介孔无机抗菌材料的制备及在棉织物上的应用
|
摘要
由于无机抗菌剂广谱抗菌,抗药性小,安全性高,耐热性好而且杀菌效果持久等优点从20世纪80年代开始迅猛发展,迅速引起了人们的关注。在所有金属中,银可以广泛应用于催化,电学和光学领域,除此之外银还是一种具有广谱杀菌作用的材料,其杀菌原理与抗生素的有机抗菌不同,属于一种无机抗菌,而且让病菌无法产生抗药性。
有序介孔氧化硅材料SBA-15具有巨大的比表面积和孔容,以及无毒、生物兼容性等特点,同其他普通缓释药物制剂相比,其有更大的药物负载量和更好的缓释效果,因此它被作为新型药物控缓释载体材料的研究越来越受到重视,并且取得了令人瞩目的进展。SBA-15孔径分布狭窄,孔道结构规则,其内表面存在活性基团,易于被修饰,非常有利于引入其他分子。这些固有的特征使它与其他无机载体相比,表现出对银离子更好的吸附性能。另外介孔材料的多孔结构,尤其是大于细菌尺度的孔道可以增大细菌与抗菌剂之间的接触概率,提高抗菌剂的杀菌效率,因此其在载银抗菌剂的研制上具有广阔的前景。
本论文采用溶胶凝胶法,以三嵌段共聚物P123作为结构导向剂,正硅酸乙酯为硅源,制备出有序介孔氧化硅SBA-15,然后用硅烷偶联剂APTES对其进行表面改性,通过共价嫁接将带有机官能团的硅烷以共价键的形式结合在介孔材料的内表面,在温和条件下制备出性能良好的金属离子型无机抗菌材料,并研究了不同条件对载银量的影响。最后优选分散剂和粘合剂,采用浸渍的整理工艺将制备的无机抗菌剂成功用于棉织物的抗菌整理,同时进行防变色整理,并对抗菌棉织物的抗菌性能及机械性能进行测试。
本文的研究内容和结论如下:
(1)实验制备的SBA-15具有高度有序二维六方孔道结构,且孔径分布单一,较大的比表面积和较大的孔容,样品的比表面积采用BET法计算可以达到611m~2/g,孔容为0.65cm~3/g。孔道长程有序,有利于提高介孔材料药物装载的能力。
(2)采用APTES对SBA-15进行了表面改性。硅烷偶联剂通过化学键的形式嫁接到介孔材料上,维持了孔道原有的长程有序结构和良好的热稳定性。
(3)采用单因素分析,探讨了AgNO_3溶液浓度、载银时间、载银温度对SBA-15载银量的关系。
(4)优选施加固着技术,对棉织物进行抗菌和防变色整理,赋予其抗菌功能。
(5)经抗菌实验表明:棉织物经过添加量为1.00%的无机抗菌剂整理后,与大肠杆菌、金黄色葡萄球菌接触1小时,杀菌率均达到100%上。抗菌棉织物除具有良好的抗菌效果外,同时还有较好的耐水洗性,经过20次水洗后抗菌率大于95%。
Inorganic antibacterial agents with good properties of long lasting, stability, safe and broad-spectrum antibiosis, overcome the drawbacks of organic antibacterial agents, and with excellent antibacterial activity against both bacteria and funguses, having attracted many researchers’interest in the field of antimicrobials since 1980s. In all metals, silver has widely applied in many fields for its advantages in catalytic, electronic and optical, otherwise, silver is good at broad-spectrum antibiosis. The principal inorganic antibacterial agents have been originated from metal ions, it will not lead up to drug resistance.
Mesoporous silicas present high superficial areas and large uniform pores, non-toxic and biological compatibility.The property of drug loading and controlled release is much better, compared with other carriers.Their silica wall surface can be modified with organic groups to adjusted their properties and achieve specific purposes. These inherent characteristics make the adsorption performance to silver ions of mesoporous silica much better than other inorganic carrier. The structure of mesoporous material, especially for the pores, which is bigger than the bacteria, can increase the chance of contacts with antibacterial agent and bacteria, improving the antibacterial efficiency and make the silver antibacterial agent an increasingly wide utilization in all fields.
Mesoporous molecular sieves SBA-15 was synthesized by sol-gel process using tri-block copolymer P123 as a template agent and TEOS as silicon source in this paper. APTES (3-aminopropyl-triethoxysilane) was grafted on the surface of the SBA-15. Then the antibacterial agent was obtained at moderate condition. Finally, the cotton fabric was finished by the synthesized compound antibacterial agent through one time dipping. Besides,the problem of Ag type antibacterial agent tamishing has been resolved. The effect on the antibacterial property of the antibacterial fabrics was also tested.
