用于饮用水体系载银抑菌球的制备与性能表征
摘要
饮用水的卫生安全是保障居民健康的基本要求。饮用水一旦发生安全问题便会导致严重的后果。目前我国城市饮用水在运输和储存过程中,很容易发生二次污染。本论文旨在研制一种成本低廉、使用方便、抑菌效果好的新型表面载纳米银抑菌球,并将其应用于居民住宅的储水箱中,达到改善饮用水水质的目的。
本研究在制备出CTS-SiO2共混膜、CTS-SiO2-Ag+共混膜以及CTS-SiO2-Ag共混膜的基础上,又使用硅胶球作为载体,制备出机械性能优良、抑菌性能优异且持续抑菌性能稳定的表面包覆CTS-SiO2-Ag功能层的抑菌球。实验过程中研究了反应温度、反应时间、Ag+加入量、热处理条件等因素对共混膜和抑菌球性能的影响,确定了最佳制备方法。同时利用傅里叶红外光谱仪IR、电子扫描电镜SEM等对共混膜进行了表征分析。
研究结果表明,SiO2和CTS之间存在较强的氢键作用,有利于SiO2和CTS共混反应的进行。另外Ag+与CTS分子结构中的氨基(-NH2)发生了配合作用,增强了共混膜的交联程度。CTS-SiO2共混膜较纯CTS膜结构更加致密,表面更加平整。CTS-SiO2-Ag共混膜内纳米Ag颗粒的粒径和分散度与Ag+加入量有关：低Ag+加入量时,纳米Ag粒径小,分散度高；高Ag+加入量时,纳米Ag粒径大,分散度低。表面包覆CTS-SiO2-Ag功能层抑菌球的抑菌性能与功能层中Ag的含量、纳米Ag颗粒的粒径及分散程度有关：粒径越小,分散性越高,抑菌性能越好；粒径越大,分散性越低,抑菌性能越差。
热处理可以有效提高功能层的交联程度,既能改善功能层的机械性能,又能防止功能层内纳米Ag组分的流失,有效地提高了抑菌球的抑菌性能。抑菌球制备过程中,Ⅰ次热处理温度为60℃,Ⅱ次热处理温度为50℃,Ⅰ次、Ⅱ次热处理时间均为2 h。
通过单因素试验确定了制备表面包覆CTS-SiO2-Ag功能层抑菌球的最佳条件：共混反应温度为30℃,共混反应时间为2 h,干燥温度为30℃,采用浓度为80%的水合肼N2H4·H2O作为还原剂,室温下反应时间为6 h。当CTS-SiO2-Ag功能层内Si02的质量浓度ρSiO2=2%,CTS的质量浓度ρCTS=2.5%,20 mL铸膜液中Ag+的加入量VAg+(0.01mol/L)=0.6 mL时,选用硅胶作为载体,可以制备出机械性能良好、抑菌性能优异且持续抑菌性能稳定的表面包覆CTS-SiO2-Ag功能层抑菌球,其质量损失率P=2.11%,抑菌率ψ=98.8%。
The health security of drinking water is the basic requirement. Drinking water of low quality will lead to serious consequences. Drinking water of residents confronts serious secondary pollution in the transport and storage. This study aims to develop a kind of new holding nano-Ag anti-bacteria balls which are low-cost, easy to use and efficient antibacterial effect. These anti-bacteria balls are applied to tanks in residential buildings, to improve the quality of drinking water.
In this study, CTS-SiO2 blend films, CTS-SiO2-Ag+ blend films and CTS-SiO2-Ag blend films was prepared based on chitosan by blend reaction, and study the physical and chemical properties and antibacterial properties of these blend films. On this basis, using silicone as the carrier of the ball, and prepare the surface coating CTS-SiO2-Ag layer of the anti-bacteria balls with excellent mechanical properties, favorable, stability and continuous antibacterial properties. This paper study the influence of blend films and anti-bacteria balls' properties on the reaction temperature of experiment, the reaction time of experiment, the input amount of Ag+ and heat treatment condition, choose the best preparation method finally. At the same time, this study characterize the blend films by using IR and SEM.
