properties, Journal of Materials Science, vol. 32, no. 4, pp. 10091015, 1997. [6] K. Oksman, L. Wallstrom, L. A. Berglund, and R. D. T. Filho, Morphology and mechanical properties of unidirectional sisal-epoxy composites, Journal of Applied Polymer Science, vol. 84, no. 13, pp. 23582365, 2002. [7] D. N. Saheb and J. P. Jog, Natural ber polymer composites: a review, Advances in Polymer Technology, vol. 18, no. 4, pp. 351363, 1999. [8] S. T. Georgopoulos, P. A. Tarantili, E. Avgerinos, A. G. Andreopoulos, and E. G. Koukios, Thermoplastic polymers reinforced with brous agricultural residues, Polymer Degradation and Stability, vol. 90, no. 2, pp. 303312, 2005. [9] R. L. Crawford, Lignin Biodegradation and Transformation, John Wiley & Sons, New York, NY, USA, 1981. [10] A. Payen, M moire sur la composition du tissu propre des e plantes et du ligneux, Comptes Rendus, vol. 7, pp. 1052 1056, 1838. [11] Dor e, The Methods of Cellulose Chemistry, Chapman & Hall, e London, UK, 1947. [12] The Merck Index, Merck & Co, Rahway, NJ, USA, 8th edition, 1968.

