Você está na página 1de 5

Biodegradability of Blend Hydrogels Based on Carboxymethyl Cellulose and Carboxymethyl Starch

Manuscript ID: Session: Date Submitted by the Author: Complete List of Authors:

r Fo
Journal: Category:

Transactions of the Materials Research Society of Japan MRSJ-2011-0131 2010 SessionJ:Advanced Softmaterials Gel Technologies and Various Functional Designs 13-Jun-2011

Hiroki, Akihiro; Japan Atomic Energy Agency, Quantum Beam Science Directorate Pham, Hong; Vietnam Atomic Energy Institute Nagasawa, Naotsugu; Japan Atomic Energy Agency, Quantum Beam Science Directorate Tamada, Masao; Japan Atomic Energy Agency, Quantum Beam Science Directorate Environmental technology/ Environmental materials-2004, Radiation science-7216

Pe

er

Re

vi

ew

Page 1 of 4

Biodegradability of Blend Hydrogels Based on Carboxymethyl Cellulose and Carboxymethyl Starch


Akihiro Hiroki, Pham Thi Thu Hong*, Naotsugu Nagasawa, and Masao Tamada
Quantum Beam Science Directorate, Japan Atomic Energy Agency, 1233 Watanuki, Takasaki, Gunma, 370-1292, Japan Fax: 81-27-346-9694, e-mail: hrioki.akihiro@jaea.go.jp * Research and Development Center for Radiation Technology, Vinagamma, VAEI Troung Tre Linh Xuan Thu Duc, Ho Chi Minh City, Vietnam

Biodegradable blend hydrogels based on carboxymethyl cellulose (CMC) and carboxymethyl starch (CMS) were prepared by the radiation-induced crosslinking technique. Properties of the crosslinked CMC/CMS blend hydrogels such as gel fraction, degree of swelling (Sw), gel strength, and biodegradability were investigated. The Sw of the CMC/CMS blend hydrogels were in the range of 10 to 800, which depended on the dose as well as the composition of CMC/CMS. The gel fraction and the Sw of the CMC/CMS blend hydrogels obtained at same dose decreased and increased with increasing the CMS content of the mixture, respectively. The biodegradability of the CMC/CMS blend hydrogels was controlled by adjusting the composition of CMC/CMS, resulting in the biodegradation ratio in the range of 5% to 20% after 30 days in controlled compost.
Key words: Hydrogel, Polysaccharide derivatives, Irradiation, Crosslinking, Biodegradability 1. INTRODUCTION Natural polysaccharides such as cellulose and starch are produced in large quantities by plants, which are abundant resources for environmental-friendly and biocompatible products. Derivatives of the polysaccharides also have been applied in industrial, medical, and agricultural fields because of their unique structure, distinctive properties, safety, and biodegradability. Carboxymethyl cellulose (CMC) and carboxymethyl starch (CMS) are typical water soluble polysaccharide derivatives, which are obtained by the carboxymethylation of cellulose and starch, respectively. CMC and CMS have been widely used as thickener, stabilizer for emulsions, and additives in foods, pharmaceuticals and cosmetics [1, 2]. The polysaccharides and their derivatives usually undergo degradation by ionizing radiation in solid state and low concentration aqueous solution. It was found, however, that hydrogels of polysaccharide derivatives such as CMC and CMS were produced by gamma or electron beam irradiation to their high concentrated aqueous solution [3]. The hydrogels swelled by absorbing more than hundred gram of water per gram of dry gel, which are expected to be useful as the medical and agricultural materials [4, 5]. Recently, M. Wang et al, have reported the preparation of blend hydrogels based on CMC and poly( N -vinyl pyrrolidone) by -irradiation and their properties for the application to wound dressing [6]. Blending is a convenient and effective method to improve the performance of polymer materials such as gel strength, swelling

Fo

rP

ee

and biodegradation [7-9]. It is also known that the biodegradability of the polysaccharide derivatives depends on the degree of substitution [10]. However, it has not been reported that the biodegradability of the hydrogels as super water absorbent was controlled by the combination of the blending and the radiation crosslinking techniques. In this work, blend hydrogels constructed from CMC and CMS were prepared by the radiation-induced crosslinking technique. The effect of the composition on the properties of the CMC/CMS blend hydrogels such as swelling, mechanical strength, and biodegradability were investigated. The biodegradation rate of the hydrogels as super water absorbent were controlled by adjusting the blend ratio. 2. EXPERIMENTAL 2.1. Materials Carboxymethyl cellulose (CMC) and carboxymethyl starch (CMS) used in this study were purchased from Daicel Chemical Industry Co. Ltd., Japan and Nippon Starch Chemical Co. Ltd., Japan, respectively. Degree of substitution of carboxymethyl group of CMC and CMS was 1.34 and 0.12, respectively. All other reagents used in this experiment were of analytical grade. 2.2. Preparation of Blend Hydrogels The preparation of CMC/CMS blend hydrogels without any crosslinker is as follows. The CMC/CMS aqueous solution of 40 wt.% (blend ratio of CMC/CMS: 100/0, 75/25, 50/50, 25/75, 0/100), which is paste-like state, were

