纳米银粉的制备工艺及抗菌应用研究
|
摘要
银是一种重要的贵金属,银被广泛应用于抗菌材料、医药材料、装饰材料、电子浆料、催化剂等领域。近年来,随着高新技术的发展,纳米银粉材料获得迅速发展。由于纳米银粉具有纳米材料所特有的体积效应、表面效应、量子尺寸效应等,在抗菌、医药、超导及光学等方面显示出普通银粉所不及的特殊功效,是一种应用前景广阔的新型材料。
本研究采用液相化学还原法制备纳米银粉。该法工艺条件易控制,设备要求相对不高,可获得粒度分布较窄的纳米银粉,且产率高,既便于实验室研究,也便于工业化大规模生产。实验中选用硝酸银为原料,次磷酸钠为还原剂,PVP为高分子保护剂,六偏磷酸钠为分散剂,制备了类球状、分散性良好的纳米银粉。实验研究发现,较佳反应温度是40 ~ 50℃,反应剂用量的较佳比例是次磷酸钠的用量为理论用量的2 ~ 3倍,PVP的用量为硝酸银质量的1.0 ~ 1.2倍,六偏磷酸钠的质量为硝酸银质量的0.1 ~ 0.2倍。对自然干燥、真空干燥及冷冻干燥三种干燥方式进行对比发现,用任一干燥方法,所得的纳米银粉经XRD检测均为纯金属银,自然干燥时间长,真空干燥所得银粉的纯度较高,冷冻干燥所得的银粉不结块、粉末细。水浴温度50℃,硝酸银3.40g加入20ml去离子水中配制硝酸银溶液,次磷酸钠1.325 g、PVP 3.80 g、六偏磷酸钠0.43 g、水125 ml配制还原液,所制得的纳米银溶胶,由有机碱性混合试剂调节pH,再使用快T溶液分散。经TEM、XRD、纳米激光粒度分析仪等检测,通过该较佳工艺条件制得的纳米银粒子纯度高,平均粒径小,粒径分布窄;粒子类球状,并且分布均匀。
分别采用定性和定量两种实验方式,研究了本实验制备的纳米银粉的抗菌
Silver is one of the important precious metals. It has been widely used as antibacterial material, medical material, optical material, ornamental material, catalytic material, electrical and electronical materials, etc. Due to their peculiar properties caused from the volume effect, the surface effect, the quantum dimension effect, and the macro-quantum tunnel effect, the silver nanoparticles might become to the prospective important materials applied potentially in many field.
There are many methods to prepare silver nanoparticles, in which the liquid-phase chemical reduction process is more controllable and easier in large-scale production. In this study, the silver colloids were prepared by the chemical reduction in liquid phase with silver nitrate, sodium hypophosphite (as reducer), sodium hexametaphosphate (as disperser), and polyvinylpyrrolidone (as protective agent). Through controlling reaction condition, the spheroid, dispersible and the stable silver colloids were prepared, and the optimum technologic has been summarized. The dispersible and stable silver colloid was synthesized at 50℃and reaction for 1 hour in the system of C(AgNO3)=1.0 mol/L, C(NaH2PO2·H2O)=0.1 mol/L, 2~3 times theoretical dosage of Na2PO4, m(PVP)/m(AgNO3) = 1.0~1.2, m([NaPO3]6)/ m(AgNO3)= 0.1~0.2, pH=1~2. The silver nanoparticles were obtained through desiccation of the colloid, and were characterized by XRD and TEM. The results showed that the product was the spherical silver particles with the mean size about 7~10 nm and without impurity almost.