reinforcement potential, Carbohydrate Polymers, vol. 79, no. 4, pp. 10861093, 2010. B. Wang and M. Sain, Dispersion of soybean stock-based nanober in a plastic matrix, Polymer International, vol. 56, no. 4, pp. 538546, 2007. A. Kaushik, M. Singh, and G. Verma, Green nanocomposites based on thermoplastic starch and steam exploded cellulose nanobrils from wheat straw, Carbohydrate Polymers, vol. 82, no. 2, pp. 337345, 2010. S. Kalia, S. Vashistha, and B. S. Kaith, Cellulose nanobers reinforced bioplastics and their applications, in Handbook of Bioplastics and Biocomposites Engineering Applications, S. Pilla, Ed., chapter 16, Wiley-Scrivener Publishing, New York, NY, USA, 2011. E. M. Teixeira, A. C. Corr a, C. R. de Oliveira et al., Cellulose e nanobers from white and naturally colored cotton bers, Cellulose, vol. 17, no. 3, pp. 595606, 2010. W. Stelte and A. R. Sanadi, Preparation and characterization of cellulose nanobers from two commercial hardwood and softwood pulps, Industrial and Engineering Chemistry Research, vol. 48, no. 24, pp. 1121111219, 2009. S. Kalia, B. S. Kaith, S. Sharma, and B. Bhardwaj, Mechanical properties of ax-g-poly(methyl acrylate) reinforced phenolic composites, Fibers and Polymers, vol. 9, no. 4, pp. 416 422, 2008. R. Agrawal, N. S. Saxena, K. B. Sharma, S. Thomas, and M. S. Sreekala, Activation energy and crystallization kinetics of untreated and treated oil palm bre reinforced phenol formaldehyde composites, Materials Science and Engineering A, vol. 277, no. 1-2, pp. 7782, 2000. F. M. B. Coutinho, T. H. S. Costa, and D. L. Carvalho, Polypropylene-wood ber composites: eect of treatment and mixing conditions on mechanical properties, Journal of Applied Polymer Science, vol. 65, no. 6, pp. 12271235, 1997. L. Gonz lez, A. Rodrguez, J. L. de Benito, and A. Marcosa Fern ndez, Applications of an azide sulfonyl silane as elasa tomer crosslinking and coupling agent, Journal of Applied Polymer Science, vol. 63, no. 10, pp. 13531359, 1997. S. R. Culler, H. Ishida, and J. L. Koenig, silane interphase of composites: eect of process conditions on gamma aminopropyltriethoxysilane, Polymer Composites, vol. 7, no. 4, pp. 231238, 1986. N. D. Ghatge and R. S. Khisti, Performance of new silane coupling agents along with phenolic nobake binder for sand core, Journal of Polymer Materials, vol. 6, no. 3, pp. 145149, 1989. M. S. Sreekala, M. G. Kumaran, S. Joseph, M. Jacob, and S. Thomas, Oil palm bre reinforced phenol formaldehyde composites: inuence of bre surface modications on the mechanical performance, Applied Composite Materials, vol. 7, no. 5-6, pp. 295329, 2000. I. Van De Weyenberg, J. Ivens, A. De Coster, B. Kino, E. Baetens, and I. Verpoest, Inuence of processing and chemical treatment of ax bres on their composites, Composites Science and Technology, vol. 63, no. 9, pp. 1241 1246, 2003. A. Valadez-Gonzalez, J. M. Cervantes-Uc, R. Olayo, and P. J. Herrera-Franco, Chemical modication of henequen bers with an organosilane coupling agent, Composites Part B, vol. 30, no. 3, pp. 321331, 1999. D. Ray, B. K. Sarkar, A. K. Rana, and N. R. Bose, Eect of alkali treated jute bres on composite properties, Bulletin of Materials Science, vol. 24, no. 2, pp. 129135, 2001.
29
[46] K. Joseph, L. H. C. Mattoso, R. D. Toledo et al., Natural ber reinforced thermoplastic composites, in Natural Polymers and Agrobers Composites, E. Frollini, A. L. Leo, and L. H. C. a Mattoso, Eds., chapter 4, pp. 159201, Embrapa, Sn Carlos, a Brazil, 2000. [47] J. Gassan and A. K. Bledzki, Alkali treatment of jute bers: relationship between structure and mechanical properties, Journal of Applied Polymer Science, vol. 71, no. 4, pp. 623629, 1999. [48] C. Garcia-Jaldon, D. Dupeyre, and M. R. Vignon, Fibres from semi-retted hemp bundles by steam explosion treatment, Biomass and Bioenergy, vol. 14, no. 3, pp. 251260, 1998. [49] E. S. Rodriguez, P. M. Stefani, and A. Vazquez, Eects of bers alkali treatment on the resin transfer molding processing and mechanical properties of JuteVinylester composites, Journal of Composite Materials, vol. 41, no. 14, pp. 17291741, 2007. [50] L. A. Pothan, C. N. George, M. Jacob, and S. Thomas, Eect of chemical modication on the mechanical and electrical properties of banana ber polyester composites, Journal of Composite Materials, vol. 41, no. 19, pp. 23712386, 2007. [51] A. Paul, S. Joseph, and S. Thomas, A study of the inuence of interfacial damage on stress concentrations in unidirectional composites, Composites Science and Technology, vol. 57, p. 67, 1997. [52] M. S. Sreekala, M. G. Kumaran, and S. Thomas, Water sorption in oil palm ber reinforced phenol formaldehyde composites, Composites Part A, vol. 33, no. 6, pp. 763777, 2002. [53] B. Wang, S. Panigrahi, L. Tabil, and W. Crerar, Pre-treatment of ax bers for use in rotationally molded biocomposites, Journal of Reinforced Plastics and Composites, vol. 26, no. 5, pp. 447463, 2007. [54] S. Kalia, V. K. Kaushik, and R. K. Sharma, Eect of benzoylation and graft copolymerization on morphology, thermal stability, and crystallinity of sisal bers, Journal of Natural Fibers, vol. 8, no. 1, p. 27, 2011. [55] B. Wang, Pre-treatment of ax bers for use in rotationally molded biocomposites, M.S. thesis, University of Saskatchewan, Saskatoon, Canada, 2004. [56] B. S. Kaith, A. S. Singha, S. Kumar, and B. N. Misra, FASH2O2 initiated graft copolymerization of methylmethacrylate onto ax and evaluation of some physical and chemical properties, Journal of Polymer Materials, vol. 22, no. 4, pp. 425432, 2005. [57] S. Kalia, A. Kumar, and B. S. Kaith, Advanced Materials Letters, vol. 2, p. 17, 2011. [58] M. Tsukada, S. Islam, T. Arai, A. Boschi, and G. Freddi, Microwave irradiation technique to enhance protein bre properties, Autex Research Journal, vol. 5, no. 1, pp. 4048, 2005. [59] B. S. Kaith and S. Kalia, Preparation of microwave radiation induced graft copolymers and their applications as reinforcing material in phenolic composites, Polymer Composites, vol. 29, no. 7, pp. 791797, 2008. [60] B. S. Kaith and S. Kalia, Graft copolymerization of MMA onto ax under dierent reaction conditions: a comparative study, Express Polymer Letters, vol. 2, no. 2, pp. 93100, 2008. [61] M. Pommet, J. Juntaro, J. Y. Y. Heng et al., Surface modication of natural bers using bacteria: depositing bacterial cellulose onto natural bers to create hierarchical ber reinforced nanocomposites, Biomacromolecules, vol. 9, no. 6, pp. 16431651, 2008.
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
30
[62] M. Shoda and Y. Sugano, Recent advances in bacterial cellulose production, Biotechnology and Bioprocess Engineering, vol. 10, no. 1, pp. 18, 2005. [63] M. Iguchi, S. Yamanaka, and A. Budhiono, Bacterial cellulosea masterpiece of natures arts, Journal of Materials Science, vol. 35, no. 2, pp. 261270, 2000. [64] E. E. Brown and M. P. G. Laborie, Bioengineering bacterial cellulose/poly(ethylene oxide) nanocomposites, Biomacromolecules, vol. 8, no. 10, pp. 30743081, 2007. [65] A. N. Nakagaito and H. Yano, Novel high-strength biocomposites based on microbrillated cellulose having nanoorder-unit web-like network structure, Applied Physics A, vol. 80, no. 1, pp. 155159, 2005. [66] D. J. Gardner, G. S. Oporto, R. Mills, and M. Samir, Adhesion and surface issues in cellulose and nanocellulose, Journal of Adhesion Science and Technology, vol. 22, pp. 545 545, 2008. [67] S. Kalia and R. Sheoran, Modication of ramie bers using microwave-assisted grafting and cellulase enzymeassisted biopolishing: a comparative study of morphology, thermal stability, and crystallinity, International Journal of Polymer Analysis and Characterization, vol. 16, no. 5, pp. 307318, 2011. [68] J. Njuguna, P. Wambua, K. Pielichowski, and K. Kayvantash, Natural Fiber-reinforced polymer composites and nanocomposites for automotive applications, in Cellulose Fibers: Bio- and Nano-Polymer Composites, S. Kalia, B. S. Kaith, and I. Kaur, Eds., Springer, Heidelberg, Germany, 2011. [69] S. Mishra, A. K. Mohanty, L. T. Drzal, M. Misra, and G. Hinrichsen, A review on pineapple leaf bers, sisal bers and their biocomposites, Macromolecular Materials and Engineering, vol. 289, no. 11, pp. 955974, 2004. [70] P. Wambua, J. Ivens, and I. Verpoest, Natural bres: can they replace glass in bre reinforced plastics? Composites Science and Technology, vol. 63, no. 9, pp. 12591264, 2003. [71] J. Summerscales, N. Dissanayake, A. Virk, and W. Hall, A review of bast bres and their composites. Part 2 composites, Composites Part A, vol. 41, no. 10, pp. 1336 1344, 2010. [72] A. K. Bledzki and J. Gassan, Composites reinforced with cellulose based bres, Progress in Polymer Science, vol. 24, no. 2, pp. 221274, 1999. [73] R. Gauthier, C. Joly, A. C. Coupas, H. Gauthier, and M. Escoubes, Interfaces in polyolen/cellulosic ber composites: chemical coupling, morphology, correlation with adhesion and aging in moisture, Polymer Composites, vol. 19, no. 3, pp. 287300, 1998. [74] J. George, M. S. Sreekala, and S. Thomas, A review on interface modication and characterization of natural ber reinforced plastic composites, Polymer Engineering & Science, vol. 41, no. 9, pp. 14711485, 2001. [75] Y. Xie, C. A. S. Hill, Z. Xiao, H. Militz, and C. Mai, Silane coupling agents used for natural ber/polymer composites: a review, Composites Part A, vol. 41, no. 7, pp. 806819, 2010. [76] J. Gassan and A. K. Bledzki, Eect of cyclic moisture absorption desorption on the mechanical properties of silanized jute-epoxy composites, Polymer Composites, vol. 20, no. 4, pp. 604611, 1999. [77] A. K. Mohanty, M. Misra, and L. T. Drzal, Eds., Natural Fibers, Biopolymers, and Biocomposites, CRC Press, Boca Raton, Fla, USA, 2005.