The main conclusions are as follows:
(1) The prepared SBA-15 had the structure of two dimensional mesoporous with highly ordered hexagonal phase. The size distribution of mesoporous pore was verynarrow and uniform, the specific surface area of SBA-15 was 611m~2/g, the pore volume of mesoporous pore was 0.65cm~3/g. Highly ordered structure did benefit to the improvement of drug loading.
(2) The surface of SBA-15 was modified by APTES. The amino groups were grafted on the surface of channels, the ordered structure and thermal ability remained.
(3) The relationship between initial concentration of silver nitrate, loading time, temperature and the amount of loaded silver was studied.
(4) Optimal design on finishing was chosen to give the cotton fabric functional finish, which made the fabric antibacterial. Besides, the problem of Ag type antibacterial agent tarnishing has been resolved.
(5) The antibacterial test showed that this powder had 100% bacterial action on E.coli, S.aures and C.albicans within 1h by adding 1.00wt% antimicrobial on the fabrics. Antibacterial fabric are excellently antibiotic against the bacteria mentioned above and fairly wash fast.After washed ten times , the antibacterial rate of the antibacterial agent remained above 95%.
有序介孔氧化硅材料SBA-15具有巨大的比表面积和孔容,以及无毒、生物兼容性等特点,同其他普通缓释药物制剂相比,其有更大的药物负载量和更好的缓释效果,因此它被作为新型药物控缓释载体材料的研究越来越受到重视,并且取得了令人瞩目的进展。SBA-15孔径分布狭窄,孔道结构规则,其内表面存在活性基团,易于被修饰,非常有利于引入其他分子。这些固有的特征使它与其他无机载体相比,表现出对银离子更好的吸附性能。另外介孔材料的多孔结构,尤其是大于细菌尺度的孔道可以增大细菌与抗菌剂之间的接触概率,提高抗菌剂的杀菌效率,因此其在载银抗菌剂的研制上具有广阔的前景。
本论文采用溶胶凝胶法,以三嵌段共聚物P123作为结构导向剂,正硅酸乙酯为硅源,制备出有序介孔氧化硅SBA-15,然后用硅烷偶联剂APTES对其进行表面改性,通过共价嫁接将带有机官能团的硅烷以共价键的形式结合在介孔材料的内表面,在温和条件下制备出性能良好的金属离子型无机抗菌材料,并研究了不同条件对载银量的影响。最后优选分散剂和粘合剂,采用浸渍的整理工艺将制备的无机抗菌剂成功用于棉织物的抗菌整理,同时进行防变色整理,并对抗菌棉织物的抗菌性能及机械性能进行测试。
本文的研究内容和结论如下:
(1)实验制备的SBA-15具有高度有序二维六方孔道结构,且孔径分布单一,较大的比表面积和较大的孔容,样品的比表面积采用BET法计算可以达到611m~2/g,孔容为0.65cm~3/g。孔道长程有序,有利于提高介孔材料药物装载的能力。
(2)采用APTES对SBA-15进行了表面改性。硅烷偶联剂通过化学键的形式嫁接到介孔材料上,维持了孔道原有的长程有序结构和良好的热稳定性。
(3)采用单因素分析,探讨了AgNO_3溶液浓度、载银时间、载银温度对SBA-15载银量的关系。
(4)优选施加固着技术,对棉织物进行抗菌和防变色整理,赋予其抗菌功能。
(5)经抗菌实验表明:棉织物经过添加量为1.00%的无机抗菌剂整理后,与大肠杆菌、金黄色葡萄球菌接触1小时,杀菌率均达到100%上。抗菌棉织物除具有良好的抗菌效果外,同时还有较好的耐水洗性,经过20次水洗后抗菌率大于95%。
Inorganic antibacterial agents with good properties of long lasting, stability, safe and broad-spectrum antibiosis, overcome the drawbacks of organic antibacterial agents, and with excellent antibacterial activity against both bacteria and funguses, having attracted many researchers’interest in the field of antimicrobials since 1980s. In all metals, silver has widely applied in many fields for its advantages in catalytic, electronic and optical, otherwise, silver is good at broad-spectrum antibiosis. The principal inorganic antibacterial agents have been originated from metal ions, it will not lead up to drug resistance.
