厚度可控的高岭土/海藻酸钙复合水凝胶膜的制备及性能表征
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摘要
为探究控制藻酸盐水凝胶膜厚度和粗糙度的方法,采用缠绕不同直径铜丝的玻璃棒制备高岭土/海藻酸钙(K/CaAlg)复合水凝胶膜,采用扫描电子显微镜、3D超景深显微镜、白光共聚焦显微镜和原子力显微镜考察高岭土/海藻酸钙(K/CaAlg)复合水凝胶膜的表面形貌,采用热重分析和X射线衍射对膜进行测试表征,并对该复合膜吸附亚甲基蓝的过程进行吸附动力学和吸附热力学分析.结果表明:采用缠绕不同直径铜丝的玻璃棒能控制膜的厚度;较薄的铸膜液在几分钟内完全交联,薄膜表面出现折叠结构,并且含有比厚膜更多的高岭土,比厚膜表面更加粗糙;而较厚的铸膜液交联较慢,形成三明治结构;该薄膜对亚甲基蓝有较高的去除率和吸附量,当膜厚为0.077 mm时,对亚甲基蓝的去除率达到79.8%,吸附量达到51.06 mg/g,吸附更符合伪二级动力学模型和Freundlich模型.
In order to explore the method to control the thickness and roughness of the alginate hydrogel film, Kaolin/calcium alginate(K/CaAlg) composite hydrogel films were prepared by the glass rod twined by copper wires with different diameters. The surface morphologies of the films were observed by ultra-depth 3D microscope, white light scanning microscope, AFM and SEM. The K/CaAlg film was characterized by TG and XRD. The thermodynamic and kinetic of methylene blue adsorption onto the composite film were analyzed. The results showed that the thickness of the film can be controlled with the glass rods twined by the copper wires with different diameters. The thinner casting solution was completely cross-linked in a few minutes and the folded structure appeared on the surface of thin film, and the thin film contained more Kaolin than the thick film, and the surface of thin film was rougher than that of thicker film. However, the thicker casting solution could not be immediately cross-linked and a sandwich structure was formed. The thin film showed higher removal rate and adsorption capacity for methylene blue. The removal rate reached 79.8% and the adsorption capacity was 51.06 mg/g when the thickness of the film was 0.077 mm, and the adsorption was more accordant with the pseudo two level kinetic model and Freundlich model.
In order to explore the method to control the thickness and roughness of the alginate hydrogel film, Kaolin/calcium alginate(K/CaAlg) composite hydrogel films were prepared by the glass rod twined by copper wires with different diameters. The surface morphologies of the films were observed by ultra-depth 3D microscope, white light scanning microscope, AFM and SEM. The K/CaAlg film was characterized by TG and XRD. The thermodynamic and kinetic of methylene blue adsorption onto the composite film were analyzed. The results showed that the thickness of the film can be controlled with the glass rods twined by the copper wires with different diameters. The thinner casting solution was completely cross-linked in a few minutes and the folded structure appeared on the surface of thin film, and the thin film contained more Kaolin than the thick film, and the surface of thin film was rougher than that of thicker film. However, the thicker casting solution could not be immediately cross-linked and a sandwich structure was formed. The thin film showed higher removal rate and adsorption capacity for methylene blue. The removal rate reached 79.8% and the adsorption capacity was 51.06 mg/g when the thickness of the film was 0.077 mm, and the adsorption was more accordant with the pseudo two level kinetic model and Freundlich model.
引文
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[23]HO Y S,MCKAY G.The kinetics of sorption of divalent metal ions onto sphagnum moss peat[J].Water Research,2000,34(3):735-742.
[2]ZHAO K,CHEN T,LIN B,et al.Adsorption and recognition of protein molecular imprinted calcium alginate/polyacrylamide hydrogel film with good regeneration performance and high toughness[J].Reactive&Functional Polymers,2015,87:7-14.
[3]GARCIA-MONTANO J,DOMENECH X,GRCIA-HORTALJ A,et al.The testing of several biological and chemical coupled treatments for cibacron red FN-R azo dye removal[J].Journal of Hazardous Materials,2008,154(1/2/3):484-490.
[4]ZHAO K,HUANG J,YING X,et al.Macromolecularly imprinted calcium phosphate/alginate hybrid polymer microspheres with the surface imprinting of bovine serum albumin in inverse-phase suspension[J].Journal of Applied Polymer Science,2008,109(4):2687-2693.