[78] H. L. Bos, J. M ssig, and M. J. A. van den Oever, Mechanical u properties of short-ax-bre reinforced compounds, Composites Part A, vol. 37, no. 10, pp. 15911604, 2006. [79] H. L. Bos, The potential of ax bers as reinforcement for composite materials, Ph.D. thesis, Technische Universiteit Eindhoven, Eindhoven, The Netherlands, 2004. [80] S. K. Garkhail, R. W. H. Heijenrath, and T. Peijs, Mechanical properties of natural-bre-mat-reinforced thermoplastics based on ax bres and polypropylene, Applied Composite Materials, vol. 7, no. 5-6, pp. 351372, 2000. [81] T. Nishino, Natural ber sources, in Green Composites: Polymer Composites and the Environment, CRC Press, Boca Raton, Fla, USA, 2004. [82] A. Espert, F. Vilaplana, and S. Karlsson, Comparison of water absorption in natural cellulosic bres from wood and one-year crops in polypropylene composites and its inuence on their mechanical properties, Composites Part A, vol. 35, no. 11, pp. 12671276, 2004. [83] M. M. Thwe and K. Liao, Durability of bamboo-glass ber reinforced polymer matrix hybrid composites, Composites Science and Technology, vol. 63, no. 3-4, pp. 375387, 2003. [84] C. Pavithran, P. S. Mukherjee, and M. Brahmakumar, Coir-glass intermingled bre hybrid composites, Journal of Reinforced Plastics and Composites, vol. 10, no. 1, pp. 91101, 1991. [85] B. C. Tobias, Tensile and Impact behaviour of natural ber-reinforced composite materials, in Proceedings of the International Conference on Advanced Composite Materials, T. D. A. K. Chandra, Ed., The Minerals, Metals and Materials Society, 1993. [86] H. D. Mueller, Improving the impact strength of natural ber reinforced composites by specically designed material and process parameters, IJN Winter, 2004. [87] J. C. M. De Bruijn, Natural bre mat thermoplastic products from a processors point of view, Applied Composite Materials, vol. 7, no. 5-6, pp. 415420, 2000. [88] J. Gassan, A study of bre and interface parameters aecting the fatigue behaviour of natural bre composites, Composites Part A, vol. 33, no. 3, pp. 369374, 2002. [89] H. Savastano Jr., S. F. Santos, M. Radonjic, and W. O. Soboyejo, Fracture and fatigue of natural ber-reinforced cementitious composites, Cement and Concrete Composites, vol. 31, no. 4, pp. 232243, 2009. [90] A. N. Towo and M. P. Ansell, Fatigue of sisal bre reinforced composites: constant-life diagrams and hysteresis loop capture, Composites Science and Technology, vol. 68, no. 3-4, pp. 915924, 2008. [91] A. N. Towo and M. P. Ansell, Fatigue evaluation and dynamic mechanical thermal analysis of sisal bre-thermosetting resin composites, Composites Science and Technology, vol. 68, no. 3-4, pp. 925932, 2008. [92] T. Yuanjian and D. H. Isaac, Impact and fatigue behaviour of hemp bre composites, Composites Science and Technology, vol. 67, no. 15-16, pp. 33003307, 2007. [93] M. Henriksson, G. Henriksson, L. A. Berglund, and T. Lindstr m, An environmentally friendly method for enzymeo assisted preparation of microbrillated cellulose (MFC) nanobers, European Polymer Journal, vol. 43, no. 8, pp. 34343441, 2007. [94] T. Saito, S. Kimura, Y. Nishiyama, and A. Isogai, Cellulose nanobers prepared by TEMPO-mediated oxidation of native cellulose, Biomacromolecules, vol. 8, no. 8, pp. 2485 2491, 2007.