rR

ev

iew

Page 2 of 4

sealed in polyethylene-nylon bags after degassing using vacuum apparatus. The samples were irradiated to total a dose of 1 to 40 kGy at room temperature to obtain CMC/CMS blend hydrogels. The irradiations were carried out using 60 Co -ray source at the Takasaki Advanced Radiation Research Institute, Japan Atomic Energy Agency. 2.3. Gel fraction and swelling of hydrogels The irradiated CMC/CMS blend samples were freeze-dried until constant weight. The dried sample was immersed into an excess amount of distilled-deionized water at room temperature for 48 h to remove uncrosslinked polymer. The gel content in the sample was estimated by measuring gravimetrically insoluble part after the extraction in distilled-deionized water. Gel fraction of the obtained blend hydrogels was calculated from the following equation, Gel fraction (%) = W 1 /W 0 x 100 where W 1 is the weight of the dry gel after the extraction and W 0 is the initial weight of the dry gel. The obtained CMC/CMS blend hydrogels were immersed in distilled deionized water for a certain time at room temperature. After wiping excess water at the surface of the hydrogel, the weight of swollen gel was measured. The degree of swelling (Sw) of the blend hydrogels was calculated from the following equation, Sw = (W s -W d )/W d

quantitatively collected by soda lime column, and water produced by the reaction was caught in the last calcium chloride column. The amount of produced CO 2 was calculated as a difference in the weight of the last two columns (containing soda lime and calcium chloride) at the beginning and during the test. Pure compost mixed with sea sand was used as a blank sample . 3. RESULTS AND DISCUSSION 3.1. Radiation crosslinking Since crosslinking and scission of the polymer chain occur simultaneously in the polymer aqueous solution as a paste-like state during the -irradiation, the gel fraction and the Sw of the CMC/CMS blend hydrogels have been influenced by the dose. Fig. 1 shows the gel fraction of CMC/CMS blend hydrogels with various concentrations of CMS as a function of the dose. As a result of comparison of FT-IR spectra in which attended to the C=O stretching band of carboxymethyl group, the composition of CMC/CMS in the obtained blend hydrogels was same with the initial ones before washing. The gel fraction of CMC/CMS blend hydrogels except for the composition of 0/100 increased sharply up to 10 kGy and reached a constant value at 30 kGy. In contrast to the CMC/CMS blend hydrogels, the gel fraction of the pure CMS hydrogel increased sharply in the range of 1 to 5 kGy, and then gradually decreased with increasing dose from 10-40 kGy. It was found that the dose required for the crosslinking of CMS is relatively smaller than that of CMC, and furthermore, CMS is degraded by the irradiation at high dose. On the other hand, an increase in the content of CMC raised the gel fraction of the CMC/CMS blend hydrogels. The crosslinking of polysaccharide derivatives such as CMC and carboxymethyl chitosan depends on a degree of substitution as well as a molecular weight. The irradiation with CMC that has a high degree of substitution gave the high gel fraction at the same dose [11, 12].
100

where W s is the weight of the swollen gel and W d is the weight of the dried gel.

Gel fraction (%)

2.4. Mechanical properties Mechanical properties of the obtained blend hydrogels were measured by using Strograph-R1 Material Tester (Toyoseiki Co. Ltd, Japan). The obtained hydrogels were cut into a cylindrical shape with a diameter of 18 mm and a height of 11.7 mm, and then compressed at a crosshead speed of 50 mm/min. The gel strength was evaluated by 50% compressing gel samples between parallel plates. At least four measurements for each sample were recorded and a mean value was calculated. 2.5. Biodegradability Microbial degradability of the obtained hydrogels was evaluated by using a microbial oxidative degradation analyzer (MODA, Saida UMS Inc.). The MODA is assembled by following ISO14855 protocol. 10 g of sample was mixed with a rinsed sea sand and compost with a moisture content of 52%, and then placed in a heated reaction column. Inside of the reaction column was at 35 C and flow of the moisturized air (carbon dioxide free) was 30 ml/min. The degradability of the sample was monitored by a produced carbon dioxide (CO 2 ) gas. The CO 2 was