The antibacterial and bacteriostatic effects of silver nanoparticles to two index-bacteria (Escherichia coli, Bacillus subtilis) have been studied qualitatively and quantitatively. The antibacterial experimental results showed that the silver nanoparticles could effectively kill and
本研究采用液相化学还原法制备纳米银粉。该法工艺条件易控制,设备要求相对不高,可获得粒度分布较窄的纳米银粉,且产率高,既便于实验室研究,也便于工业化大规模生产。实验中选用硝酸银为原料,次磷酸钠为还原剂,PVP为高分子保护剂,六偏磷酸钠为分散剂,制备了类球状、分散性良好的纳米银粉。实验研究发现,较佳反应温度是40 ~ 50℃,反应剂用量的较佳比例是次磷酸钠的用量为理论用量的2 ~ 3倍,PVP的用量为硝酸银质量的1.0 ~ 1.2倍,六偏磷酸钠的质量为硝酸银质量的0.1 ~ 0.2倍。对自然干燥、真空干燥及冷冻干燥三种干燥方式进行对比发现,用任一干燥方法,所得的纳米银粉经XRD检测均为纯金属银,自然干燥时间长,真空干燥所得银粉的纯度较高,冷冻干燥所得的银粉不结块、粉末细。水浴温度50℃,硝酸银3.40g加入20ml去离子水中配制硝酸银溶液,次磷酸钠1.325 g、PVP 3.80 g、六偏磷酸钠0.43 g、水125 ml配制还原液,所制得的纳米银溶胶,由有机碱性混合试剂调节pH,再使用快T溶液分散。经TEM、XRD、纳米激光粒度分析仪等检测,通过该较佳工艺条件制得的纳米银粒子纯度高,平均粒径小,粒径分布窄;粒子类球状,并且分布均匀。
分别采用定性和定量两种实验方式,研究了本实验制备的纳米银粉的抗菌
Silver is one of the important precious metals. It has been widely used as antibacterial material, medical material, optical material, ornamental material, catalytic material, electrical and electronical materials, etc. Due to their peculiar properties caused from the volume effect, the surface effect, the quantum dimension effect, and the macro-quantum tunnel effect, the silver nanoparticles might become to the prospective important materials applied potentially in many field.
There are many methods to prepare silver nanoparticles, in which the liquid-phase chemical reduction process is more controllable and easier in large-scale production. In this study, the silver colloids were prepared by the chemical reduction in liquid phase with silver nitrate, sodium hypophosphite (as reducer), sodium hexametaphosphate (as disperser), and polyvinylpyrrolidone (as protective agent). Through controlling reaction condition, the spheroid, dispersible and the stable silver colloids were prepared, and the optimum technologic has been summarized. The dispersible and stable silver colloid was synthesized at 50℃and reaction for 1 hour in the system of C(AgNO3)=1.0 mol/L, C(NaH2PO2·H2O)=0.1 mol/L, 2~3 times theoretical dosage of Na2PO4, m(PVP)/m(AgNO3) = 1.0~1.2, m([NaPO3]6)/ m(AgNO3)= 0.1~0.2, pH=1~2. The silver nanoparticles were obtained through desiccation of the colloid, and were characterized by XRD and TEM. The results showed that the product was the spherical silver particles with the mean size about 7~10 nm and without impurity almost.
The antibacterial and bacteriostatic effects of silver nanoparticles to two index-bacteria (Escherichia coli, Bacillus subtilis) have been studied qualitatively and quantitatively. The antibacterial experimental results showed that the silver nanoparticles could effectively kill and
引文
[1] 孙戬.金银冶金[M].北京:冶金工业出版社,1998,23-26.
[2] 黄礼煌.金银提取技术[M].北京:冶金工业出版社,2001,7-12.
[3] 薛光.银的分析化学[M],北京:科学出版社,1998,23-25.
[4] 赵怀志.银的主要应用领域和发展现状[J].云南冶金,2001,31(3):118 – 127.
[5] 杨遇春.银在高新技术中的若干应用[J].稀有金属,1996,20(6):451-454,458.
[6] 刘世友.银的生产、应用和发展[J].上海有色金属,1996,17(2):86-90.