[95] L. W gberg, G. Decher, M. Norgren, T. Lindstr m, M. a o Ankerfors, and K. Axn s, The build-up of polyelectrolyte a multilayers of microbrillated cellulose and cationic polyelectrolytes, Langmuir, vol. 24, no. 3, pp. 784795, 2008. [96] M. E. Malainine, M. Mahrouz, and A. Dufresne, Thermoplastic nanocomposites based on cellulose microbrils from opuntia cus-indica parenchyma cell, Composites Science and Technology, vol. 65, no. 10, pp. 15201526, 2005. [97] Y. Habibi, A. L. Gon, N. Schiltz, E. Duquesne, P. Dubois, and A. Dufresne, Bionanocomposites based on poly(caprolactone)-grafted cellulose nanocrystals by ring-opening polymerization, Journal of Materials Chemistry, vol. 18, no. 41, pp. 50025010, 2008. [98] M. Grunert and W. T. Winter, Nanocomposites of cellulose acetate butyrate reinforced with cellulose nanocrystals, Journal of Polymers and the Environment, vol. 10, no. 1-2, pp. 2730, 2002. [99] N. L. Garcia de Rodriguez, W. Thielemans, and A. Dufresne, Sisal cellulose whiskers reinforced polyvinyl acetate nanocomposites, Cellulose, vol. 13, no. 3, pp. 261 270, 2006. [100] I. Kvien, B. S. Tanem, and K. Oksman, Characterization of cellulose whiskers and their nanocomposites by atomic force and electron microscopy, Biomacromolecules, vol. 6, no. 6, pp. 31603165, 2005. [101] M. A. S. A. Samir, F. Alloin, M. Paillet, and A. Dufresne, Tangling eect in brillated cellulose reinforced nanocomposites, Macromolecules, vol. 37, no. 11, pp. 43134316, 2004. [102] M. N. Angl` s and A. Dufresne, Plasticized starch/tuniein e whiskers nanocomposites. 1. Structural analysis, Macromolecules, vol. 33, no. 22, pp. 83448353, 2000. [103] W. Helbert, J. Y. Cavaill , and A. Dufresne, Thermoplastic e nanocomposites lled with wheat straw cellulose whiskers. Part I: processing and mechanical behavior, Polymer Composites, vol. 17, no. 4, pp. 604611, 1996. [104] K. Fleming, D. Gray, S. Prasannan, and S. Matthews, Cellulose crystallites: a new and robust liquid crystalline medium for the measurement of residual dipolar couplings, Journal of the American Chemical Society, vol. 122, no. 21, pp. 52245225, 2000. [105] Y. Pu, J. Zhang, T. Elder, Y. Deng, P. Gatenholm, and A. J. Ragauskas, Investigation into nanocellulosics versus acacia reinforced acrylic lms, Composites Part B, vol. 38, no. 3, pp. 360366, 2007. [106] A. B. Elmabrouk, T. Wim, A. Dufresne, and S. Bou, Preparation of poly(styrene-co-hexylacrylate)/cellulose whiskers nanocomposites via miniemulsion polymerization, Journal of Applied Polymer Science, vol. 114, no. 5, pp. 29462955, 2009. [107] J. F. Revol, On the cross-sectional shape of cellulose crystallites in valonia ventricosa, Carbohydrate Polymers, vol. 2, no. 2, pp. 123134, 1982. [108] S. J. Hanley, J. Giasson, J. F. Revol, and D. G. Gray, Atomic force microscopy of cellulose microbrils: comparison with transmission electron microscopy, Polymer, vol. 33, no. 21, pp. 46394642, 1992. [109] C. Tokoh, K. Takabe, M. Fujita, and H. Saiki, Cellulose synthesized by acetobacter xylinum in the presence of acetyl glucomannan, Cellulose, vol. 5, no. 4, pp. 249261, 1998. [110] M. Roman and W. T. Winter, Eect of sulfate groups from sulfuric acid hydrolysis on the thermal degradation behavior of bacterial cellulose, Biomacromolecules, vol. 5, no. 5, pp. 16711677, 2004.
31
[111] R. Zuluaga, J. L. Putaux, A. Restrepo, I. Mondragon, and P. Ganan, Cellulose microbrils from banana farming residues: isolation and characterization, Cellulose, vol. 14, no. 6, pp. 585592, 2007. [112] K. Oksman, J. A. Etang, A. P. Mathew, and M. Jonoobi, Cellulose nanowhiskers separated from a bio-residue from wood bioethanol production, Biomass & Bioenergy, vol. 35, no. 1, pp. 146152, 2011. [113] G. Siqueira, H. Abdillahi, J. Bras, and A. Dufresne, High reinforcing capability cellulose nanocrystals extracted from Syngonanthus nitens (Capim Dourado), Cellulose, vol. 17, no. 2, pp. 289298, 2010. [114] E. D. M. Teixeira, D. Pasquini, A. A. S. Curvelo, E. Corradini, M. N. Belgacem, and A. Dufresne, Cassava bagasse cellulose nanobrils reinforced thermoplastic cassava starch, Carbohydrate Polymers, vol. 78, no. 3, pp. 422431, 2009. [115] U. J. Kim, S. Kuga, M. Wada, T. Okano, and T. Kondo, Periodate oxidation of crystalline cellulose, Biomacromolecules, vol. 1, no. 3, pp. 488492, 2000. [116] M. F. Rosa, E. S. Medeiros, J. A. Malmonge et al., Cellulose nanowhiskers from coconut husk bers: eect of preparation conditions on their thermal and morphological behavior, Carbohydrate Polymers, vol. 81, no. 1, pp. 8392, 2010. [117] X. M. Dong, J. F. Revol, and D. G. Gray, Eect of microcrystallite preparation conditions on the formation of colloid crystals of cellulose, Cellulose, vol. 5, no. 1, pp. 1932, 1998. [118] T. Ebeling, M. Paillet, R. Borsali et al., Shear-induced orientation phenomena in suspensions of cellulose microcrystals, revealed by small angle X-ray scattering, Langmuir, vol. 15, no. 19, pp. 61236126, 1999. [119] J. Araki, M. Wada, and S. Kuga, Steric Stabilization of a Cellulose Microcrystal Suspension by Poly(ethylene glycol) Grafting, Langmuir, vol. 17, no. 1, pp. 2127, 2001. [120] Y. Lu, L. Weng, and X. Cao, Biocomposites of plasticized starch reinforced with cellulose crystallites from cottonseed linter, Macromolecular Bioscience, vol. 5, no. 11, pp. 1101 1107, 2005. [121] A. C. Corr a, E. M. Teixeira, L. A. Pessan, and L. H. C. e Mattoso, Cellulose nanobers from curaua bers, Cellulose, vol. 17, no. 6, pp. 11831192, 2010. [122] A. Bendahou, Y. Habibi, H. Kaddami, and A. Dufresne, Physico-chemical characterization of palm from Phoenix Dactylifera-L, preparation of cellulose whiskers and natural rubber-based nanocomposites, Journal of Biobased Materials and Bioenergy, vol. 3, no. 1, pp. 8190, 2009. [123] J. P. De Mesquita, C. L. Donnici, and F. V. Pereira, Biobased nanocomposites from layer-by-layer assembly of cellulose nanowhiskers with chitosan, Biomacromolecules, vol. 11, no. 2, pp. 473480, 2010. [124] X. Cao, H. Dong, and C. M. Li, New nanocomposite materials reinforced with ax cellulose nanocrystals in waterborne polyurethane, Biomacromolecules, vol. 8, no. 3, pp. 899904, 2007. [125] J. K. Pandey, J. W. Lee, W. S. Chu, C. S. Kim, C. S. Lee, and S. H. Ahn, Cellulose nanowhiskers from grass of Korea, Macromolecular Research, vol. 16, no. 5, pp. 396498, 2008. [126] J. K. Pandey, W. S. Chu, C. S. Kim, C. S. Lee, and S. H. Ahn, Bio-nano reinforcement of environmentally degradable polymer matrix by cellulose whiskers from grass, Composites Part B, vol. 40, no. 7, pp. 676680, 2009. [127] B. Wang, M. Sain, and K. Oksman, Study of structural morphology of hemp ber from the micro to the nanoscale, Applied Composite Materials, vol. 14, no. 2, pp. 89103, 2007.
32
[128] G. Siqueira, J. Bras, and A. Dufresne, Lua cylindrica as a lignocellulosic source of ber, microbrillated cellulose, and cellulose nanocrystals, BioResources, vol. 5, no. 2, pp. 727 740, 2010. [129] R. Li, J. Fei, Y. Cai, Y. Li, J. Feng, and J. Yao, Cellulose whiskers extracted from mulberry: a novel biomass production, Carbohydrate Polymers, vol. 76, no. 1, pp. 9499, 2009. [130] G. Chen, A. Dufresne, J. Huang, and P. R. Chang, A novel thermoformable bionanocomposite based on cellulose nanocrystal-graft-poly(-caprolactone), Macromolecular Materials and Engineering, vol. 294, pp. 5967, 2009. [131] Y. Lu, L. Weng, and X. Cao, Morphological, thermal and mechanical properties of ramie crystallitesreinforced plasticized starch biocomposites, Carbohydrate Polymers, vol. 63, no. 2, pp. 198204, 2006. [132] Y. Habibi and A. Dufresne, Highly lled bionanocomposites from functionalized polysaccharide nanocrystals, Biomacromolecules, vol. 9, no. 7, pp. 19741980, 2008. [133] P. B. Filson, B. E. Dawson-Andoh, and D. Schwegler-Berry, Enzymatic-mediated production of cellulose nanocrystals from recycled pulp, Green Chemistry, vol. 11, no. 11, pp. 18081814, 2009. [134] G. Siaueira, J. Bras, and A. Dufresne, Cellulose whiskers versus microbrils: inuence of the nature of the nanoparticle and its surface functionalization on the thermal and mechanical properties of nanocomposites, Biomacromolecules, vol. 10, no. 2, pp. 425432, 2009. [135] G. Siqueira, J. Bras, and A. Dufresne, New process of chemical grafting of cellulose nanoparticles with a long chain isocyanate, Langmuir, vol. 26, no. 1, pp. 402411, 2010. [136] E. M. Teixeira, T. J. Bondancia, K. B. R. Teodoro, A. C. Corr a, e J. M. Marconcini, and L. H. C. Mattoso, Sugarcane bagasse whiskers: extraction and characterizations, Industrial Crops and Products, vol. 33, no. 1, pp. 6366, 2011. [137] V. Favier, G. R. Canova, J. Y. Cavaill , H. Chanzy, A. Dufresne, e and C. Gauthier, Nanocomposite materials from latex and cellulose whiskers, Polymers for Advanced Technologies, vol. 6, no. 5, pp. 351355, 1995. [138] J. Araki, M. Wada, S. Kuga, and T. Okano, Inuence of surface charge on viscosity behavior of cellulose microcrystal suspension, Journal of Wood Science, vol. 45, no. 3, pp. 258 261, 1999. [139] S. Beck-Candanedo, M. Roman, and D. G. Gray, Eect of reaction conditions on the properties and behavior of wood cellulose nanocrystal suspensions, Biomacromolecules, vol. 6, no. 2, pp. 10481054, 2005. [140] M. A. S. A. Samir, F. Alloin, and A. Dufresne, Review of recent research into cellulosic whiskers, their properties and their application in nanocomposite eld, Biomacromolecules, vol. 6, no. 2, pp. 612626, 2005. [141] A. Dufresne, Comparing the mechanical properties of high performances polymer nanocomposites from biological sources, Journal of Nanoscience and Nanotechnology, vol. 6, no. 2, pp. 322330, 2006. [142] A. Dufresne, Polysaccharide nanocrystals reinforced nanocomposites, Canadian Journal of Chemistry, vol. 86, pp. 484494, 2008. [143] M. A. Hubbe, O. J. Rojas, L. A. Lucia, and M. Sain, Cellulosic nanocomposites: a review, Bioresources, vol. 3, pp. 929980, 2008. [144] A. Sturcova, G. R. Davies, and S. J. Eichhorn, Elastic modulus and stress-transfer properties of tunicate cellulose whiskers, Biomacromolecules, vol. 6, no. 2, pp. 10551061, 2005.