Mesoporous silicas present high superficial areas and large uniform pores, non-toxic and biological compatibility.The property of drug loading and controlled release is much better, compared with other carriers.Their silica wall surface can be modified with organic groups to adjusted their properties and achieve specific purposes. These inherent characteristics make the adsorption performance to silver ions of mesoporous silica much better than other inorganic carrier. The structure of mesoporous material, especially for the pores, which is bigger than the bacteria, can increase the chance of contacts with antibacterial agent and bacteria, improving the antibacterial efficiency and make the silver antibacterial agent an increasingly wide utilization in all fields.
Mesoporous molecular sieves SBA-15 was synthesized by sol-gel process using tri-block copolymer P123 as a template agent and TEOS as silicon source in this paper. APTES (3-aminopropyl-triethoxysilane) was grafted on the surface of the SBA-15. Then the antibacterial agent was obtained at moderate condition. Finally, the cotton fabric was finished by the synthesized compound antibacterial agent through one time dipping. Besides,the problem of Ag type antibacterial agent tamishing has been resolved. The effect on the antibacterial property of the antibacterial fabrics was also tested.
The main conclusions are as follows:
(1) The prepared SBA-15 had the structure of two dimensional mesoporous with highly ordered hexagonal phase. The size distribution of mesoporous pore was verynarrow and uniform, the specific surface area of SBA-15 was 611m~2/g, the pore volume of mesoporous pore was 0.65cm~3/g. Highly ordered structure did benefit to the improvement of drug loading.
(2) The surface of SBA-15 was modified by APTES. The amino groups were grafted on the surface of channels, the ordered structure and thermal ability remained.
(3) The relationship between initial concentration of silver nitrate, loading time, temperature and the amount of loaded silver was studied.
(4) Optimal design on finishing was chosen to give the cotton fabric functional finish, which made the fabric antibacterial. Besides, the problem of Ag type antibacterial agent tarnishing has been resolved.
(5) The antibacterial test showed that this powder had 100% bacterial action on E.coli, S.aures and C.albicans within 1h by adding 1.00wt% antimicrobial on the fabrics. Antibacterial fabric are excellently antibiotic against the bacteria mentioned above and fairly wash fast.After washed ten times , the antibacterial rate of the antibacterial agent remained above 95%.
引文
[1]季君晖,史维明.抗菌材料[M].化学工业出版社,2003.
[2] Lee Sung Min, Lee Bum Suk, Byun Tae Gang. Preparation and antibacterial activity of silver-doped organic-inorganic hybrid coatings on glass substrates[J]. Physicochemical and Engineering Aspects, 2010, 355(1):167-171.
[3] Goy Rejane C, De Britto Douglas, Assis Odilio B G. A review of the antimicrobial activity of chitosan[J]. Polimeros, 2009, 19(3):241-247.
[4]高盛超.新型银系无机抗菌剂及抗菌胶衣树脂的制备和性能研究[D].浙江:浙江大学,2005.
[5] Li Jing, Zheng Lifang, Zhang Kaifeng Synthesis of Ag modified vanadium oxide nanotubes and their antibacterial properties[J]. Materials Research Bulletin, 2008, 43(10):2810-2817.
[6]冯乃谦,严建华.银型无机抗菌剂的发展及其应用[J].材料导报,1998,122:1-3.
[7] Tang Xiaoning, Zhang Bin, Xie Gang et al. Study on Antibacterial Mechanism of Ag-Inorganic Antibacterial Material Containing Lanthanum[J]. Advanced Materials Research, 2009, 79:1799-1802.
[8]王小健,乔学亮,陈建国等.无机抗菌剂的研究现状及发展趋势[J].陶瓷学报,2003,24(4):239.
[9]马承银,杨翠纯.新型无机抗菌材料[J].化工新型材料,19964:41-42.
[10]薛光.银的分析化学[M].科学出版社,1998.
[11]张文钲,张羽天.载银饮水杀菌技术的研究与开发[J].新型材料,2000,27(12):33-34.
[12] Yang hui, Wang ke, Ding xingeng. Study on relationship between antibacterial property and silver ions in inorganic antibacterial powders[J]. Journal of the Chinese Ceramic Society, 2002,30(5):585-588.
[13]王海兵.抗菌搪瓷的制备及性能研究[D].浙江:浙江大学,2004.
[14]仪建华,黄岳元,谢建榕等.多步沉淀法制备纳米无机复合抗菌粉体[J].西北大学学报:自然科学版,2007,37(2):235-238.
[15] Liu Hairong, Chen Qi. Effects of heat treatment on structure and properties of antibacterial porous materials of silver-carrying silica[J]. Journal of the Chinese Ceramic Society, 2005, 33(4):438-442.
