聚酯表面氯化银抗菌溶胶薄膜的制备及性能研究
摘要
本论文采用溶胶-凝胶(Sol-Gel)工艺,以聚乙烯吡咯烷酮(PVP)作为活性分散剂,通过优化溶液的成分、pH值以及烘干时间、烘干温度等制备出稳定性和抗变色性良好的AgCl抗菌溶胶。采用浸渍提拉法在聚酯(PET)表面进行涂膜试验,成功地制备出表面均匀无裂纹,抗变色性能良好的抗菌溶胶薄膜。
利用金相显微镜(OM)和扫描电镜(SEM)对薄膜进行形貌分析;傅立叶红外光谱仪(FTIR)、X射线衍射仪和X射线能谱仪(EDS)对表面膜层的元素分布、相结构进行了分析。通过润湿角测量仪对溶胶和溶胶薄膜分别进行了润湿性和耐水性分析;机械折叠试验和摩擦磨损试验对膜基结合力及耐磨性进行了检测;力学万能试验机对有抗菌薄膜的PET进行拉伸性能的检测。最后利用平板计数法对表面抗大肠肝菌以及金黄色葡萄球菌的性能进行了评估和分析。
FTIR检测结果表明,PVP侧链上的-C=O处峰值发生10cm-1红移,证明AgCl粒子与PVP的分子链相连;在1570cm-1和922cm-1两处产生了新的吸收峰,表明分散剂PVP和基体PET之间产生了化学键结合。EDS分析结果表明,抗菌溶胶薄膜的主要组成元素为C、H、O、N、Ag和Cl。XRD结果表明,AgCl和PVP发生了络合反应形成PVP·AgCl,溶胶膜层总体上表现出PVP·AgCl(111)、AgCl(200)和AgO(311)的晶向。溶胶的pH值和烘干温度对溶胶薄膜的晶型和晶化度有影响,较高的烘干温度有利于晶化度的提高。
采用的分级干燥法(80℃～60℃～40℃)使大量溶剂在干燥过程中快速充分排出,同时又防止了膜层发生龟裂。二次烘干温度和烘干时间对膜基结合力有重要影响;溶胶的PH值,烘干温度和烘干时间对溶胶薄膜的耐磨性有主要影响。用pH=3.0的溶胶,在120℃烘干2h～8h的条件下制备的溶胶薄膜具有较好的耐磨性能。在溶胶中加入丙烯酸乙酯可以大幅度提高溶胶薄膜的强度、韧性、耐磨性能和耐水性能。
抗菌检测结果表明,所有试样均显示出良好的抗菌作用,氯化银胶体具有很强的抗菌能力。在24小时内,对大肠杆菌和金黄色葡萄球菌的抗菌作用都达到99%以上。在对试样进行抗菌速率的检测中发现,溶胶的pH值和烘干温度对抗菌速率有一定的影响。高烘干温度有利于形成AgO的{311}和AgClO2{200}衍射晶面,由于Ag2+和ClO2的氧化性能高于AgCl中的Ag+,从而使得薄膜的抗菌速率提高。折叠实验对溶胶薄膜的抗菌率几乎没有影响。对加入耐水性物质的溶胶薄膜抗菌检测表明,没加入耐水性物质的AgCl溶胶薄膜和加入丙烯酸乙酯的溶胶薄膜经过生理盐水浸泡1.5h小时后两者的抗菌率分别为降低到60%和92.5%,证明丙烯酸乙酯的加入提高了溶胶薄膜的耐水性,使溶胶薄膜具有持久的抗菌性能。
In this paper, antibacterial films containing AgCl were fabricated on PET substrate by Sol-Gel method. Polyvinyl pyrrolidone (PVP) was used as the dispersant and protected agent in the Sol-Gel solution. Dipping coating method was applied during the process. The component of solution, pH value, drying temperature and drying time, etc. were optimized to obtain uniform coatings with good antibacterial properties and anti-color change ability.