[145] Liu Dagang, Zhong Tuhua, R. Chang Peter, Li Kaifu, and Wu Qinglin, Starch composites reinforced by bamboo cellulosic crystals, Bioresource Technology, vol. 101, no. 7, pp. 2529 2536, 2010. [146] M. N. Angl` s and A. Dufresne, Plasticized starch/tunicin e whiskers nanocomposite materials. 2. Mechanical behavior, Macromolecules, vol. 34, no. 9, pp. 29212931, 2001. [147] A. P. Mathew and A. Dufresne, Morphological investigation of nanocomposites from sorbitol plasticized starch and tunicin whiskers, Biomacromolecules, vol. 3, no. 3, pp. 609 617, 2002. [148] W. J. Orts, J. Shey, S. H. Imam, G. M. Glenn, M. E. Guttman, and J. F. Revol, Application of cellulose microbrils in polymer nanocomposites, Journal of Polymers and the Environment, vol. 13, no. 4, pp. 301306, 2005. [149] A. P. Mathew, W. Thielemans, and A. Dufresne, Mechanical properties of nanocomposites from sorbitol plasticized starch and tunicin whiskers, Journal of Applied Polymer Science, vol. 109, no. 6, pp. 40654074, 2008. [150] A. J. Svagan, M. S. Hedenqvist, and L. Berglund, Reduced water vapour sorption in cellulose nanocomposites with starch matrix, Composites Science and Technology, vol. 69, no. 3-4, Article ID 10.1016/j.compscitech.2008.11.016, pp. 500506, 2009. [151] Y. Noishiki, Y. Nishiyama, M. Wada, S. Kuga, and J. Magoshi, Mechanical properties of silk broin-microcrystalline cellulose composite lms, Journal of Applied Polymer Science, vol. 86, no. 13, pp. 34253429, 2002. [152] M. A. S. A. Samir, F. Alloin, J. Y. Sanchez, and A. Dufresne, Cellulose nanocrystals reinforced poly(oxyethylene), Polymer, vol. 45, no. 12, pp. 41494157, 2004. [153] M. A. S. A. Samir, F. Alloin, W. Gorecki, J. Y. Sanchez, and A. Dufresne, Nanocomposite polymer electrolytes based on poly(oxyethylene) and cellulose nanocrystals, The Journal of Physical Chemistry B, vol. 108, no. 30, pp. 1084510852, 2004. [154] M. A. S. A. Samir, A. M. Mateos, F. Alloin, J. Y. Sanchez, and A. Dufresne, Plasticized nanocomposite polymer electrolytes based on poly(oxyethylene) and cellulose whiskers, Electrochimica Acta, vol. 49, no. 26, pp. 46674677, 2004. [155] M. A. S. A. Samir, L. Chazeau, F. Alloin, J. Y. Cavaill , A. e Dufresne, and J. Y. Sanchez, POE-based nanocomposite polymer electrolytes reinforced with cellulose whiskers, Electrochimica Acta, vol. 50, no. 19, pp. 38973903, 2005. [156] M. A. S. A. Samir, F. Alloin, and A. Dufresne, High performance nanocomposite polymer electrolytes, Composite Interfaces, vol. 13, no. 46, pp. 545559, 2006. [157] T. Zimmermann, E. P hler, and T. Geiger, Cellulose brils o for polymer reinforcement, Advanced Engineering Materials, vol. 6, no. 9, pp. 754761, 2004. [158] T. Zimmermann, E. P hler, and P. Schwaller, Mechanical o and morphological properties of cellulose bril reinforced nanocomposites, Advanced Engineering Materials, vol. 7, no. 12, pp. 11561161, 2005. [159] M. Roohani, Y. Habibi, N. M. Belgacem, G. Ebrahim, A. N. Karimi, and A. Dufresne, Cellulose whiskers reinforced polyvinyl alcohol copolymers nanocomposites, European Polymer Journal, vol. 44, no. 8, pp. 24892498, 2008. [160] S. A. Paralikar, J. Simonsen, and J. Lombardi, Poly(vinyl alcohol)/cellulose nanocrystal barrier membranes, Journal of Membrane Science, vol. 320, no. 1-2, pp. 248258, 2008. [161] J. Lu, T. Wang, and L. T. Drzal, Preparation and properties of microbrillated cellulose polyvinyl alcohol composite materials, Composites Part A, vol. 39, no. 5, pp. 738746, 2008.