[16]陆春华,倪亚茹,许仲梓,张其土.无机抗菌材料及其抗菌机理[J].南京工业大学学报,2003,251: 107-110.
[17]肖士民,李玲华,祁雁蓉等.用天然沸石离子交换制备抗菌沸石[J].华南理工大学学报,1997,25(12):12-16.
[18]何娟.载银沸石抗菌剂的研究[J].中国陶瓷工业,2002,94:15-17.
[19]内田真志.无机系抗菌剂バクテキラヘ[J].化学工业,1995,9:736.
[20]马玉龙,许梓荣.离子型无机抗菌材料研究进展[J].材料导报,2004,18(2):16-18.
[21] Oya A et al. An antimicrobial and antifungal agent derived from montmorillonite [J]. Appl.Clay Sci.1991, 16:135-142.
[22]吕国玉,李玉宝,魏杰,张利,杨爱萍,周钢.载银羟基磷灰石抗菌织物的研究[J].功能材料,2005,6(36): 888-891.
[23]冯晋阳,吴建锋,徐晓虹.羟基磷灰石抗菌剂的研究[J].硅酸盐通报,2004,23(4):6-10.
[24]富各冈敏一等.チォスルヮァメ银错ィォンな用ぃた抗菌剂の合成[J].日本化学会志,1995,10: 848-850.
[25]董兵海,李鹤鸣,吴建峰.高效硅胶抗菌防霉剂的研究[J].国外建材科技,2002,23(2):11-13.
[26]王洪水,乔学亮,王小健等.载银沸石抗菌剂的制备及其抗菌性能[J].材料科学与工程学报.2006, 24(1):40-43.
[27]秦伟庭,沈勇,张惠芳,王黎明,丁颖.改性纳米氧化物在织物抗菌整理上的应用研究[J].印染,2005,20: 4-6.
[28] Yang Huifang, Ren Shuxia, Li Zhifang. Synthesis of composite antibacterial agent by chemical method Proceedings[J]. International Conference on Information Engineering, 2010,1:89-92.
[29] Hagiwara Z, Nohara S. Particle-packed fiber article having antibacterial property[P].U.S.4525410, 1985.
[30] Kang in-sook, Yang, C.Q., Wei W.Mechanical Strength of Durable Press Finished Cotton Fabrics[J]. Textile Res.J, 1998(6):865-870.
[31] Saravanapavan P, Hench L L. Effect of composition and texture on controlled rate of release of an antibacterial agent from bioactive gel-glasses[J].Key Engineering Materials, 2003,240:233-236.
[32]郑修成,袁程远,赵文平,杨春艳,叶文豪,王向宇.介孔分子筛SBA-15的合成与表征[J].郑州大学学报. 2008, 40(1):101-106.
[33]翟庆洲,于辉,秦亮等.SBA-15分子筛的合成研究[J].硅酸盐学报,2006,34(3):385-388.
[34] Kresge C T, Leonowicz M E, Roth W J et al. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism [J]. Nature, 1992, 359 (6397): 710-712.
[35]盖利刚.介孔分子筛制备表征及应用[D].济南:山东大学,2006.
[36] Zhao D Y, Huo J L, Stucky G D et al. Triblock copolymer syntheses of mesoporous silica with periodic50 to 300 angstrom pores [J]. Science, 1998, 279 (5350):548-552.
[37]赵会玲,胡军,汪建军等.介孔材料氨基表面修饰及其对CO2的吸附性能[J].物理化学学报,2007,23 (6):801-806.
[38] Hiyoshi N, Yogo K. Adsorption of carbon dioxide on amine modified SBA-15 in the presence of water vapor[J].Chem Lett, 2004,33 (5):510-511.
[39] Zhao Huiling, Hu Jun, Wang Jianjun et al.CO2 capture by the amine-modified mesoporous materials[J]. Acta Phys Chim Sin, 2007,23(6):801-806.
[40] J S Beck, J C Vartuli, W J Roth, M E Leonowicz, C T Kresge et al. A new family of mesoporous molecular sieves prepared with liquid crystal templates [J]. Chem. Soc, 1992, 114:10834-10843.
[41] J S Lettow, Y J Han, P Schmidt-Winkel, P Yang, D Zhao, G D Stucky et al. Hexagonal to mesocellular foam phase transition in poymer-templated mesoporous silicas [J]. Langmuir, 2000, 16:8291-8295.
[42] Dongyuan Zhao, Jianglin Feng, Qisheng Huo et al. Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores[J]. Science, 1998, 279: 548-552.
