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2015; 2(6):43-50
Published online November 3, 2015 (http://www.openscienceonline.com/journal/nano)
Email address
gxsui@imr.ac.cn (Guoxin Sui), dyliu@imr.ac.cn (Dongyan Liu), nma@imr.ac.cn (Na Ma)
Abstract
Nanocellulse as a kind of biomaterial with nanoscale, performs considerable potential applications in a many fields. Extracting
nanocellulose might create a novel path to use of Xanthoceras sorbifolia husks. In this work, nanocellulose was extracted from
Xanthoceras sorbifolia husks through a series of chemical treatments. The morphology, chemical structure, thermal behaviors
and crystallinity of untreated husks, cellulose fibers and nanocellulose were compared. The mechanical properties of
nanocellulose film were investigated. The nanocellulose of Xanthoceras sorbifolia husks had a rod-like aspect, the diameter was
about 38nm. The essential chemical structure of cellulose was not broken during the treatments. The chemical treatments for
Xanthoceras sorbifolia husks caused the changes of the thermal properties and crystallinity. The transparent nanocellulose film
made by Xanthoceras sorbifolia husks nanocellulose showed high storage modulus at low temperature. The tensile strength and
Youngs modulus of nanocellulose film were 75.9MPa and 15.9GPa, respectively.
Keywords
Nanocellulose, Xanthoceras Sorbifolia Husks, Extracting, Nanocellulose Film, Properties
diameter [7] with a network form. cellulose fibers were dispersed in water by ultrasound. The
Xanthoceras sorbifolia, is also called yellow horn, shiny mixed liquor was poured onto plastic petri dish, cellulose
leaf yellow horn, golden horn and Chinese flowering chestnut, fibers film could be peeled for use after the water fully
which belongs to the family of Sapindaceae. It is a small tree evaporated.
and endemic to northern China, wild or cultivated trees are
found in 18 provinces of China, including Beijing, Inner 2.2.4. Preparation of Nanocellulose
Mongolia, Shandong, Liaoning, Jilin etc. The seed of The fibers were heated at a ratio of 1:50 (w:w) of 60wt%
Xanthoceras sorbifolia contents abundant oil. As a source of sulfuric acid solution with magnetic stirring at 55C for 2h.
biodiesel, its development has receives special support from Then 500ml cold deionized water was poured into the solution
Chinese governments [14]. However, Xanthoceras sorbifolia to stop the reaction. The suspension was washed with
husks, which are the residua of biodiesel production, has not deionized water by centrifugation at 10,000 rpm for 10 min.
be utilized sufficiently yet. Extracting nanocellulose might When the nanocellulose could not be separated by
create a novel path to use of Xanthoceras sorbifolia husks. centrifugation, 5wt% sodium hydroxide solution was dropped
In this work, nanocellulose was extracted from Xanthoceras in the suspension to neutralize the free acid until the PH value
sorbifolia husks through a series of chemical treatments for of the suspension was 7. The nanocellulose suspension was
the first time. The morphology, chemical structure, thermal obtained. The suspension was poured onto plastic petri dish,
behaviors and crystallinity of the nanocellulose and the the transparent nanocellulose film could be peeled for use
mechanical properties of nanocellulose film were after the water fully evaporated.
investigated. 2.3. Characterizations
Fig. 1. Morphologies of untreated husks (a), cellulose fibers (b), nanocellulose suspension (c) and nanocellulose film (d) from Xanthoceras sorbifolia husks.
The photos of untreated husks, cellulose fibers, was some non-cellulosic substance on the surface. The size of
nanocellulose suspension and nanocellulose film of cellulose fiber was smaller obviously. The surface became
Xanthoceras sorbifolia husks were shown in Fig. 1. Untread smoother, which implied the removal of the non-cellulosic
husks were brown chippings. They looked to be fluffy. After substance through the treatments processing. After acid
delignification, white colored cellulose fibers with compact hydrolysis, the diameter of the fiber became much smaller,
structures were obtained, indicating purer cellulose, which which was under 100nm. It meant that the nanocellulose of
was more suitable for extracting nanocellulose [2]. The Xanthoceras sorbifolia husks was obtained.
nanocellulose presented white coloring in the suspension
through the hydrolysis by sulfuric acid. Because the 3.2. Atomic Force Microscopy (AFM)
incorporation of sulfate groups on cellulose surface created a Fig. 3 showed the AFM micrographs of nanocellulose
negative electrostatic layer, the nanocellulose could suspend obtained by sulfuric acid hydrolysis. Two modes were used to
steadily in water [7]. The nanocellulose film showed good record the data, one was height image, the other was amplitude
film integrity and high transparency, which could be image. It could be seen that the nanocellulose extracted from
functionalized for using in transparent electrode materials. Xanthoceras sorbifolia husks had a rod-like aspect.
Fig. 2 showed the SEM morphologies. It could be seen that
surface of untreated husk was very rough and porous. There
Fig. 2. SEM morphologies of untreated husks (a), cellulose fibers (b) and nanocellulose (c) from Xanthoceras sorbifolia husks.
The dimension of nanocellulose was influenced by many image. The result was shown in Fig.4. The diameters of all the
factors, such as reagents, conditions of the treatments, nanocellulose calculated were below 100nm. Almost 85%
however, the most important factor was the raw materials [15, nanofibers had the diameters between 30nm to 45nm. The
16]. The diameters of the nanocellulose were calculated using average diameter of the nanocellulose extracted from
Nano Measurer software from 100 nanofibers in the amplitude Xanthoceras sorbifolia husks was 37.6nm.