[162] Y. Choi and J. Simonsen, Cellulose nanocrystal-lled carboxymethyl cellulose nanocomposites, Journal of Nanoscience and Nanotechnology, vol. 6, no. 3, pp. 633639, 2006. [163] Y. Wang, X. Cao, and L. Zhang, Eects of cellulose whiskers on properties of soy protein thermoplastics, Macromolecular Bioscience, vol. 6, no. 7, pp. 524531, 2006. [164] A. Dufresne, J. Y. Cavaill , and W. Helbert, Thermoplastic e nanocomposites lled with wheat straw cellulose whiskers. Part II: eect of processing and modeling, Polymer Composites, vol. 18, no. 2, pp. 198210, 1997. [165] D. Dubief, E. Samain, and A. Dufresne, Polysaccharide microcrystals keinforced amorphous poly(/3-hydroxyoctanoate) nanocomposite materials, Macromolecules, vol. 32, no. 18, pp. 57655771, 1999. [166] A. Dufresne, M. B. Kellerhals, and B. Witholt, Transcrystallization in Mcl-PHAs/cellulose whiskers composites, Macromolecules, vol. 32, no. 22, pp. 73967401, 1999. [167] A. Dufresne, Dynamic mechanical analysis of the interphase in bacterial polyester/cellulose whiskers natural composites, Composite Interfaces, vol. 7, no. 1, pp. 5367, 2000. [168] L. Chazeau, J. Y. Cavaill , G. Canova, R. Dendievel, and B. e Boutherin, Viscoelastic properties of plasticized PVC reinforced with cellulose whiskers, Journal of Applied Polymer Science, vol. 71, no. 11, pp. 17971808, 1999. [169] L. Chazeau, J. Y. Cavaill , and P. Terech, Mechanical e behaviour above T(g) of a plasticised PVC reinforced with cellulose whiskers; a SANS structural study, Polymer, vol. 40, no. 19, pp. 53335344, 1999. [170] L. Chazeau, M. Paillet, and J. Y. Cavaill , Plasticized PVC e reinforced with cellulose whiskers. I. Linear viscoelastic behavior analyzed through the quasi-point defect theory, Journal of Polymer Science Part B, vol. 37, no. 16, pp. 2151 2164, 1999. [171] L. Chazeau, J. Y. Cavaill , and J. Perez, Plasticized PVC e reinforced with cellulose whiskers. II. Plastic behavior, Journal of Polymer Science Part B, vol. 38, no. 3, pp. 383392, 2000. [172] M. M. Ruiz, J. Y. Cavaill , A. Dufresne, C. Graillat, and J. F. e G rard, New waterborne epoxy coatings based on cellulose e nanollers, Macromolecular Symposia, vol. 169, pp. 211222, 2001. [173] A. Bendahou, H. Kaddami, and A. Dufresne, Investigation on the eect of cellulosic nanoparticles morphology on the properties of natural rubber based nanocomposites, European Polymer Journal, vol. 46, no. 4, pp. 609620, 2010. [174] M. F. Rosa, E. S. Medeiros, J. A. Malmonge et al., Nanocomposites based on natural rubber and cellulose nanocrystals from coconut bers, in Proceedings of the 11th International Conference on Advanced Materials (ICAM 09), Rio de Janeiro, Brazil, September 2009. [175] K. Oksman, A. P. Mathew, D. Bondeson, and I. Kvien, Manufacturing process of cellulose whiskers/polylactic acid nanocomposites, Composites Science and Technology, vol. 66, no. 15, pp. 27762784, 2006. [176] D. Bondeson and K. Oksman, Polylactic acid/cellulose whisker nanocomposites modied by polyvinyl alcohol, Composites Part A, vol. 38, no. 12, pp. 24862492, 2007. [177] A. J. de Menezes, G. Siqueira, A. A. S. Curvelo, and A. Dufresne, Extrusion and characterization of functionalized cellulose whiskers reinforced polyethylene nanocomposites, Polymer, vol. 50, no. 19, pp. 45524563, 2009. [178] A. L. Gon, J. M. Raquez, E. Duquesne, Y. Habibi, A. Dufresne, and P. Dubois, Poly(-caprolactone) based nanocomposites reinforced by surface-grafted cellulose nano-
33
whiskers via extrusion processing: morphology, rheology, and thermo-mechanical properties, Polymer, vol. 52, no. 7, Article ID 10.1016/j.polymer.2011.02.004, pp. 15321538, 2011. L. Lemahieu, L. Bras, P. Tiquet, S. Augier, and A. Dufresne, Extrusion of nanocellulose-reinforced nanocomposites using the dispersed nano-objects protective encapsulation (DOPE) process , Macromolecular Materials and Engineerinjournal name. In press. G. Chauve, L. Heux, R. Arouini, and K. Mazeau, Cellulose poly(ethylene-co-vinyl acetate) nanocomposites studied by molecular modelling and mechanical spectroscopy, Biomacromolecules, vol. 6, no. 4, pp. 20252031, 2005. N. Ljungberg, C. Bonini, F. Bortolussi, C. Boisson, L. Heux, and J. Y. Cavaill , New nanocomposite materials reinforced e with cellulose whiskers in atactic polypropylene: Eect of surface and dispersion characteristics, Biomacromolecules, vol. 6, no. 5, pp. 27322739, 2005. R. N. Rowell, A new generationof composite materials from agro-based bers, in Polymers and Other Advanced Materials: Emerging Technologies and Business Opportunity, P. N. Prasas, M. E. James, and T. F. Joo, Eds., pp. 6669, Plenum Press, New York, NY, USA, 1995. R. N. Rowell, A new generation of composite materials from agro-based bers, in Proceedings of the Third International Conference on Frontiers of Polymers and Advanced Materials, Kuala Lumpur, Malaysia, January 1995. M. A. Dweib, B. Hu, H. W. Shenton, and R. P. Wool, Bio-based composite roof structure: manufacturing and processing issues, Composite Structures, vol. 74, no. 4, pp. 379388, 2006. V. M. H. Govindarao, Utilization of rice huska preliminary analysis, Journal of Scientic & Industrial Research, vol. 39, no. 9, pp. 495515, 1980. R. Burgue o, M. J. Quagliata, G. M. Mehta, A. K. Mohanty, n M. Misra, and L. T. Drzal, Sustainable cellular biocomposites from natural bers and unsaturated polyester resin for housing panel applications, Journal of Polymers and the Environment, vol. 13, no. 2, pp. 139149, 2005. R. M. Brown, Microbial Cellulose: a new resource for wood, paper, textiles, food and specialty products, Position Paper, 1998, http://www.botany.utexas.edu/facsta/facpages/mbrown/position1.htm. R. Jonas and L. F. Farah, Production and application of microbial cellulose, Polymer Degradation and Stability, vol. 59, no. 13, pp. 101106, 1998. J. Shah and R. M. Brown Jr., Towards electronic paper displays made from microbial cellulose, Applied Microbiology and Biotechnology, vol. 66, no. 4, pp. 352355, 2005. H. Yano, J. Sugiyama, A. N. Nakagaito et al., Optically transparent composites reinforced with networks of bacterial nanobers, Advanced Materials, vol. 17, no. 2, pp. 153155, 2005. C. Legnani, H. S. Barud, W. G. Quirino et al., Transparent nanocomposite bacterial cellulose used as exible substrate for OLED, in Proceedings of the 11th International Conference on Advanced Materials, Rio de Janeiro, Brazil, September 2009. B. R. Evans, H. M. ONeill, V. P. Malyvanh, I. Lee, and J. Woodward, Palladium-bacterial cellulose membranes for fuel cells, Biosensors and Bioelectronics, vol. 18, no. 7, pp. 917923, 2003. D. G. Olson, S. A. Tripathi, R. J. Giannone et al., Deletion of the Cel48S cellulase from Clostridium thermocellum,
[179]
[180]
[181]
[182]
[183]
[184]
[185]
[186]
[187]
[188]
[189]
[190]
[191]
[192]
[193]
34
Proceedings of the National Academy of Sciences of the United States of America, vol. 107, no. 41, pp. 1772717732, 2010. D. A. A. Alderman, A review of cellulose ethers in hydrophilic matrices for oral controlled-release dosage forms, International Journal of Pharmaceutical Technology and Product Manufacture, vol. 5, no. 3, pp. 19, 1984. J. Heller, Use of polymers in controlled release of active agents in controlled drug delivery, in Fundamentals and Applications, J. R. Robinson and V. H. L. Lee, Eds., pp. 210 180, Marcel Dekker, New York, NY, USA, 2nd edition, 1987. M. A. Longer and J. R. Robinson, Sustained-release drug delivery systems, in Remingtons Pharmaceutical Sciences, J. P. Remington, Ed., pp. 16761693, Mack Publishing, Easton, Pa, USA, 18th edition, 1990. M. D. Baumann, C. E. Kang, J. C. Stanwick et al., An injectable drug delivery platform for sustained combination therapy, Journal of Controlled Release, vol. 138, no. 3, pp. 205213, 2009. Y. Watanabe, B. Mukai, K. I. Kawamura et al., Preparation and evaluation of press-coated aminophylline tablet using crystalline cellulose and polyethylene glycol in the outer shell for timed-release dosage forms, Yakugaku Zasshi, vol. 122, no. 2, pp. 157162, 2002. S. Shaikh, A. Birdi, S. Qutubuddin, E. Lakatosh, and H. Baskaran, Controlled release in transdermal pressure sensitive adhesives using organosilicate nanocomposites, Annals of Biomedical Engineering, vol. 35, no. 12, pp. 21302137, 2007. H. L nnberg, L. Fogelstr m, M. A. S. A. Samir, L. Berglund, o o E. Malmstr m, and A. Hult, Surface grafting of microbo rillated cellulose with poly(-caprolactone)synthesis and characterization, European Polymer Journal, vol. 44, no. 9, pp. 29912997, 2008. J. D. Fontana, A. M. de Souza, C. K. Fontana et al., Acetobacter cellulose pellicle as a temporary skin substitute, Applied Biochemistry and Biotechnology, vol. 24-25, pp. 253 264, 1990. L. R. Mello, Y. Feltrin, R. Selbach, G. Macedo Jr., C. Spautz, and L. J. Haas, Use of lyophilized cellulose in peripheral nerve lesions with loss of substance, Arquivos de NeuroPsiquiatria, vol. 59, no. 2, pp. 372379, 2001. W. K. Czaja, D. J. Young, M. Kawecki, and R. M. Brown Jr., The future prospects of microbial cellulose in biomedical applications, Biomacromolecules, vol. 8, no. 1, pp. 112, 2007. S. W. Negro, R. R. L. Bueno, E. E. Gu rios et al., A Ec cia a e a do stent recoberto com celulose biossint tica comparado e ao stent convencional em angioplastia em coelhos, Revista Brasileira de Cardiologia Invasiva, vol. 14, no. 1, pp. 1019, 2006. D. Klemm, D. Schumann, U. Udhardt, and S. Marsch, Bacterial synthesized cellulosearticial blood vessels for microsurgery, Progress in Polymer Science, vol. 26, no. 9, pp. 15611603, 2001. M. A. Croce, C. Silvestri, D. Guerra et al., Adhesion and proliferation of human dermal broblasts on collagen matrix, Journal of Biomaterials Applications, vol. 18, no. 3, pp. 209222, 2004. S. V. Madihally and H. W. T. Matthew, Porous chitosan scaolds for tissue engineering, Biomaterials, vol. 20, no. 12, pp. 11331142, 1999. S. Nehrer, H. A. Breinan, A. Ramappa et al., Canine chondrocytes seeded in type I and type II collagen implants inves-