[7] 唐武军,石和清.中国白银生产、流通消费现状及发展前景[J].有色金属再生与利用,2004,(11):17-19.
[8] A Kail,WA Merl,E Vinaricky.电接触和电接触材料[M].北京:机械工业出版社, 1993.
[9] 白祖海,周方钦,周含英,等.银(I)催化抗坏血酸还原偶氮胂Ⅲ反应的研究及痕量银的测定[J].分析实验室,2004,23(11):56-58.
[10] 张文钲.银的杀菌功能[J].金属世界,2002,3:20-21.
[11] 朱荫莲,张翠媚.宫颈糜烂微波治疗后应用纳米银促进创面愈合[J].中国基层医药,2004,11(3):318-319
[12] 胡骁骅,张普柱,孙永华,等.纳米银抗菌医用敷料银离子吸收和临床应用[J].中华医学杂志,2003,83(24):2178-2179
[13] 许霞.纳米组装无机抗菌剂的制备及其抗菌效果研究[J].中国非金属矿工业导刊,2004,42:19-20
[14] 徐国财,张立德.纳米复合材料[M].北京:化学工业出版社,2002,31-32.
[15] 郦希.超细银粉的制备及应用[J].湖南化工,1994,24(4):24-26.
[16] 胡建强,吴继红,任斌等.纯化学还原方法制备纳米棒及其SERS活性[J].光散射学报,2002,13(4):226-229.
[17] 宁远涛,赵怀志.银纳米材料[J].贵金属,2003,24(3):54-60.
[18] Bennner L S,Suzuki T,Meguro K,et al.Precious Metals Science and Technology [M].IPMI,1991.
[19] 秦晓英.纳米固体银在高温下的热膨胀行为[J].物理学报,1995,44 (2):244.
[20] 刘绍璞,陈飒.银原子团簇的共振散射光谱研究[J].贵金属,2001,22 (3) :8-13.
[21] 蔡伟平,张立德.纳米银P介孔二氧化硅复合体的光学特性[A].中国材料研究学会 96’中国材料研讨会论文集:功能材料I-2[C].北京:化学工业出版社,1997.
[22] 吴锦雷,吴全德.几种新型薄膜材料[M].北京:北京大学出版社,1999.
[23] Lee Myung-Han,Oh Seong-Geun,Suh Kyung-Do,et.al..Preparation of silver nanoparticles in hexagonal phase formed by nonionic Triton X-100 surfactant[J].Colloids and Surfaces,2002,210:49-60.
[24] Vorobyova S.A,Lennikvich A.I,Sobal N.S..Preparation of silver nanoparticles by interphase reduction[J].Colloids and Surfaces,1999,152:375-379.
[25] 顾大明, 高农, 程谨宁.次磷酸盐液相还原法快速制备纳米银粉[J].精细化工,2002,19(11):634-635.
[26] Nersisyan H.H.,Lee J.H.,Son H.T.,et al.A new and effective chemical reduction method for preparation of nanosized silver powder and colloid dispersion[J].Materials Research Bulletin,2003,(38):949-956.
[27] Sondi Ivan,Goia Dan V.,Matijevic.Preparation of highly concentrated stable dispersions of uniform silver nanoparticles[J].Journal of Colloid and Interface Science,2003,260:75-81.
[28] 杨玉旺,刘敬利.纳米银研究和应用新进展[J].工业催化,2003,11(12):7-12.
[29] 廖立,熊继,谢克难.液相还原法制备纳米银粉的研究[J].稀有金属材料与工程, 2004,33(5):558-560.
[30] 司民真,武荣国,等.负电性纳米银的制备及性质研究[J].化学物理学报,2001,14 (4):465-468.
[31] 张庆敏,李彦,等.聚氧乙烯类表面活性剂体系中银纳米颗粒的合成[J].物理化学学报,2001,17 (6):537-541.