International Journal of Nanoscience and Nanoengineering 2015; 2(6): 43-50 46
3.4. Differential Scanning Calorimetry(DSC) would sulfate the accessible hydroxyl groups on cellulose
fibers and dissolve the amorphous region. To some degrees,
The thermal behaviors of the Xanthoceras sorbifolia husks, the structure of cellulose might be changed and the molecular
cellulose fibers and nanocellolose were compared using weight or degree of polymerization would decrease [1]. The
differential scanning calorimetry (DSC). Fig. 6 showed the molecular weight and size distribution of cellulose crystals
DSC results of the husks, cellulose fibers and nanocellulose. would became wider [4]. These could explain why there was
In the order to remove the absorbed water in cellulose an earlier and wider endothermic peak in the curve of
completely, the samples were kept at 120C for 5min. It could nanocellulose
be seen that the three curves were different because of the
different components. 3.5. Thermogravimetric Analysis (TGA)
The decomposition of untreated husks could be divided into angle close to 22 representing crystalline material and I (am)
three stages. There was a shoulder peak between 225C and is the counter reading at peak intensity at a 2 angle close to 18
320C in the DTG curve. According to the literature [23], it representing amorphous material in this research.
mainly presented the decomposition of hemicellulose. In this The pattern of untreated husks was blurring and the
stage, almost 20% weight was lost. The second stage was crystallinity index was just 35.7%, both of which implied that
probably from 310C to 385C, which was at the temperature there were much amorphous substance in Xanthoceras
of cellulose decomposition. The solid residues was close to sorbifolia husks. Due to the decreasing of non-cellulosic
40% at 385C. The weight lost above 385C was not apparent, substance, the peak in the pattern of cellulose fibers was
and most lost was attributed to the lignin decomposition. narrow and sharp, the crystallinity index went up to 70.2%. In
Finally, there was about 30% weight left for untreated husks. the pattern of nanocellulose, there were a sharper peak and a
The cellulose fibers underwent a two-step degradation higher crystallinity index (77.6%), which meant the removal
process. The shoulder peak around 280C in the DTG curve of of amorphous phase and the excellent mechanical properties
untreated husks disappeared, which implied the decreasing of of the nanocellulose from Xanthoceras sorbifolia husks.
hemicellulose. The decomposition started around 260C.
From 260C to 385C, almost 75% weight lost with the
temperature increasing. About 22% weight left at 700C.
Actually, hemicellulose, lignin and other non-cellulosic
substance started their decompositions at low temperature.
The reduction of these substance would cause the
decomposition happened at higher temperature. Otherwise,
the removal of these non-cellulosic substances through the
treatments would make the structure of cellulose more dense
and compact. These factors might be the reasons cellulose
fibers had better thermal stability than that of untreated husks.
The decomposition process of nanocellulose was
complicated. It presented multiple steps. About 30% weight
left at 700C. The nanocellulose from Xanthoceras sorbifolia
husks began to decompose at about 190C, which was the
lowest of three materials. The poor thermal stability might
result from the drastic reduction in molecular weight and the
Fig. 8. XRD patterns of untreated husks, cellulose fibers and nanocellulose
sulfonation by sulfuric acid [5, 7, 24], which would make the from Xanthoceras sorbifolia husks.
nanocellulose decompose at lower temperature. Otherwise,
sulfuric acid also acted as flame retardants, which led to the
increasing in char fraction [24]. There were mainly two peaks
in the curve of DTG. One was at around 220C, which was
attributed to the sulfated and/or small molecular weight
cellulose. The other was at around 350C, which presented the
degradation of unsulfated cellulose. The broad distribution of
molecular weight [4] and different sulfonation degrees [25]
would make multiple peaks appear in the DTG curves.
3.6. X-ray Diffraction
nanocellulose films were shown in Fig. 9. The storage properties of nanocellulose film. The tensile strength and
modulus of nanocellulose film was much higher than that of Youngs modulus of nanocellulose film were shown in Fig. 10.
cellulose fiber film at the whole range of temperature, which In this work, the largest values were 75.9MPa and 15.9GPa.
might contributed by compact interconnected network of The average tensile strength was 62.6MPa. It approached to
nanocellulose whiskers [29]. The storage modulus of cellulose 74.55MPa, which was the tensile strength of bacterial
fiber film decreased with temperature rising. The storage cellulose film in Martinez-Sanzs work [31]. However, the
modulus of nanocellulose film increased a little first and then tensile strength is still lower than that of nanofibrillated
decreased with temperature rising. The highest storage cellulose films, which is probably due to the lower aspect ratio
modulus of nanocellulose film was about 9500MPa at around of the nanocellulose obtained by acid hydrolysis method. The
90C, which might result from the water loss of the film. average Youngs modulus was 12.0GPa, which was in the
range of 12-19 GPa reported by Henriksson [11].
4. Conclusion
Nanocellulose suspension of Xanthoceras sorbifolia husks
was obtained by several steps. The nanocellulose of
Xanthoceras sorbifolia husks had a rod-like shape, the
diameter was about 38nm. Much non-cellulosic and
amorphous substance in the husks was removed during the
treatments. However, FTIR showed the chemical structure of
cellulose was almost not changed. Cellulose fibers from
Xanthoceras sorbifolia husks had high cellulose purity and
better thermal stability. Due to the effect of hydrolyzation by
sulfuric acid, the fusion point and the thermal stability of
nanocellulose were lower. The crystallinity index of
nanocellulose was as high as 71.5%, which implied the
excellent mechanical properties and application prospects of
the nanocellulose from Xanthoceras sorbifolia husks. The film
made by Xanthoceras sorbifolia husks nanocellulose was
transparent. The maximum tensile strength and Youngs
modulus of the nanocellulose film were 75.9MPa and
15.9GPa.
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