[5]BAYER C L,HERRERO E P,PEPPAS N A.Alginate films as macromolecular imprinted matrices[J].Journal of Biomaterials Science Polymer Edition,2011,22(11):1523-1534.
[6]ZHAO K,ZHANG X,WEI J,et al.Calcium alginate hydrogel filtration membrane with excellent anti-fouling property and controlled separation performance[J].Journal of Membrane Science,2015,492:536-546.
[7]ZHENG H,XIE H,WU H,et al.Investigation of spherical hydrogel surface with optical interferometer[J].Colloids&Surfaces A Physicochemical&Engineering Aspects,2015,484:457-462.
[8]GUO J,ZHAO K,ZHANG X,et al.Preparation and characterization of carboxyl multi-walled carbon nanotubes/calcium alginate composite hydrogel nano-filtration membrane[J].Materials Letters,2015,157:112-115.
[9]TEHRANI-BAGHAA R,NIKKAR H,MAHMOODI N M,et al.The sorption of cationic dyes onto Kaolin:Kinetic,isotherm and thermodynamic studies[J].Desalination,2011,266(1/2/3):274-280.
[10]NANDI B K,GOSWAMI A,PURKAIT M K.Removal of cationic dyes from aqueous solutions by Kaolin:Kinetic and equilibrium studies[J].Applied Clay Science,2009,42(3/4):583-590.
[11]RIDA K,BOURAOUI S,HADNINE S.Adsorption of methylene blue from aqueous solution by Kaolin and zeolite[J].Applied Clay Science,2013,83/84(10):99-105.
[12]DAI H,LI X,LONG Y,et al.Multi-membrane hydrogel fabricated by facile dynamic self-assembly[J].Soft Matter,2009,5(10):1987-1989.
[13]VOO W P,OOI C W,ISLAM A,et al.Calcium alginate hydrogel beads with high stiffness and extended dissolution behaviour[J].European Polymer Journal,2016,75:343-353.
[14]XIE H G,ZHENG J N,LI X X,et al.Effect of surface morphology and charge on the amount and conformation of fibrinogen adsorbed onto alginate/chitosan microcapsules[J].Langmuir,2010,26(8):5587-5594.
[15]傅轶凡,冯灵智,赵孔银,等.TiO2/海藻酸钙复合膜的制备表征及力学性能[J].高分子材料科学与工程,2015,31(4):87-91.FU Y F,FENG L Z,ZHAO K Y,et al.Preparation,characterization and mechanical properties of TiO2/calcium alginate composite membrane[J].Polymer Materials Science and Engineering,2015,31(4):87-91(in Chinese)
[16]POURIAVADI A,GHASEMZADEH H,SOLEYMAN R.Synthesis,characterization,and swelling behavior of alginateg-poly(sodium acrylate)/Kaolin superabsorbent hydrogel composites[J].Journal of Applied Polymer Science,2010,105(5):2631-2639.
[17]BARRECA S,ORECCHIO S,PACE A.The effect of montmorillonite clay in alginate gel beads for polychlorinated biphenyl adsorption:Isothermal and kinetic studies[J].Applied Clay Science,2014,99(9):220-228.
[18]FROST R L,HA T T,KRISTOF J.FT-Raman spectroscopy of the lattice region of Kaolinite and its intercalates[J].Vibrational Spectroscopy,1997,13(2):175-186.
[19]VA MAKO,KOVACS A,HATO Z,et al.Simulation assistedˇGcharacterization of Kaolinite-methanol intercalation complexes synthesized using cost-efficient homogenization method[J].Applied Surface Science,2015,357:626-634.
[20]张天乐,王宗良.龙岩高岭土矿床地质特征及成矿作用[J].地球学报,1996(3):292-301.ZHANG T L,WANG Z L.The geological characteristics and mineralization of the Longyan Kaolin deposit[J].Journal of the Earth,1996(3):292-301(in Chinese).
[21]张敬阳,叶玲.龙岩高岭土矿物学特征及插层复合物的制备[J].岩石矿物学杂志,2011,30(2):307-312.ZHANG J Y,YE L.Mineralogical characteristics of Longyan Kaolin and the preparation of intercalated complex[J].Petromineralogy Journal,2011,30(2):307-312(in Chinese).
[22]TUTEM E,APAK R,覶A ATAY F.Adsorptive removal of chlorophenols from water by bituminous shale[J].Water Research,1998,32(8):2315-2324.
[23]HO Y S,MCKAY G.The kinetics of sorption of divalent metal ions onto sphagnum moss peat[J].Water Research,2000,34(3):735-742.