[43] Hui Sun, Junxing Han, Yuqi Ding.One-pot synthesized mesoporous Ca/SBA-15 solid base for transe- sterification of sun?ower oil with methanol[J].Applied Catalysis, 2010,390:26-34.
[44] D Y Zhao, J Y Sun, Q Z Li, G D Stucky. Morphological control of highly ordered mesoporous silica SBA-15[J].Chem.Mater, 2000, 12:275-279.
[45]赵起龙,沈健,袁兴东,杨立娜.介孔分子筛SBA-15的研究进展[J].广州化工,2005,33(1):12-15.
[46] Sayari A, Hamoudi S, Periodic mesoporous silica-based organic-Inorganic nanocomposite materials [J].Chem.Mater, 2001, 13:3151-3168.
[47]朱建华,吴正颖.介孔硅分子筛原位改性功能化的研究进展[J].石油化工.2007, 36(5):425-432.
[48]李健芳,吴晓金,孟长功.介孔分子筛MCM-41的硅烷化改性及吸附性能研究[J].化学研究与应用, 2008,20(7):916-918.
[49]刘妍,侯经国,田锐等.介孔分子筛SBA-15的乙基化修饰和表征[J].化学工程师,2005,8:1-3.
[50] Smith J V, Topochemistry of zeolites and related material [J].Topology and geometry, Chem.Rev, 1988, 88:149-182.
[51] Awander R, Palm C, Stelzer J,Groeger O,Engethardt G,Silazane-silylation of silicates: towards tailor-made support materials[J]. Sci.Catal, 1998, 117:135-142.
[52] Ryoo R,Jun S. Improvement of hydrothermal stability of MCM-41 using salt effects during the crystallization process[J]. Journal of Physical Chemistry B, 1997, 101:317-320.
[53] Taguchi A, Sch F, Ordered mesoporous materials in catalysis [J]. Micropor. Mesopor.Mater, 2005,77: l-45.
[54] Moller K, Bein T. Internal modification of ordered mesoporous host [J].Stud.Surf. sci.Catal, 1998, 117:53-64.
[55] TanevP T, Pinnavaia T J. Biomimetic Templating of Porous Lamellar Silieas by Vesicular Surfactant Assemblies [J]. Science, 1996, 271:1267-1269.
[56] Lyubomira, Ivanov, Jessica, Rosenholm, Tanya, Tsoncheva etc. Iron oxide nanoparticles supported on NH2- and COOH- functionalized SBA-15[J]. Reaction kinetics and catalysis letters, 2008, 95(2): 329-336.
[57]王文生,高保娇,王梦心.纳米SiO2表面接枝改性研究[J].山西化工,2007,27(2):3-6.
[58]王美英,佘庆彦,刘国栋,瞿雄伟.硅烷偶联剂表面接枝[J].高分子材料科学与工程,2005,21(6):228-231.
[59]刘秀芹,张云艳,常勇刚,徐承天,陈邦林.介孔SiO2表面的氨基修饰及吸附性能研究[J].化学世界, 2009,2:70-73.
[60]付新,李军平,赵宁,肖福魁,魏伟,孙予罕.氨基修饰的介孔分子筛对CO2的吸附性能[J].石油化工,2008,37(10):1021-1025.
[61]王燕,高林.缓释型无机抗菌材料的研究综述[J].精细石油化工进展,2009,108:52-55.
[62] Maroneze, Luiz P, Yoshitaka. One-step preparation of silver nanoparticles confined in functionalizedfree SBA-15 channels[J].Synthetic Metals, 2010,160(19):2099-2103.
[63]张国范,陈启元,冯其明等.温度对油酸钠在一水硬铝石矿物表面吸附的影响[J].中国有色金属学报,2004,14(6):1042-1044.
[64]薛晓明,李风亭,喻本宏.功能化介孔吸附剂的制备及其对银离子吸附性能的研究[J].材料导报,2008, 22:375-378.
[65]吕艳萍,李临生.无机抗菌剂及其在纺织品上的应用[J].印染助剂,2003,6:1-4.
[66]顾志明,姬广斌,李凤生.超细无机粉体的水中分散研究综述[J].南京理工大学学报,1999,23(5): 470-473.
[67]罗永明,潘伟,陈健.分散剂对纳米碳化硅粉末在水中分散的影响[J].材料导报,2000,(3):349-359.
[68]袁文俊,周勇敏.纳米颗粒团聚的原因及解决措施[J].材料导报,2008,22:59-61.
[69]郭小龙,陈沙鸥,戚凭,潘秀红.纳米陶瓷粉末分散的微观过程和机理[J].青岛大学学报,2002,15(1): 78-88.