Optical microscope (OM) and scanning electronic microscope(SEM) were used to observe the surface topography. Fourier Transform Infrared Spectrometer(FTIR), X-ray energy spectrum(EDS) and X-ray diffraction (XRD) were used to analysis the phase structures as well as chemical bonds. The contact-measuring device was used to analysis the surface wettability and water resistance of sol thin films containing AgCl. The adhesion strength and tribological properties of the fabricated film were investigated by mechanical folding test and the pin-on-disk tester. Antibacterial ability against Escherichia coli and staphylococcus aureus of the films was evaluated using plate-counting method.
The FTIR results indicate that the peak of -C=O related to PVP molecules chains moves 10cm-1 towards low wave number, which imply that AgCl nanoparticles links with PVP molecules chains.The new peaks of 1570 cm-1and 922 cm-1 illustrate that the dispersant PVP reacts with the PET and generates new chemical bonds and cross-linking.The EDS results demonstrate that the antibacterial thin films are mainly composed of C, O, N, Ag and Cl elements. The XRD results show that AgCl binds with PVP to form PVP·AgCl. The sol films are mainly composed of PVP·AgCl (111), AgCl (200) and AgO (311). Higher drying temperature can improve the crystallization of films.
Classification-drying method (80℃～60℃～40℃) is used to release the solvent completely, as well as avoid the crack of coatings. In order to improve the adhesion strength between the thin films and the PET substrate, the AgCl sol thin films were finally dried at higher temperature after classification-drying. The final drying temperature and drying time greatly affect the adhesion strength. The tribological properties are dependent on the pH values, drying temperature and drying time. The AgCl sol films treated with pH =3.0 and dried at 120℃for above 2h exhibit good bonding strength and wear resistance. Adding the ethylacrylate (EA) into the AgCl sol films can improve the strength, toughness, wear resistance and water resistance of the fabricated films.
The antibacterial effect of all sol thin films containing AgCl are 99.9% after 24-hour antibacterial tests. The pH values and drying temperature play important roleS in the antibacterial rate. The high drying temperature can induce the formation of AgO (311) and AgClO2 (200), which may improve the antibacterial rate of the coatings. The folding test shows slight effect on the antibacterial ability. The antibacterial effect of sample Y22 and Y20 immersed in the 0.87% brine for 1.5 hours drops to 60% and 92.5% respectively, which demonstrate that adding the ethylacrylate(EA) into the AgCl sol films can improve water resistance and prolong the antibacterial life of the thin films containing AgCl.
利用金相显微镜(OM)和扫描电镜(SEM)对薄膜进行形貌分析;傅立叶红外光谱仪(FTIR)、X射线衍射仪和X射线能谱仪(EDS)对表面膜层的元素分布、相结构进行了分析。通过润湿角测量仪对溶胶和溶胶薄膜分别进行了润湿性和耐水性分析;机械折叠试验和摩擦磨损试验对膜基结合力及耐磨性进行了检测;力学万能试验机对有抗菌薄膜的PET进行拉伸性能的检测。最后利用平板计数法对表面抗大肠肝菌以及金黄色葡萄球菌的性能进行了评估和分析。
FTIR检测结果表明,PVP侧链上的-C=O处峰值发生10cm-1红移,证明AgCl粒子与PVP的分子链相连;在1570cm-1和922cm-1两处产生了新的吸收峰,表明分散剂PVP和基体PET之间产生了化学键结合。EDS分析结果表明,抗菌溶胶薄膜的主要组成元素为C、H、O、N、Ag和Cl。XRD结果表明,AgCl和PVP发生了络合反应形成PVP·AgCl,溶胶膜层总体上表现出PVP·AgCl(111)、AgCl(200)和AgO(311)的晶向。溶胶的pH值和烘干温度对溶胶薄膜的晶型和晶化度有影响,较高的烘干温度有利于晶化度的提高。
采用的分级干燥法(80℃～60℃～40℃)使大量溶剂在干燥过程中快速充分排出,同时又防止了膜层发生龟裂。二次烘干温度和烘干时间对膜基结合力有重要影响;溶胶的PH值,烘干温度和烘干时间对溶胶薄膜的耐磨性有主要影响。用pH=3.0的溶胶,在120℃烘干2h～8h的条件下制备的溶胶薄膜具有较好的耐磨性能。在溶胶中加入丙烯酸乙酯可以大幅度提高溶胶薄膜的强度、韧性、耐磨性能和耐水性能。