[32] 廖学红,朱俊杰,赵小宁,等.纳米银的电化学合成[J].高等学校化学学报,2000,[12]:1837-1839.
[33] 郑丰,梁勇,李家麟,等.激光气相制备纳米银粒子方法和装置[P].中国专利:CN 1359775A.
[34] 杜勇,杨小成,方炎.激光烧蚀法制备纳米银胶体及其特征研究[J].光电子·激光, 2003,14(4):383-386.
[35] 杨玉旺,刘敬利.纳米银研究和应用新进展[J].工业催化,2003,11(12):7-12.
[36] 中建.俄罗斯研制出纳米银杀菌涂料[J].建材工业信息,2003, 2:49.
[37] 何坤荣.金/ 银纳米粉涂料上市[J].精细与专用化学品,2003,17:25
[38] 刘维良,陈汴琨.纳米抗菌粉体材料的制备与应用研究[J].江苏陶瓷.2002,35(1):9-12.
[39] 李喜宏,成国祥.PE/ 纳米银防霉保鲜膜研制[J].食品科学,2002,23(2):129-132.
[40] 黄玉玲.一种塑胶抗菌添加剂的制造方法[P].中国专利:CN1084530A.
[41] 张堂德,詹清松,邱贤文等.纳米银祛痘凝胶治疗寻常痤疮的疗效观察.临床皮肤科杂志[J] .2004,33(4):53
[42] 石川,程谟杰,等.纳米银催化的甲烷选择还原NO反应研究[J].复旦学报(自然科学版),2002,41(3):269-273,279.
[43] 曾戎,石智敏.纳米银粒子/有机溶剂的界面作用:分散性及光学性能[J].材料研究学报,2001,15(6):654-658.
[44] Han Minghan,Lin Hongfei,Yuan Yanhui,et al.Pressure drop for two phase counter current flow in a packed column with a novel internal[J].Chemical Engineering Journal,2003,94(3):171-260.
[45] Egorova E.M.,Revina A.A..Synthesis of metallic nanoparticles in reverse micelles in the presence of quercetin[J].Colloids and Surfaces,2000,(168):87-96.
[46] 熊金钰,徐国财.纳米银粉的制备及表征[J].金属功能材料,2004,11(2):38-42.
[47] 宋文海,姜柳笛,赵兵.纳米银掺杂对Bi(2223)导体的影响[J].温物理学报,1999,21(6):456-459.
[48] Kruszewsk S.Vaccum,1997,48(3):363-364.
[49] Carotenuto G.The European Physics Journal B Condensed Matter,2000,16(1):11-17.
[50] 高倩,王兆利,等.绿色内墙涂料[J].四川建材,2002,2:21-22.
[51] Strametz, Helmut. Non-polluting industrial coating technologies - a challenge to engineers or resin chemists [J]. Progress in Organic Coatings,1992,20(3-4): 447-457。
[52] 张超灿,何东铭,巫辉,等.21世纪高性能外墙涂料的发展趋势[J] .国外建筑科技,2000,21(4): 1-3.
[53] 明伟华,府寿宽.对应于绿色环境保护的涂料发展动向[J] .化学进展,1998, 2:26.
[54] 陈钟岱.我国建筑涂料的发展[J] .涂料工业,1999,增刊:4-7.
[55] 张保利.建筑涂料的技术发展及趋势[J] .中国涂料,1999,6:7-9.
[56] 刘平德,牛亚斌,张 梅.疏水缔合耐温抗盐絮凝剂共聚物的研究现状[P].钻井液与完井液,2002,19(3):41-43.
[57] 刘秀晨,安成强.金属腐蚀学[M].北京:国防工业出版社,2002.
[58] 孙磊.张治军.党鸿辛.油溶性Ag纳米微粒的制备及表征[J].化学物理学报2004,17(5):618-622.
[59] 王志德,王 福.现代物理测试技术[M].北京:冶金工业出版社,2003.