[70]曹雪琴,钱国坻,娄颖.Zeta电位与分散染料的分散稳定性[J].印染助剂,1998,15(6):9-13.
[71]张文钲,王广文.载银无机抗菌剂变色抑制剂研发现状[J].化工新型材料,2002,30(4):23-25.
[72] Dai JinMing, Hou WenSheng, Wei LiQiao. Study on the color change resistant property of silver and zinc-loading zeolite 4A antibacterial agent[J].Journal of Inorganic Materials,2008,23(5):1011-1015.
[73] Onda Koki, Kubokawa Hiroh, Shinozawa Takao.Color fastness and antibacterial activity of the fibers treated with culture medium of Pseudomonas Aeruginosa[J]. Sen'i Gakkaishi, 2005, 61(5):132-137.
[74]中华人民共和国纺织工业部FZ/T 01021-92,织物抗菌性能试验方法[S].
[75]中华人民共和国纺织工业部GB 8629-2001,纺织品试验时采用的家庭洗涤及干燥程序[S].
[2] Lee Sung Min, Lee Bum Suk, Byun Tae Gang. Preparation and antibacterial activity of silver-doped organic-inorganic hybrid coatings on glass substrates[J]. Physicochemical and Engineering Aspects, 2010, 355(1):167-171.
[3] Goy Rejane C, De Britto Douglas, Assis Odilio B G. A review of the antimicrobial activity of chitosan[J]. Polimeros, 2009, 19(3):241-247.
[4]高盛超.新型银系无机抗菌剂及抗菌胶衣树脂的制备和性能研究[D].浙江:浙江大学,2005.
[5] Li Jing, Zheng Lifang, Zhang Kaifeng Synthesis of Ag modified vanadium oxide nanotubes and their antibacterial properties[J]. Materials Research Bulletin, 2008, 43(10):2810-2817.
[6]冯乃谦,严建华.银型无机抗菌剂的发展及其应用[J].材料导报,1998,122:1-3.
[7] Tang Xiaoning, Zhang Bin, Xie Gang et al. Study on Antibacterial Mechanism of Ag-Inorganic Antibacterial Material Containing Lanthanum[J]. Advanced Materials Research, 2009, 79:1799-1802.
[8]王小健,乔学亮,陈建国等.无机抗菌剂的研究现状及发展趋势[J].陶瓷学报,2003,24(4):239.
[9]马承银,杨翠纯.新型无机抗菌材料[J].化工新型材料,19964:41-42.
[10]薛光.银的分析化学[M].科学出版社,1998.
[11]张文钲,张羽天.载银饮水杀菌技术的研究与开发[J].新型材料,2000,27(12):33-34.
[12] Yang hui, Wang ke, Ding xingeng. Study on relationship between antibacterial property and silver ions in inorganic antibacterial powders[J]. Journal of the Chinese Ceramic Society, 2002,30(5):585-588.
[13]王海兵.抗菌搪瓷的制备及性能研究[D].浙江:浙江大学,2004.
[14]仪建华,黄岳元,谢建榕等.多步沉淀法制备纳米无机复合抗菌粉体[J].西北大学学报:自然科学版,2007,37(2):235-238.
[15] Liu Hairong, Chen Qi. Effects of heat treatment on structure and properties of antibacterial porous materials of silver-carrying silica[J]. Journal of the Chinese Ceramic Society, 2005, 33(4):438-442.
[16]陆春华,倪亚茹,许仲梓,张其土.无机抗菌材料及其抗菌机理[J].南京工业大学学报,2003,251: 107-110.
[17]肖士民,李玲华,祁雁蓉等.用天然沸石离子交换制备抗菌沸石[J].华南理工大学学报,1997,25(12):12-16.
[18]何娟.载银沸石抗菌剂的研究[J].中国陶瓷工业,2002,94:15-17.
[19]内田真志.无机系抗菌剂バクテキラヘ[J].化学工业,1995,9:736.
[20]马玉龙,许梓荣.离子型无机抗菌材料研究进展[J].材料导报,2004,18(2):16-18.
[21] Oya A et al. An antimicrobial and antifungal agent derived from montmorillonite [J]. Appl.Clay Sci.1991, 16:135-142.
[22]吕国玉,李玉宝,魏杰,张利,杨爱萍,周钢.载银羟基磷灰石抗菌织物的研究[J].功能材料,2005,6(36): 888-891.
[23]冯晋阳,吴建锋,徐晓虹.羟基磷灰石抗菌剂的研究[J].硅酸盐通报,2004,23(4):6-10.