tigated in vitro, Journal of Biomedical Materials Research, vol. 38, no. 2, pp. 95104, 1997. T. V. Kumari, U. Vasudev, A. Kumar, and B. Menon, Cell surface interactions in the study of biocompatibility, Trends in Biomaterials and Articial Organs, vol. 15, no. 2, pp. 3741, 2001. Y. Ikada, Challenges in tissue engineering, Journal of the Royal Society Interface, vol. 3, no. 10, pp. 589601, 2006. G. Q. Chen and Q. Wu, The application of polyhydroxyalkanoates as tissue engineering materials, Biomaterials, vol. 26, no. 33, pp. 65656578, 2005. K. Anselme, Osteoblast adhesion on biomaterials, Biomaterials, vol. 21, no. 7, pp. 667681, 2000. H. S. Barud, Development and evaluation of Biocure obtained from bacterial cellulose and standardized extract of propolis (EPP-AF) for the treatment of burns and / or skin lesions, So Paulo Research FoundationFAPESP, Brazil, a 2009. W. Czaja, A. Krystynowicz, S. Bielecki, and R. M. Brown Jr., Microbial cellulosethe natural power to heal wounds, Biomaterials, vol. 27, no. 2, pp. 145151, 2006. L. E. Millon and W. K. Wan, The polyvinyl alcohol-bacterial cellulose system as a new nanocomposite for biomedical applications, Journal of Biomedical Materials Research Part B, vol. 79, no. 2, pp. 245253, 2006. Z. Cai and J. Kim, Bacterial cellulose/poly(ethylene glycol) composite: characterization and rst evaluation of biocompatibility, Cellulose, vol. 17, no. 1, pp. 8391, 2010. A. Seves, G. Testa, A. M. Bonfatti, E. D. Paglia, E. Selli, and B. Marcandalli, Characterization of native cellulose/poly(ethylene glycol) lms, Macromolecular Materials and Engineering, vol. 286, no. 9, pp. 524528, 2001. Y. Z. Wan, L. Hong, S. R. Jia et al., Synthesis and characterization of hydroxyapatite-bacterial cellulose nanocomposites, Composites Science and Technology, vol. 66, no. 11-12, pp. 18251832, 2006. K. Yasuda, J. P. Gong, Y. Katsuyama et al., Biomechanical properties of high-toughness double network hydrogels, Biomaterials, vol. 26, no. 21, pp. 44684475, 2005. S. B. Lin, C. P. Hsu, L. C. Chen, and H. H. Chen, Adding enzymatically modied gelatin to enhance the rehydration abilities and mechanical properties of bacterial cellulose, Food Hydrocolloids, vol. 23, no. 8, pp. 21952203, 2009. J. Huia, J. Yuanyuan, W. Jiao, H. Yuan, Z. Yuan, and J. Shiru, Potentiality of bacterial cellulose as the scaold of tissue engineering of cornea, in Proceedings of the 2nd International Conference on Biomedical Engineering and Informatics, (BMEI 09), China, October 2009. D. A. Schumann, J. Wippermann, D. O. Klemm et al., Articial vascular implants from bacterial cellulose: preliminary results of small arterial substitutes, Cellulose, vol. 16, no. 5, pp. 877885, 2009. W. L. Amorim, H. O. Costa, F. C. Souza, M. G. Castro, and L. Silva, Experimental study of the tissue reaction caused by the presence of cellulose produced, Brazilian Journal of Otorhinolaryngology, vol. 75, no. 2, pp. 200207, 2009. J. Hart, D. Silcock, S. Gunnigle, B. Cullen, N. D. Light, and P. W. Watt, The role of oxidised regenerated cellulose/collagen in wound repair: eects in vitro on broblast biology and in vivo in a model of compromised healing, International Journal of Biochemistry and Cell Biology, vol. 34, no. 12, pp. 15571570, 2002. G. Helenius, H. Backdahl, A. Bodin, U. Nannmark, P. Gatenholm, and B. Risberg, In vivo biocompatibility of
[194]
[209]
[195]
[210] [211]
[196]
[212] [213]
[197]
[198]
[214]
[215]
[199]
[216]
[200]
[217]
[218]
[201]
[219]
[202]
[220]
[203]
[221]
[204]
[222]
[205]
[223]
[206]
[224]
[207]
[208]
[225]