[60] 杨玉颖,谢庆红,赵 红,等.LS230 激光粒度仪及其应用[J].现代科学仪器,2002,(3):41-43.
[61] 王英华.X光衍射技术基础[M].北京:原子能出版社,1993:264.
[62] 董亦斌, 束嘉秀, 王素萍. 化动力学——火焰原子吸收原理及应用[J]. 云南冶金. 2005, 34(2): 69-71.
[63] 高濂,孙静,刘阳桥.纳米粉体的分散及表面改性[M].北京:化学工业出版社,2003.
[64] 沈萍,范秀容,李广武.微生物实验[M].北京:高等教育出版社,1999:52-53.
[65] 张卓然.医学微生物实验学[M].北京:科学出版社,1998:4-5.
[66] 唐珊熙,刘锡光.微生物学及微生物检验[M].北京:人民卫生出版社,1998.
[67] 冯树异,程松高,于修平.医学微生物学[M].北京:北京医科大学出版社,1998.
[68] 贾文祥.医学微生物学[M].北京:人民卫生出版社,2001.
[69] 代群威,董发勤,李国武,等.铜型有源抗菌剂的扩大试验及其抗菌效果的应用研究[J].材料科学与工程学报,2004,22(5):738-741
[70] 张文钲,王广文.纳米银抗菌材料研发现状[J].化工新型材料,2003,31(2):42-44.
[71] 许霞.纳米组装无机抗菌剂的制备及其抗菌效果研究[J].中国非金属矿工业导刊,2004,4:19-20.
[72] 杨荣兴,王刚,李论哲,等.抗菌陶瓷的制备工艺及抗菌性能[J].桂林工学院学报,2000,20(2):199-202.
[2] 黄礼煌.金银提取技术[M].北京:冶金工业出版社,2001,7-12.
[3] 薛光.银的分析化学[M],北京:科学出版社,1998,23-25.
[4] 赵怀志.银的主要应用领域和发展现状[J].云南冶金,2001,31(3):118 – 127.
[5] 杨遇春.银在高新技术中的若干应用[J].稀有金属,1996,20(6):451-454,458.
[6] 刘世友.银的生产、应用和发展[J].上海有色金属,1996,17(2):86-90.
[7] 唐武军,石和清.中国白银生产、流通消费现状及发展前景[J].有色金属再生与利用,2004,(11):17-19.
[8] A Kail,WA Merl,E Vinaricky.电接触和电接触材料[M].北京:机械工业出版社, 1993.
[9] 白祖海,周方钦,周含英,等.银(I)催化抗坏血酸还原偶氮胂Ⅲ反应的研究及痕量银的测定[J].分析实验室,2004,23(11):56-58.
[10] 张文钲.银的杀菌功能[J].金属世界,2002,3:20-21.
[11] 朱荫莲,张翠媚.宫颈糜烂微波治疗后应用纳米银促进创面愈合[J].中国基层医药,2004,11(3):318-319
[12] 胡骁骅,张普柱,孙永华,等.纳米银抗菌医用敷料银离子吸收和临床应用[J].中华医学杂志,2003,83(24):2178-2179
[13] 许霞.纳米组装无机抗菌剂的制备及其抗菌效果研究[J].中国非金属矿工业导刊,2004,42:19-20
[14] 徐国财,张立德.纳米复合材料[M].北京:化学工业出版社,2002,31-32.
[15] 郦希.超细银粉的制备及应用[J].湖南化工,1994,24(4):24-26.
[16] 胡建强,吴继红,任斌等.纯化学还原方法制备纳米棒及其SERS活性[J].光散射学报,2002,13(4):226-229.
[17] 宁远涛,赵怀志.银纳米材料[J].贵金属,2003,24(3):54-60.
[18] Bennner L S,Suzuki T,Meguro K,et al.Precious Metals Science and Technology [M].IPMI,1991.