[24]富各冈敏一等.チォスルヮァメ银错ィォンな用ぃた抗菌剂の合成[J].日本化学会志,1995,10: 848-850.
[25]董兵海,李鹤鸣,吴建峰.高效硅胶抗菌防霉剂的研究[J].国外建材科技,2002,23(2):11-13.
[26]王洪水,乔学亮,王小健等.载银沸石抗菌剂的制备及其抗菌性能[J].材料科学与工程学报.2006, 24(1):40-43.
[27]秦伟庭,沈勇,张惠芳,王黎明,丁颖.改性纳米氧化物在织物抗菌整理上的应用研究[J].印染,2005,20: 4-6.
[28] Yang Huifang, Ren Shuxia, Li Zhifang. Synthesis of composite antibacterial agent by chemical method Proceedings[J]. International Conference on Information Engineering, 2010,1:89-92.
[29] Hagiwara Z, Nohara S. Particle-packed fiber article having antibacterial property[P].U.S.4525410, 1985.
[30] Kang in-sook, Yang, C.Q., Wei W.Mechanical Strength of Durable Press Finished Cotton Fabrics[J]. Textile Res.J, 1998(6):865-870.
[31] Saravanapavan P, Hench L L. Effect of composition and texture on controlled rate of release of an antibacterial agent from bioactive gel-glasses[J].Key Engineering Materials, 2003,240:233-236.
[32]郑修成,袁程远,赵文平,杨春艳,叶文豪,王向宇.介孔分子筛SBA-15的合成与表征[J].郑州大学学报. 2008, 40(1):101-106.
[33]翟庆洲,于辉,秦亮等.SBA-15分子筛的合成研究[J].硅酸盐学报,2006,34(3):385-388.
[34] Kresge C T, Leonowicz M E, Roth W J et al. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism [J]. Nature, 1992, 359 (6397): 710-712.
[35]盖利刚.介孔分子筛制备表征及应用[D].济南:山东大学,2006.
[36] Zhao D Y, Huo J L, Stucky G D et al. Triblock copolymer syntheses of mesoporous silica with periodic50 to 300 angstrom pores [J]. Science, 1998, 279 (5350):548-552.
[37]赵会玲,胡军,汪建军等.介孔材料氨基表面修饰及其对CO2的吸附性能[J].物理化学学报,2007,23 (6):801-806.
[38] Hiyoshi N, Yogo K. Adsorption of carbon dioxide on amine modified SBA-15 in the presence of water vapor[J].Chem Lett, 2004,33 (5):510-511.
[39] Zhao Huiling, Hu Jun, Wang Jianjun et al.CO2 capture by the amine-modified mesoporous materials[J]. Acta Phys Chim Sin, 2007,23(6):801-806.
[40] J S Beck, J C Vartuli, W J Roth, M E Leonowicz, C T Kresge et al. A new family of mesoporous molecular sieves prepared with liquid crystal templates [J]. Chem. Soc, 1992, 114:10834-10843.
[41] J S Lettow, Y J Han, P Schmidt-Winkel, P Yang, D Zhao, G D Stucky et al. Hexagonal to mesocellular foam phase transition in poymer-templated mesoporous silicas [J]. Langmuir, 2000, 16:8291-8295.
[42] Dongyuan Zhao, Jianglin Feng, Qisheng Huo et al. Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores[J]. Science, 1998, 279: 548-552.
[43] Hui Sun, Junxing Han, Yuqi Ding.One-pot synthesized mesoporous Ca/SBA-15 solid base for transe- sterification of sun?ower oil with methanol[J].Applied Catalysis, 2010,390:26-34.
[44] D Y Zhao, J Y Sun, Q Z Li, G D Stucky. Morphological control of highly ordered mesoporous silica SBA-15[J].Chem.Mater, 2000, 12:275-279.
[45]赵起龙,沈健,袁兴东,杨立娜.介孔分子筛SBA-15的研究进展[J].广州化工,2005,33(1):12-15.
[46] Sayari A, Hamoudi S, Periodic mesoporous silica-based organic-Inorganic nanocomposite materials [J].Chem.Mater, 2001, 13:3151-3168.
[47]朱建华,吴正颖.介孔硅分子筛原位改性功能化的研究进展[J].石油化工.2007, 36(5):425-432.
[48]李健芳,吴晓金,孟长功.介孔分子筛MCM-41的硅烷化改性及吸附性能研究[J].化学研究与应用, 2008,20(7):916-918.
