SUPERABSORBENT ALGINATE AEROGELS

Rajendar R. Mallepally*,1,3, Mark A. McHugh1,3 and Kevin R. Ward2,3

1

Department of Chemical and Life Science Engineering, Virginia Commonwealth University, Richmond, VA 23284, USA 2 Department of Emergency Medicine, Virginia Commonwealth University Medical Center, Richmond, VA 23298-0614, USA 3 Material Science Division, VCU Reanimation Engineering Science Center, Virginia Commonwealth University Medical Center, Richmond, VA 23298-0614, USA Corresponding author: rrmallepally@vcu.edu

ABSTRACT Polysaccharides are biopolymers that have excellent biocompatibility and biodegradability and have been considered for a wide range of pharmaceutical and biomedical applications. In this work polysaccharide-based superabsorbent aerogels are prepared using a combination of sol-gel and supercritical fluid technology. The advantage of supercritical drying is the reduced gel shrinkage, higher porosity, and three-dimensional network of the aerogel that are obtained compared to the morphology obtained with conventional air or vacuum drying methods. The aerogel open porous structure and high surface area promotes extremely rapid water absorption into the aerogel matrix by capillary force and it promotes the absorption of large quantities of water or physiological fluids. In the studies reported here, the effect of structural properties on water absorption capacity is systematically investigated and controlled by the type of cross-linking agent and processing conditions used in the aerogel synthesis. Scanning electron microscopy is used to obtain information on the surface morphology and particle size, and nitrogen adsorption/desorption measurements are used to obtain information on the aerogel surface area, pore size, and pore volume. In addition, data are presented on the water absorption capacity and uptake rate for the polysaccharide aerogels. The results from these analytical methods highlight the improved product characteristics of the aerogels synthesized using sol-gel processing technology combined with supercritical fluid technology. INTRODUCTION Superabsorbent materials are lightly cross-linked, three dimensional polymeric networks which absorb large quantities of water, especially pure distilled water [1], whereas the water absorption decreases significantly in saline or physiological fluids. Superabsorbent materials have potential applications in the pharmaceutical, agricultural, and textile fields [2]. Most of the commercially available superabsorbent materials are cross-linked polyacrylic acid or polyacrylamide which are not biodegradable and which account for considerable amounts of environmental pollution [3, 4]. Polysaccharide based superabsorbent materials have specific advantages, such as excellent biocompatibility, biodegradability, and abundant availability. Hence, polysaccharides can be used as alternatives to synthetic polymers. Polysaccharides such as starch, chitosan, cellulose, pectin, and alginate have been investigated as useful hydrogel materials for various applications [5-7]. Likewise, polysaccharide based aerogels have been prepared with starch, alginate, chitosan, and carrageenan [8-11]. Alginate is a natural anionic polysaccharide mainly derived from brown algae. It is a linear random copolymer of (1,4')-linked -D-mannuronic acid and -L-guluronic acid monomers with the chemical structure shown in Figure 1. Alginates have the ability to form strong gels with divalent and trivalent cations and these gels can be readily converted into aerogels by supercritical drying. The highly porous polymeric network of the aerogel provides a large surface area that can be derivatized for a wide range of applications, such as drug delivery, catalysis, and chemical separation processes. The aim of this study is to investigate the performance characteristics of superabsorbent alginate aerogels formed by crosslinking with Ca2+ ions followed by supercritical drying with carbon dioxide.