bacterial cellulose, Journal of Biomedical Materials Research Part A, vol. 76, no. 2, pp. 431438, 2006. E. C. Silva, Hidroxiapatita Sinttica em alvolo dent rio e e a aps exodontia em Felis catus: estudo clnico, radiolgico e o o histomorfomtrico, M.S. Dissertation, Universidade Federal e de Vicosa, Vicosa, Brazil, 2009. H. O. Costa and F. C. de Souza, Evaluation of the tissue regeneration of the burned pig skin followed by BiotissueTM s grafting, Acta ORL/Tcnicas em Otorrinolaringologia, vol. 23, e no. 4, pp. 192196, 2005. A. P. Nemetz, D. R. R. Loures, J. C. U. Coelho et al., Efeito estrutural da utilizacao de celulose biossint tica e polite e trauoroetileno expandido como substitutos do peritonio em ces, Arquivos Brasileiros De Cirugia Digestiva, vol. 14, a no. 2, pp. 139142, 2001. A. B. Novaes Jr. and A. B. Novaes, Soft tissue management for primary closure in guided bone regeneration: sugical technique and case report, The International Journal of Oral and Maxillofacial Implants, vol. 12, no. 1, pp. 8487, 1997. A. B. Novaes Jr. and A. B. Novaes, IMZ implants placed into extraction sockets in association with membrane therapy (Gengiex) and porous hydroxyapatite: a case report, The International Journal of Oral and Maxillofacial Implants, vol. 7, no. 4, pp. 536540, 1992. L. A. Salata, G. T. Craig, and I. M. Brook, In vivo evaluation of a new memnbrane (Gengiex) for guided bone regeneratien (GBR), Journal of Dental Research, vol. 74, no. 3, p. 825, 1995. C. Dahlin, A. Linde, J. Gottlow, and S. Nyman, Healing of bone defects by guided tissue regeneration, Plastic and Reconstructive Surgery, vol. 81, no. 5, pp. 672676, 1988. N. L. Macedo, F. S. Matuda, L. G. S. Macedo, A. S. F. Monteiro, M. C. Valera, and Y. R. Carvalho, Evaluation of two membranes in guided bone tissue regeneration: histological study in rabbits, Brazilian Journal of Oral Sciences, vol. 3, no. 8, pp. 395400, 2004.
35
[226]
[227]
[228]
[229]
[230]
[231]
[232]
[233]

Cellulose-Based Bio - and Nanocomposites: A Review

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Hindawi Publishing Corporation International Journal of Polymer Science Volume 2011, Article ID 837875, 35 pages doi:10.

Review Article Cellulose-Based Bio- and Nanocomposites: A Review

International Journal of Polymer Science

Primary wall Amorphous region mainly consisting of lignin and hemicellulose

Disorderly arranged crystalline cellulose microbrils networks

Figure 1: Structural constitution of natural ber cell [17].

Raw material (soybean stock)

Pretreatment (17.5% w/w NaOH, 2h)

Acid hydrolysis (1M HCl, 7080 C, 2h)

Alkaline treatment (2% w/w NaOH, 2h, 7080 C)

Cryocrushing in liquid nitrogen

High pressure debrillation

Figure 2: Isolation of nanobers by chemomechanical treatment [31].

4. Surface Modication of Cellulose Fibers

International Journal of Polymer Science

International Journal of Polymer Science

Figure 6: Atomic force micrograph of soybean stock nanobers [31].

International Journal of Polymer Science

O Cellulose O Si O O Fiber Hemicellulose O Si O O Lignin O Si O

H CH H H CH H H CH H CH2 CH2 CH2

International Journal of Polymer Science

International Journal of Polymer Science

O HO OH Cellulose ber n + NaOH

O Na+ Mercerized ber

Figure 7: Structure of cellulose [57].

International Journal of Polymer Science

International Journal of Polymer Science

Figure 10: Hemp ber after bacterial cellulose modication [61].

13 in matrix material as a result of improved interfacial bonding.

6. Cellulose Nanober-Reinforced Nanocomposites

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International Journal of Polymer Science

International Journal of Polymer Science

67 39 10 13-17 43/30 24 15 47 34 [97, 131, 132] 60/43 42 64 67 45 50

7. Applications of Polymer Composites

International Journal of Polymer Science

Cross section of SIP form

Figure 15: Stay-in-place bridge form.

International Journal of Polymer Science

Insulted structural Cellular biopanel panel

International Journal of Polymer Science

Infusing electrochromic material into the paper

Attaching electrode and protecting layer

Figure 18: Fabrication process of the display using nanocellulose.

International Journal of Polymer Science

International Journal of Polymer Science

Figure 22: Nanocellulose and propolis-based bandage [213].

International Journal of Polymer Science

International Journal of Polymer Science

International Journal of Polymer Science

Figure 27: Explantation of implants after 1 week [225].

International Journal of Polymer Science

International Journal of Polymer Science

International Journal of Polymer Science

International Journal of Polymer Science

International Journal of Polymer Science

International Journal of Polymer Science

International Journal of Polymer Science

International Journal of Polymer Science