[49]刘妍,侯经国,田锐等.介孔分子筛SBA-15的乙基化修饰和表征[J].化学工程师,2005,8:1-3.
[50] Smith J V, Topochemistry of zeolites and related material [J].Topology and geometry, Chem.Rev, 1988, 88:149-182.
[51] Awander R, Palm C, Stelzer J,Groeger O,Engethardt G,Silazane-silylation of silicates: towards tailor-made support materials[J]. Sci.Catal, 1998, 117:135-142.
[52] Ryoo R,Jun S. Improvement of hydrothermal stability of MCM-41 using salt effects during the crystallization process[J]. Journal of Physical Chemistry B, 1997, 101:317-320.
[53] Taguchi A, Sch F, Ordered mesoporous materials in catalysis [J]. Micropor. Mesopor.Mater, 2005,77: l-45.
[54] Moller K, Bein T. Internal modification of ordered mesoporous host [J].Stud.Surf. sci.Catal, 1998, 117:53-64.
[55] TanevP T, Pinnavaia T J. Biomimetic Templating of Porous Lamellar Silieas by Vesicular Surfactant Assemblies [J]. Science, 1996, 271:1267-1269.
[56] Lyubomira, Ivanov, Jessica, Rosenholm, Tanya, Tsoncheva etc. Iron oxide nanoparticles supported on NH2- and COOH- functionalized SBA-15[J]. Reaction kinetics and catalysis letters, 2008, 95(2): 329-336.
[57]王文生,高保娇,王梦心.纳米SiO2表面接枝改性研究[J].山西化工,2007,27(2):3-6.
[58]王美英,佘庆彦,刘国栋,瞿雄伟.硅烷偶联剂表面接枝[J].高分子材料科学与工程,2005,21(6):228-231.
[59]刘秀芹,张云艳,常勇刚,徐承天,陈邦林.介孔SiO2表面的氨基修饰及吸附性能研究[J].化学世界, 2009,2:70-73.
[60]付新,李军平,赵宁,肖福魁,魏伟,孙予罕.氨基修饰的介孔分子筛对CO2的吸附性能[J].石油化工,2008,37(10):1021-1025.
[61]王燕,高林.缓释型无机抗菌材料的研究综述[J].精细石油化工进展,2009,108:52-55.
[62] Maroneze, Luiz P, Yoshitaka. One-step preparation of silver nanoparticles confined in functionalizedfree SBA-15 channels[J].Synthetic Metals, 2010,160(19):2099-2103.
[63]张国范,陈启元,冯其明等.温度对油酸钠在一水硬铝石矿物表面吸附的影响[J].中国有色金属学报,2004,14(6):1042-1044.
[64]薛晓明,李风亭,喻本宏.功能化介孔吸附剂的制备及其对银离子吸附性能的研究[J].材料导报,2008, 22:375-378.
[65]吕艳萍,李临生.无机抗菌剂及其在纺织品上的应用[J].印染助剂,2003,6:1-4.
[66]顾志明,姬广斌,李凤生.超细无机粉体的水中分散研究综述[J].南京理工大学学报,1999,23(5): 470-473.
[67]罗永明,潘伟,陈健.分散剂对纳米碳化硅粉末在水中分散的影响[J].材料导报,2000,(3):349-359.
[68]袁文俊,周勇敏.纳米颗粒团聚的原因及解决措施[J].材料导报,2008,22:59-61.
[69]郭小龙,陈沙鸥,戚凭,潘秀红.纳米陶瓷粉末分散的微观过程和机理[J].青岛大学学报,2002,15(1): 78-88.
[70]曹雪琴,钱国坻,娄颖.Zeta电位与分散染料的分散稳定性[J].印染助剂,1998,15(6):9-13.
[71]张文钲,王广文.载银无机抗菌剂变色抑制剂研发现状[J].化工新型材料,2002,30(4):23-25.
[72] Dai JinMing, Hou WenSheng, Wei LiQiao. Study on the color change resistant property of silver and zinc-loading zeolite 4A antibacterial agent[J].Journal of Inorganic Materials,2008,23(5):1011-1015.
[73] Onda Koki, Kubokawa Hiroh, Shinozawa Takao.Color fastness and antibacterial activity of the fibers treated with culture medium of Pseudomonas Aeruginosa[J]. Sen'i Gakkaishi, 2005, 61(5):132-137.
[74]中华人民共和国纺织工业部FZ/T 01021-92,织物抗菌性能试验方法[S].
[75]中华人民共和国纺织工业部GB 8629-2001,纺织品试验时采用的家庭洗涤及干燥程序[S].