The results show that, there are strong hydrogen bonds between SiO2 and the CTS, and favor the CTS blend SiO2 reaction. There are coordination bonds between Ag+ and amino(-NH2) in the molecular structure of CTS, enhanc the cross-linked extent of blend films. CTS-SiO2 blend films compared with pure CTS films structure is more compact, surface is smoother. The scatter properties and size of nano-Ag particle in CTS-SiO2-Ag blend films lie on the input amount of Ag+:fewer input amount of Ag+, the nano-Ag particle's size is smaller, scattered better; more input amount of Ag+, the nano-Ag particles'size is larger, scattered more badly. The antibacterial properties of surface coating CTS-SiO2-Ag layer anti-bacteria balls lie on nano-Ag particles' size and scatteration degree:the smaller the particle size, the higher the scatteration degree, the better antibacterial properties; the greater the particle size, the lower the scatteration degree, the worse the antibacterial properties.
Heat treatment can improve the cross-linked extent of function layer, on the one hand, it can improve the mechanical properties of function layer, on the other hand it can prevent losing of nano-Ag in function layer, effectively promote the antibacterial properties of anti-bacteria balls. On the preparation process of anti-bacteria balls, first heat treatment temperature is 60℃, second heat treatment temperature is 50℃, first& second heat treatment time is 2 h conformably.
Determined the best method by single-factor test preparation surface coating CTS-SiO2-Ag layer anti-bacteria balls:the blend reaction temperature is 30℃, the blend reaction time is 2 h, drying temperature is 30℃, with concentrations of 80% hydrazine hydrate N2H4·H2O as a reducing agent, at room temperature and reaction time is 6h. When SiO2 concentration of massρSiO2=2%, CTS concentration of massρCTS=2.5%, Ag+ concentration of volumeφAg+(0.01mol/L)=3%, in the CTS-SiO2-Ag functional layer, choosing silicone as a carrier, can be prepared surface coating CTS-SiO2-Ag layer anti-bacteria balls with excellent mechanical properties, favorable, stability&continuous antibacterial properties, its mass loss rate P=2.11%, antibacterial rateψ=98.8%.
本研究在制备出CTS-SiO2共混膜、CTS-SiO2-Ag+共混膜以及CTS-SiO2-Ag共混膜的基础上,又使用硅胶球作为载体,制备出机械性能优良、抑菌性能优异且持续抑菌性能稳定的表面包覆CTS-SiO2-Ag功能层的抑菌球。实验过程中研究了反应温度、反应时间、Ag+加入量、热处理条件等因素对共混膜和抑菌球性能的影响,确定了最佳制备方法。同时利用傅里叶红外光谱仪IR、电子扫描电镜SEM等对共混膜进行了表征分析。
研究结果表明,SiO2和CTS之间存在较强的氢键作用,有利于SiO2和CTS共混反应的进行。另外Ag+与CTS分子结构中的氨基(-NH2)发生了配合作用,增强了共混膜的交联程度。CTS-SiO2共混膜较纯CTS膜结构更加致密,表面更加平整。CTS-SiO2-Ag共混膜内纳米Ag颗粒的粒径和分散度与Ag+加入量有关：低Ag+加入量时,纳米Ag粒径小,分散度高；高Ag+加入量时,纳米Ag粒径大,分散度低。表面包覆CTS-SiO2-Ag功能层抑菌球的抑菌性能与功能层中Ag的含量、纳米Ag颗粒的粒径及分散程度有关：粒径越小,分散性越高,抑菌性能越好；粒径越大,分散性越低,抑菌性能越差。
热处理可以有效提高功能层的交联程度,既能改善功能层的机械性能,又能防止功能层内纳米Ag组分的流失,有效地提高了抑菌球的抑菌性能。抑菌球制备过程中,Ⅰ次热处理温度为60℃,Ⅱ次热处理温度为50℃,Ⅰ次、Ⅱ次热处理时间均为2 h。
通过单因素试验确定了制备表面包覆CTS-SiO2-Ag功能层抑菌球的最佳条件：共混反应温度为30℃,共混反应时间为2 h,干燥温度为30℃,采用浓度为80%的水合肼N2H4·H2O作为还原剂,室温下反应时间为6 h。当CTS-SiO2-Ag功能层内Si02的质量浓度ρSiO2=2%,CTS的质量浓度ρCTS=2.5%,20 mL铸膜液中Ag+的加入量VAg+(0.01mol/L)=0.6 mL时,选用硅胶作为载体,可以制备出机械性能良好、抑菌性能优异且持续抑菌性能稳定的表面包覆CTS-SiO2-Ag功能层抑菌球,其质量损失率P=2.11%,抑菌率ψ=98.8%。
The health security of drinking water is the basic requirement. Drinking water of low quality will lead to serious consequences. Drinking water of residents confronts serious secondary pollution in the transport and storage. This study aims to develop a kind of new holding nano-Ag anti-bacteria balls which are low-cost, easy to use and efficient antibacterial effect. These anti-bacteria balls are applied to tanks in residential buildings, to improve the quality of drinking water.