Fo

rP

ee

rR

ev
80 60 40 20 0 0

Fig. 1 Effect of dose on the gel fraction of CMC/CMS blend hydrogels. The compositions of CMC/CMS in samples were as follows: ( ) 0/100, ( ) 25/75, ( ) 50/50, ( ) 75/25, and ( ) 100/0.

iew
10

20 Dose (kGy)

30

40

Page 3 of 4

Saiki et al reported that CMC polymer radicals produced by the irradiation were mainly in a methyl of the carboxymethyl group, in which the crosslinking structure was formed [13]. CMC and CMS used in this study are 1.34 and 0.12 of the degree of substitution, respectively. Therefore, the crosslinking of the CMC in compared with CMS occurred with high frequency, resulting in the increase in the gel fraction with increasing the content of CMC. The network structure of polysaccharide derivatives formed by the crosslinking can absorb and hold a large amount of water. The swelling property of the hydrogel is an important factor for the applications. Fig. 2 shows the Sw of the CMC/CMS blend hydrogels swollen to the equilibrium state as a function of the dose. The obtained CMC/CMS blend hydrogels exhibited the Sw in the range of 10 to 800. The Sw of the CMC/CMS blend hydrogels, except CMS hydrogel, decreased significantly with increasing the dose, and leveled off in the range of 20 kGy to 40 kGy. The decrease in the Sw is due to the increase in a number of crosslinking points. Since the formation of crosslinking depends on not only the dose but also the degree of substitution of polysaccharide derivatives, the Sw of the CMC/CMS blend hydrogels at the same dose decreased with increase in the concentration of CMC that has a higher degree of substitution. On the other hand, the Sw of the CMS hydrogel without CMC decreased sharply up to 5 kGy, and then increased with increasing the dose. The Sw of CMS hydrogels obtained at 2 kGy exhibited about 630, which was higher than Sw of 500 reported by Nagasawa et al. This is why the degree of substitution of CMS used in this work is lower than that in the previous report. The increase in the Sw at high dose results from the scission of the polymer chain [7]. It is considered that the degradation occurred predominantly rather than the crosslinking because of the low degree of substitution.

3.0 Gel strength (MPa) 2.5 2.0 1.5 1.0 0.5 0 100 / 0

75 / 25

50 / 50

25 / 75

Composition of CMC / CMS

Fig. 3 Composition dependence on gel strength of CMC/CMS blend hydrogels obtained at various doses: ( ) 10 kGy, ( ) 20 kGy, ( ) 30 kGy, and ( ) 40 kGy. 3.2. Mechanical strength of CMC/CMS blend hydrogels Mechanical properties of some pure polysaccharide derivatives hydrogels obtained by the irradiation have been reported [14, 15]. Mechanical strength of the hydrogels is one of the important factors in the handling of the gel. Therefore, it is necessary to investigate the mechanical properties of the CMC/CMS blend hydrogels in order to apply to the super water absorbents. Effects of the composition of the CMC/CMS blend hydrogels on gel strength are shown in Fig. 3. The gel strength of the CMC/CMS blend hydrogels obtained at same dose decreased with increase in the CMS content in the CMC/CMS blend hydrogels, after reaching the minimum and then increased again. The gel strength of the CMC/CMS blend hydrogels increased with increasing the dose, in which that of CMC/CMS of 25/75 reached 2.3 MPa at 40 kGy. This is due to the increase in the

Fo
20 Dose (kGy)

rP
30

ee

rR

ev

iew

800 600 400 200 0 0 10 40

Amount of carbon dioxide (g)

4.0 3.0 2.0 1.0 0

Degree of swelling

10 15 20 25 Aeration period (days)

30

Fig. 2 Effect of dose on the degree of swelling of the crosslinked CMC/CMS blend hydrogels. The compositions of CMC/CMS in samples were as follows: ( ) 0/100, ( ) 25/75, ( ) 50/50, ( ) 75/25, and ( ) 100/0.

Fig. 4 Biodegradation of CMC/CMS blend hydrogels in compost at 35C. The compositions of CMC/CMS in samples were as follows: ( ) 100/0, ( ) 25/75, ( ) 50/50, ( ) 25/75, and ( ) 0/100.