[19] 秦晓英.纳米固体银在高温下的热膨胀行为[J].物理学报,1995,44 (2):244.
[20] 刘绍璞,陈飒.银原子团簇的共振散射光谱研究[J].贵金属,2001,22 (3) :8-13.
[21] 蔡伟平,张立德.纳米银P介孔二氧化硅复合体的光学特性[A].中国材料研究学会 96’中国材料研讨会论文集:功能材料I-2[C].北京:化学工业出版社,1997.
[22] 吴锦雷,吴全德.几种新型薄膜材料[M].北京:北京大学出版社,1999.
[23] Lee Myung-Han,Oh Seong-Geun,Suh Kyung-Do,et.al..Preparation of silver nanoparticles in hexagonal phase formed by nonionic Triton X-100 surfactant[J].Colloids and Surfaces,2002,210:49-60.
[24] Vorobyova S.A,Lennikvich A.I,Sobal N.S..Preparation of silver nanoparticles by interphase reduction[J].Colloids and Surfaces,1999,152:375-379.
[25] 顾大明, 高农, 程谨宁.次磷酸盐液相还原法快速制备纳米银粉[J].精细化工,2002,19(11):634-635.
[26] Nersisyan H.H.,Lee J.H.,Son H.T.,et al.A new and effective chemical reduction method for preparation of nanosized silver powder and colloid dispersion[J].Materials Research Bulletin,2003,(38):949-956.
[27] Sondi Ivan,Goia Dan V.,Matijevic.Preparation of highly concentrated stable dispersions of uniform silver nanoparticles[J].Journal of Colloid and Interface Science,2003,260:75-81.
[28] 杨玉旺,刘敬利.纳米银研究和应用新进展[J].工业催化,2003,11(12):7-12.
[29] 廖立,熊继,谢克难.液相还原法制备纳米银粉的研究[J].稀有金属材料与工程, 2004,33(5):558-560.
[30] 司民真,武荣国,等.负电性纳米银的制备及性质研究[J].化学物理学报,2001,14 (4):465-468.
[31] 张庆敏,李彦,等.聚氧乙烯类表面活性剂体系中银纳米颗粒的合成[J].物理化学学报,2001,17 (6):537-541.
[32] 廖学红,朱俊杰,赵小宁,等.纳米银的电化学合成[J].高等学校化学学报,2000,[12]:1837-1839.
[33] 郑丰,梁勇,李家麟,等.激光气相制备纳米银粒子方法和装置[P].中国专利:CN 1359775A.
[34] 杜勇,杨小成,方炎.激光烧蚀法制备纳米银胶体及其特征研究[J].光电子·激光, 2003,14(4):383-386.
[35] 杨玉旺,刘敬利.纳米银研究和应用新进展[J].工业催化,2003,11(12):7-12.
[36] 中建.俄罗斯研制出纳米银杀菌涂料[J].建材工业信息,2003, 2:49.
[37] 何坤荣.金/ 银纳米粉涂料上市[J].精细与专用化学品,2003,17:25
[38] 刘维良,陈汴琨.纳米抗菌粉体材料的制备与应用研究[J].江苏陶瓷.2002,35(1):9-12.
[39] 李喜宏,成国祥.PE/ 纳米银防霉保鲜膜研制[J].食品科学,2002,23(2):129-132.
[40] 黄玉玲.一种塑胶抗菌添加剂的制造方法[P].中国专利:CN1084530A.
[41] 张堂德,詹清松,邱贤文等.纳米银祛痘凝胶治疗寻常痤疮的疗效观察.临床皮肤科杂志[J] .2004,33(4):53
[42] 石川,程谟杰,等.纳米银催化的甲烷选择还原NO反应研究[J].复旦学报(自然科学版),2002,41(3):269-273,279.
[43] 曾戎,石智敏.纳米银粒子/有机溶剂的界面作用:分散性及光学性能[J].材料研究学报,2001,15(6):654-658.