Figure 1. Chemical structure of alginate where G is the -L-guluronate unit and M is the -D-mannuronate unit. MATERIALS AND METHODS Materials Alginic acid sodium salts with two different grades, based on the viscosity of 2 wt% solutions, were obtained from Sigma Aldrich and used as received. Calcium chloride (Sigma Aldrich), zinc chloride (Fischer Scientific), and barium chloride dihydrate (Acros Organics) were used as received. Methods First, hydrogel beads are synthesized. Alginic acid sodium salt is dissolved in distilled water at 25 C and added drop wise to a stirred CaCl2 solution, also at 25 C, using a syringe pump (KD Scientific) at a flow rate of 3 mL/min. The hydrogel beads are formed instantaneously and are cured in the same solution for one hour under mild stirring. Next, the hydrogel beads are dehydrated to form alcogel beads. The hydrogel beads are suspended in a series of ethanol-water solutions of increasing ethanol concentration (20, 40, 60, 80 v/v%) for 15 minutes in each solution and overnight in 100 % ethanol solution. The final step is to dry the alcogel beads using supercritical CO2 at 40 C and 1,400 psig. The CO2 flows through the solution at a rate of 3.5 L (STP)/min for six hours. Aerogel characterization Nitrogen adsorption/desorption measurements are used to determine the aerogel surface area and pore size distribution. Approximately 100 mg of aerogel are weighed and heated at 60 C under vacuum for four hours. The nitrogen adsorption/desorption measurements are carried out at 77 K (Quantachrome Instruments, Nova 2200e). The specific surface area of the aerogel is calculated with the multipoint BET model in the relative pressure range of 0.05 to 0.30. The pore size distribution is calculated with the BJH model using a desorption isotherm for a relative pressure of less than 0.35. Aerogel beads are immersed in liquid nitrogen for two minutes and crushed to a fine powder with a mortar and pestle. The powder is mounted on aluminum stubs with a carbon tape. A 10 nm platinum coating is spun coated (Denton Vacuum, LLC - USA, Model: Desk V TSC) onto the sample on the stub. Scanning electron microscopic images are obtained with a HITACHI SU-70 SEM with an accelerating voltage of 5 keV. Thermal Gravimetric Analysis (TGA) (PerkinElmer USA, Model Pyris 1 TGA) is performed from 20 to 300 C with a heating rate of 10 C/min in a nitrogen atmosphere. A gravimetric method is used to determine the water uptake rate and water absorption capacity of the aerogel. Approximately 50 mg of aerogel beads are loaded into a preweighed, wet tea bag that is then immersed in 100 mL of saline solution or DI water at room temperature. The weight of the loaded tea bag, after removal of excess water, is determined at predefined times. The water absorption of the aerogel is then calculated according to the following formula:

Water Absorption (g/g) =

Wt (Wwet bag Wdry aerogel ) Wdry aerogel

where Wt = weight of sample at time t, Wwet bag = weight of wet tea bag, and Wdry aerogel = initial weight of dry aerogel.

RESULTS AND DISCUSSION Formation of aerogels The formation of alginate hydrogels in the presence of divalent cations is depicted by the well-known egg-box model, in which cations are coordinated with negatively charged carboxylate ions of alginate (Figure 2) [12]. When a hydrogel is allowed to dry under ambient conditions, a shrunken gel is obtained with complete loss of the porous structure due to the capillary forces exerted on the pore walls. Hence, supercritical carbon dioxide drying is essential to retain a porous structure and to achieve high surface areas, which are important properties for a material to be superabsorbent. The aerogels synthesized in this study with supercritical CO2 typically have surface areas of ~500 m2/g and average pore sizes of ~20 nm. TGA is used to determine the thermal stability of the alginate aerogel synthesized in this study compared with the as-received alginate (see Figure 3). The analysis shows an initial mass loss of about ~20 wt% from 20 to 200 C, which corresponds to desorption of water. Thermal decomposition begins at ~200 C for the as-received alginate and the alginate aerogels synthesized in this study. Alginate aerogel has a moderately slower decomposition rate compared to the rate of the as-received alginate, which is likely due to the presence of Ca2+ ions in the alginate aerogel.

Figure 2. Schematic representation of ionic interactions between Ca2+ and COO of alginate [12].