Page 4 of 4

21 Degradation ratio (%) 18 15 12 9 6 3 0 100/0 75/25 50/50 25/75 0/100 Composition of CMC/CMS

were prepared by the -irradiation to the concentrated aqueous solution as a paste state without any additives. The gel fraction and the Sw of the CMC/CMS blend hydrogels increased and decreased with increase in the dose, respectively. The obtained blend hydrogels exhibited a super water absorbability, moderate mechanical strength, and biodegradability in compost. The biodegradability of blend hydrogels could be controlled by adjusting the composition of the CMC/CMS as well as dose. Therefore, the hydrogels prepared by blending and radiation-induced crosslinking techniques could be suitable to use as a super water absorbent for agriculture. References [1] T. M. Greenway, Cellulosic Polymers, Ed. by D. R. Gilbert, New York, Honser (1994) pp. 243-255. [2] M. C. Levy and M. C. Andry, Inter. J. Pharm. , 62 , 27-35 (1990). [3] F. Yoshii, L. Zhao, R. A. Wach, N, Nagasawa, H. Mitomo, and T. Kume, Nucl. Instr. and Meth. B , 208 , 320-324 (2003). [4] R. A. Wach, H. Mitomo, F. Yoshii, and T. Kume, J. Appl. Polym. Sci. , 81 , 3030-3037 (2001). [5] N. Nagasawa, T. Yagi, T. Kume, and F. Yoshii, Carbohydrate Polymers , 58 , 109-113 (2004). [6] M. Wang, L. Xu, H. Hu, M. Zhai, J. Peng, Y. Nho, J. Li, and G. Wei, Nucl. Instr. and Meth. B , 265 , 385-389 (2007). [7] L. Fan, Y. Du, B. Zhang, J. Yang, J. Zhou, J. Kennedy, Carbohydrate Polymers , 65 , 447-452 (2006). [8] L. Zhao, L. Xu, H. Mitomo, F. Yoshii, Carbohydrate Polymers , 64 , 473-480 (2006). [9] Y. Tahibana, N. T. T. Giang, F. Ninomiya, M. Funabashi, and M. Kunioka, Polym. Degr. Stab. , 95 , 1406-1413 (2010). [10] R. G. H. Siu, R. T. Darby, P. R. Burkholder, and E. S. Barghoorn, Textile Res. J. , 19 , 484-488 (1949). [11] B.Fei, R. A. Wach, H. Mitomo, F. Yoshii, and T. Kume, J. Appl. Polym. Sci. , 78 , 278-283 (2000). [12] A. Hiroki, H. T. Trun, N. Nagasawa, and M. Tamada, Radiat. Phys. Chem. , 78 , 1076-1080 (2009). [13] S. Saiki, N. Nagasawa, A. Hiroki, N. Morishita, M. Tamada, H. Kudo, and Y. Katsumura, Radiat. Phys. Chem. , 80 , 149-152 (2011). [14] R. A. Wach, H. Mitomo, N. Nagasawa, and F. Yoshii, Radiat. Phys. Chem. , 68 , 771-779 (2003). [15] L. Zhao, H. Mitomo, M. Zhai, F. Yoshii, N. Nagasawa, T. Kume, Carbohydrate Polymers , 53 , 439-446 (2003).

Fig. 5 Relationship between the biodegradation ratio and the composition of CMC/CMS blend hydrogels. crosslinking density. The changes in the gel strength of the CMC/CMS blend hydrogels were similar with that of CMC/carboxymethyl chitosan blend hydrogels [12]. The gel strength of the CMC/CMS blend hydrogels was controlled by adjusting the composition as well as the dose. 3.3. Biodegradation of CMC/CMS blend hydrogels Biodegradation of the polymer is a desirable property for applications in the environmental and agricultural fields. It is known that polysaccharides and their derivatives are degraded by microorganism in compost, even though the crosslinking structure is formed in each polymer [3]. The crosslinked polysaccharide derivatives are finally converted to carbon dioxide and water by microbial degradation in compost. Fig. 4 shows the result of the biodegradation test with the CMC/CMS blend hydrogels. The biodegradability of the CMC/CMS blend hydrogels was evaluated from the amount of released carbon dioxide. The CMC/CMS blend hydrogels of 100/0, 75/25, 50/50, 25/75, 0/100 used in the test were prepared by -irradiation with 5, 10, 20, 20, 20 kGy, respectively, which exhibited the almost same gel fraction, about 50%, and the Sw in the range of about 70 to 180. The discharge of carbon dioxide generated by the biodegradation of the blend hydrogels gradually increased with time. Increase in the CMS content raised up the degradability. It was found that the degradation rate of CMC/CMS blend hydrogel (0/100) at the initial 3 days was 6.4 times faster than that of 100/0. Fig. 5 shows the degradation ratio of the CMC/CMS blend hydrogels after 30 days in the controlled compost. The degradation ratio gradually increased with increasing the CMS content, and reached 20% at 0/100 of CMC/CMS blend hydrogels. Therefore, the biodegradability of the CMC/CMS blend hydrogels was controlled by adjusting the composition of the CMC/CMS. 4. CONCLUSION The blend hydrogels based on CMC and CMS

Fo

rP

ee

rR

ev

iew

Você também pode gostar