[44] Han Minghan,Lin Hongfei,Yuan Yanhui,et al.Pressure drop for two phase counter current flow in a packed column with a novel internal[J].Chemical Engineering Journal,2003,94(3):171-260.
[45] Egorova E.M.,Revina A.A..Synthesis of metallic nanoparticles in reverse micelles in the presence of quercetin[J].Colloids and Surfaces,2000,(168):87-96.
[46] 熊金钰,徐国财.纳米银粉的制备及表征[J].金属功能材料,2004,11(2):38-42.
[47] 宋文海,姜柳笛,赵兵.纳米银掺杂对Bi(2223)导体的影响[J].温物理学报,1999,21(6):456-459.
[48] Kruszewsk S.Vaccum,1997,48(3):363-364.
[49] Carotenuto G.The European Physics Journal B Condensed Matter,2000,16(1):11-17.
[50] 高倩,王兆利,等.绿色内墙涂料[J].四川建材,2002,2:21-22.
[51] Strametz, Helmut. Non-polluting industrial coating technologies - a challenge to engineers or resin chemists [J]. Progress in Organic Coatings,1992,20(3-4): 447-457。
[52] 张超灿,何东铭,巫辉,等.21世纪高性能外墙涂料的发展趋势[J] .国外建筑科技,2000,21(4): 1-3.
[53] 明伟华,府寿宽.对应于绿色环境保护的涂料发展动向[J] .化学进展,1998, 2:26.
[54] 陈钟岱.我国建筑涂料的发展[J] .涂料工业,1999,增刊:4-7.
[55] 张保利.建筑涂料的技术发展及趋势[J] .中国涂料,1999,6:7-9.
[56] 刘平德,牛亚斌,张 梅.疏水缔合耐温抗盐絮凝剂共聚物的研究现状[P].钻井液与完井液,2002,19(3):41-43.
[57] 刘秀晨,安成强.金属腐蚀学[M].北京:国防工业出版社,2002.
[58] 孙磊.张治军.党鸿辛.油溶性Ag纳米微粒的制备及表征[J].化学物理学报2004,17(5):618-622.
[59] 王志德,王 福.现代物理测试技术[M].北京:冶金工业出版社,2003.
[60] 杨玉颖,谢庆红,赵 红,等.LS230 激光粒度仪及其应用[J].现代科学仪器,2002,(3):41-43.
[61] 王英华.X光衍射技术基础[M].北京:原子能出版社,1993:264.
[62] 董亦斌, 束嘉秀, 王素萍. 化动力学——火焰原子吸收原理及应用[J]. 云南冶金. 2005, 34(2): 69-71.
[63] 高濂,孙静,刘阳桥.纳米粉体的分散及表面改性[M].北京:化学工业出版社,2003.
[64] 沈萍,范秀容,李广武.微生物实验[M].北京:高等教育出版社,1999:52-53.
[65] 张卓然.医学微生物实验学[M].北京:科学出版社,1998:4-5.
[66] 唐珊熙,刘锡光.微生物学及微生物检验[M].北京:人民卫生出版社,1998.
[67] 冯树异,程松高,于修平.医学微生物学[M].北京:北京医科大学出版社,1998.
[68] 贾文祥.医学微生物学[M].北京:人民卫生出版社,2001.
[69] 代群威,董发勤,李国武,等.铜型有源抗菌剂的扩大试验及其抗菌效果的应用研究[J].材料科学与工程学报,2004,22(5):738-741
[70] 张文钲,王广文.纳米银抗菌材料研发现状[J].化工新型材料,2003,31(2):42-44.
[71] 许霞.纳米组装无机抗菌剂的制备及其抗菌效果研究[J].中国非金属矿工业导刊,2004,4:19-20.
[72] 杨荣兴,王刚,李论哲,等.抗菌陶瓷的制备工艺及抗菌性能[J].桂林工学院学报,2000,20(2):199-202.