Figure 3. TGA curves of the alginate aerogel and as-received sodium alginate both obtained at a heating rate of 10 C/min. Figure 4 shows a typical scanning electron micrograph of an aerogel synthesized in this study. The micrograph image shows that the aerogel is highly porous with an interconnected network of fibrils. Water absorption measurements Figure 5 shows a typical water absorption rate for an alginate aerogel synthesized in this study. The equilibrium water absorption of the alginate aerogel reached a maximum of 105 g/g in 24 hours in saline solution, whereas the absorption of DI water only reaches a maximum of 16 g/g. It is interesting that with alginate aerogels, water absorption in saline solution (0.9 wt% NaCl solution) is much higher than the adsorption of DI water. The alginate aerogel absorption behavior is opposite to that observed with typical synthetic or biopolymer based superabsorbent materials.

Figure 4. Scanning electron micrograph of an alginate aerogel synthesized in this study.

Figure 5. Saline and DI water absorption at room temperature for the alginate aerogel synthesized in this study. Effect of crosslinking agent concentration Aerogels are prepared with different concentrations of Ca2+ ions to investigate the effect of crosslinking agent concentration on the water absorbency. Figure 6 shows the typical water absorbency of an aerogel after soaking for 10 minutes in saline solution. As shown in the graph, the higher the crosslinking agent concentration, the lower the water absorption. As the crosslinking agent concentration increases, the crosslinking density of polymer network also increases, which ultimately retards the swelling of the aerogel.

Figure 6. Effect of Ca2+ concentration on the water absorbency of alginate aerogel. The water absorption data are obtained in each case after soaking the aerogel for 10 minutes in saline solution.

CONCLUSIONS Only polysaccharide based superabsorbent aerogels have been successfully prepared using sol-gel processing technology combined with supercritical fluid technology. The unique property of superabsorbent materials created in the present study is they exhibit much higher water absorbency in 0.9 wt% NaCl compared to pure distilled water. The high water absorbency and fast uptake rate in saline and the biodegradability of these biosuperabsorbent materials are highly favorable materials characteristics for many industrial applications. Further work on the influence other parameters such as polymer concentration, polymer molecular weight, pH, and temperature on the absorbency behavior is in progress and will be presented at the conference. ACKNOWLEDGMENT The authors gratefully acknowledge support from the Office of Naval Research from Grant N000140710526. REFERENCES [1] Kabiri, K. and M.J. Zohuriaan-Mehr, Macromol. Mater. Eng., Vol. 289, 2004, p. 653. [2] Kabiri, K., H. Omidian, M.J. Zohuriaan-Mehr and S. Doroudiani, Polym. Compos., Vol. 32, 2011, p. 277. [3] Yoshimura, T., M. Matsunaga and R. Fujioka, e-Polymers, Vol. 080, 2009, p. 1. [4] Yoshimura, T., K. Sengoku and R. Fujioka, Polym. Bull., Vol. 55, 2005, p. 123. [5] Li, H., J. Yang, X. Hu, J. Liang, Y. Fan, and X. Zhang, J. Biomed. Mater. Res., Part A, Vol. 98A, 2011, p. 31. [6] Yoshimura, T., A. Itou and R. Fujioka, Fukuoka Joshi Daigaku Ningen Kankyogakubu Kiyo, Vol. 40, 2009, p. 21. [7] Demitri, C., R. Del Sole, F. Scalera, A. Sannino, G. Vasapollo, A. Maffezzoli, L. Ambrosio, and L. Nicolais, J. Appl. Polym. Sci., Vol. 110, 2008, p. 2453. [8] Quignard, F., R. Valentin and R.F. Di, New Journal of Chemistry, Vol. 32, 2008, p. 1300. [9] Rinki, K., P. Dutta, A. Hunt, D. Macquarrie and J. Clark, International Journal Polymeric Materials, Vol. 60, 2011, p. 988. [10] Ahmed, M.S. and Y.A. Attia, Applied Thermal Engineering, Vol. 18, 1998, p. 787. [11] Hosseinzadeh, H., A. Pourjavadi and G.R. Madhavinia, J. Polym. Mater., Vol. 23, 2006, p. 61. [12] Bajpai, S.K. and S. Sharma, React. Funct. Polym., Vol. 59, 2004, p. 129.