In this study, CTS-SiO2 blend films, CTS-SiO2-Ag+ blend films and CTS-SiO2-Ag blend films was prepared based on chitosan by blend reaction, and study the physical and chemical properties and antibacterial properties of these blend films. On this basis, using silicone as the carrier of the ball, and prepare the surface coating CTS-SiO2-Ag layer of the anti-bacteria balls with excellent mechanical properties, favorable, stability and continuous antibacterial properties. This paper study the influence of blend films and anti-bacteria balls' properties on the reaction temperature of experiment, the reaction time of experiment, the input amount of Ag+ and heat treatment condition, choose the best preparation method finally. At the same time, this study characterize the blend films by using IR and SEM.
The results show that, there are strong hydrogen bonds between SiO2 and the CTS, and favor the CTS blend SiO2 reaction. There are coordination bonds between Ag+ and amino(-NH2) in the molecular structure of CTS, enhanc the cross-linked extent of blend films. CTS-SiO2 blend films compared with pure CTS films structure is more compact, surface is smoother. The scatter properties and size of nano-Ag particle in CTS-SiO2-Ag blend films lie on the input amount of Ag+:fewer input amount of Ag+, the nano-Ag particle's size is smaller, scattered better; more input amount of Ag+, the nano-Ag particles'size is larger, scattered more badly. The antibacterial properties of surface coating CTS-SiO2-Ag layer anti-bacteria balls lie on nano-Ag particles' size and scatteration degree:the smaller the particle size, the higher the scatteration degree, the better antibacterial properties; the greater the particle size, the lower the scatteration degree, the worse the antibacterial properties.
Heat treatment can improve the cross-linked extent of function layer, on the one hand, it can improve the mechanical properties of function layer, on the other hand it can prevent losing of nano-Ag in function layer, effectively promote the antibacterial properties of anti-bacteria balls. On the preparation process of anti-bacteria balls, first heat treatment temperature is 60℃, second heat treatment temperature is 50℃, first& second heat treatment time is 2 h conformably.
Determined the best method by single-factor test preparation surface coating CTS-SiO2-Ag layer anti-bacteria balls:the blend reaction temperature is 30℃, the blend reaction time is 2 h, drying temperature is 30℃, with concentrations of 80% hydrazine hydrate N2H4·H2O as a reducing agent, at room temperature and reaction time is 6h. When SiO2 concentration of massρSiO2=2%, CTS concentration of massρCTS=2.5%, Ag+ concentration of volumeφAg+(0.01mol/L)=3%, in the CTS-SiO2-Ag functional layer, choosing silicone as a carrier, can be prepared surface coating CTS-SiO2-Ag layer anti-bacteria balls with excellent mechanical properties, favorable, stability&continuous antibacterial properties, its mass loss rate P=2.11%, antibacterial rateψ=98.8%.
引文
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