抗菌检测结果表明,所有试样均显示出良好的抗菌作用,氯化银胶体具有很强的抗菌能力。在24小时内,对大肠杆菌和金黄色葡萄球菌的抗菌作用都达到99%以上。在对试样进行抗菌速率的检测中发现,溶胶的pH值和烘干温度对抗菌速率有一定的影响。高烘干温度有利于形成AgO的{311}和AgClO2{200}衍射晶面,由于Ag2+和ClO2的氧化性能高于AgCl中的Ag+,从而使得薄膜的抗菌速率提高。折叠实验对溶胶薄膜的抗菌率几乎没有影响。对加入耐水性物质的溶胶薄膜抗菌检测表明,没加入耐水性物质的AgCl溶胶薄膜和加入丙烯酸乙酯的溶胶薄膜经过生理盐水浸泡1.5h小时后两者的抗菌率分别为降低到60%和92.5%,证明丙烯酸乙酯的加入提高了溶胶薄膜的耐水性,使溶胶薄膜具有持久的抗菌性能。
In this paper, antibacterial films containing AgCl were fabricated on PET substrate by Sol-Gel method. Polyvinyl pyrrolidone (PVP) was used as the dispersant and protected agent in the Sol-Gel solution. Dipping coating method was applied during the process. The component of solution, pH value, drying temperature and drying time, etc. were optimized to obtain uniform coatings with good antibacterial properties and anti-color change ability.
Optical microscope (OM) and scanning electronic microscope(SEM) were used to observe the surface topography. Fourier Transform Infrared Spectrometer(FTIR), X-ray energy spectrum(EDS) and X-ray diffraction (XRD) were used to analysis the phase structures as well as chemical bonds. The contact-measuring device was used to analysis the surface wettability and water resistance of sol thin films containing AgCl. The adhesion strength and tribological properties of the fabricated film were investigated by mechanical folding test and the pin-on-disk tester. Antibacterial ability against Escherichia coli and staphylococcus aureus of the films was evaluated using plate-counting method.
The FTIR results indicate that the peak of -C=O related to PVP molecules chains moves 10cm-1 towards low wave number, which imply that AgCl nanoparticles links with PVP molecules chains.The new peaks of 1570 cm-1and 922 cm-1 illustrate that the dispersant PVP reacts with the PET and generates new chemical bonds and cross-linking.The EDS results demonstrate that the antibacterial thin films are mainly composed of C, O, N, Ag and Cl elements. The XRD results show that AgCl binds with PVP to form PVP·AgCl. The sol films are mainly composed of PVP·AgCl (111), AgCl (200) and AgO (311). Higher drying temperature can improve the crystallization of films.
Classification-drying method (80℃～60℃～40℃) is used to release the solvent completely, as well as avoid the crack of coatings. In order to improve the adhesion strength between the thin films and the PET substrate, the AgCl sol thin films were finally dried at higher temperature after classification-drying. The final drying temperature and drying time greatly affect the adhesion strength. The tribological properties are dependent on the pH values, drying temperature and drying time. The AgCl sol films treated with pH =3.0 and dried at 120℃for above 2h exhibit good bonding strength and wear resistance. Adding the ethylacrylate (EA) into the AgCl sol films can improve the strength, toughness, wear resistance and water resistance of the fabricated films.
The antibacterial effect of all sol thin films containing AgCl are 99.9% after 24-hour antibacterial tests. The pH values and drying temperature play important roleS in the antibacterial rate. The high drying temperature can induce the formation of AgO (311) and AgClO2 (200), which may improve the antibacterial rate of the coatings. The folding test shows slight effect on the antibacterial ability. The antibacterial effect of sample Y22 and Y20 immersed in the 0.87% brine for 1.5 hours drops to 60% and 92.5% respectively, which demonstrate that adding the ethylacrylate(EA) into the AgCl sol films can improve water resistance and prolong the antibacterial life of the thin films containing AgCl.
引文
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