WO2023087634A1 - 一种银胶体及制备方法 - Google Patents
一种银胶体及制备方法 Download PDFInfo
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- WO2023087634A1 WO2023087634A1 PCT/CN2022/091857 CN2022091857W WO2023087634A1 WO 2023087634 A1 WO2023087634 A1 WO 2023087634A1 CN 2022091857 W CN2022091857 W CN 2022091857W WO 2023087634 A1 WO2023087634 A1 WO 2023087634A1
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- silver
- mixed solution
- silver colloid
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 93
- 239000004332 silver Substances 0.000 title claims abstract description 93
- 239000000084 colloidal system Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000000366 colloid method Methods 0.000 title 1
- 239000011259 mixed solution Substances 0.000 claims abstract description 56
- 239000002245 particle Substances 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000006228 supernatant Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 19
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- AYKOTYRPPUMHMT-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag] AYKOTYRPPUMHMT-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000006866 deterioration Effects 0.000 abstract description 2
- 229920000742 Cotton Polymers 0.000 description 13
- 241000219146 Gossypium Species 0.000 description 11
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 10
- 241000588724 Escherichia coli Species 0.000 description 9
- 230000000844 anti-bacterial effect Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000006199 nebulizer Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 206010059866 Drug resistance Diseases 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 240000000047 Gossypium barbadense Species 0.000 description 1
- 235000009429 Gossypium barbadense Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Definitions
- the invention belongs to the technical field of colloid chemistry, and in particular relates to a silver colloid and a preparation method thereof.
- nanosilver is one of the metal nanomaterials that have been studied more in recent years. Due to its small size effect, quantum size effect, surface effect and macroscopic quantum tunneling effect, nano silver exhibits many unique properties. When the particle size of silver reaches the nanometer level, its antibacterial performance will increase to thousands of times due to the surface effect and quantum effect. Nanosilver below 25 nanometers has a particle size smaller than that of bacteria and viruses, so it can penetrate the cell wall and combine with the base enzymes they use for respiration, suffocating bacteria and viruses to death without leaving the possibility of changing genes sex.
- nano-silver has the characteristics of high-efficiency broad-spectrum sterilization, strong permeability, no drug resistance, repair and regeneration, long-lasting antibacterial, safe and non-toxic, and has great potential in the fields of plastic toys, household products, fruit preservation, air purification, and medical materials. Broad application prospects.
- silver colloids as the target product, have broader industrial and commercial applications. Due to its small particle size and high surface energy, nano-silver has a strong tendency to agglomerate.
- the preparation process of the existing silver colloid mainly starts from a silver salt solution, and generates silver particles through a reducing agent and a silver salt.
- a large amount of additives in the solution such as Patent CN201210258492.5 provides a silver colloid and its preparation method
- the prepared colloid in addition to silver salt and reducing agent, also contains dispersant, protective agent, pH regulator and so on. The existence of a large number of additives will not only increase the cost of silver colloid.
- the object of the present invention is to provide a method for preparing silver colloid, which has simple raw materials, simple process and low cost, and the prepared silver colloid only contains nano-silver particles and a dispersant.
- Another object of the present invention is to provide a silver colloid containing only nano-silver particles and a dispersant.
- a preparation method of silver colloid comprising,
- S1 Dissolve the dispersant in water to obtain solution 1; uniformly disperse silver powder and water to obtain mixed solution 2;
- the silver powder and water are uniformly dispersed by ultrasonic, and the ultrasonic time is 15-20 min.
- the concentration of the silver powder in the mixed solution 2 is 0.05-0.75 g/L, and the particle size of the silver particles in the silver powder is 80 ⁇ 20 nm.
- the mixed solution 2 is dropped into the solution 1 at a rate of 3-5 mL/min.
- the mass ratio of the dispersant to the silver powder is 10:1-20:1; the mass concentration of the silver powder is 0.01-0.15g/L.
- said mixed solution 3 is uniformly dispersed in a sealed state to obtain mixed solution 4, comprising:
- the ultrasonic dispersion time is 3.5-4.5 hours
- the stirring time is 24 to 48 hours
- the ultrasonic dispersion time is 3.5-4.5 hours.
- the ultrasonic dispersion time is 4h
- the stirring time is 36h
- the ultrasonic dispersion time is 4 hours.
- the centrifugation speed is 4000-7000r/min, and the centrifugation time is 10-15min.
- a silver colloid is prepared by the aforementioned method for preparing silver colloid.
- the preparation method of silver colloid provided by the present invention has simple raw materials, simple process and low cost, and the prepared silver colloid only contains nano-silver particles and dispersant; and the prepared silver colloid has good stability and can be stored for a long time no deterioration;
- the nano antibacterial cotton prepared by adopting the silver colloid provided by the present invention has a good bactericidal effect.
- Fig. 1 is the TEM figure of the silver colloid that embodiment one prepares
- Fig. 2 is the TEM enlargement figure of the silver colloid that embodiment one prepares
- Fig. 3 is the ultraviolet absorption spectrogram of the silver colloid that embodiment one, embodiment two, embodiment three prepare;
- Fig. 4 is under 7k magnification, the Escherichia coli SEM photograph of the nano antibacterial cotton surface that embodiment four prepares;
- Fig. 5 is under 10k magnification, the Escherichia coli SEM photo of the surface of the nano antibacterial cotton prepared in embodiment four.
- the embodiment of the present invention provides a kind of preparation method of silver colloid, comprises the following steps:
- the dispersant is sodium dodecyl sulfate (SDS), and the concentration of the dispersant in solution one is 2.5 g/L.
- SDS sodium dodecyl sulfate
- concentration of the dispersant in solution one is 2.5 g/L.
- SDS can effectively prevent the agglomeration of nano-silver particles.
- the concentration of the silver powder in the mixed solution 2 is 0.05-0.75 g/L
- the particle size of the silver particles in the silver powder is 80 ⁇ 20 nm
- the specific surface area is ⁇ 3.0 m 3 /g.
- step S1 the silver powder and water are uniformly dispersed by ultrasonic or stirring to obtain the mixed liquid 2. It is preferred to disperse uniformly by ultrasonic, and the ultrasonic time is 15-20 minutes.
- step S2 the mixed solution 2 is dripped into the solution 1 at a rate of 3-5 mL/min, preferably at a rate of 4 mL/min.
- the mass ratio of the dispersant to the silver powder is 10:1 ⁇ 20:1, preferably 20:1.
- the mass concentration of silver powder in the mixed liquid three is 0.01-0.15 g/L, preferably 0.1 g/L.
- the mixed liquid 3 is in a sealed state, and the mixed liquid 3 is uniformly dispersed through the composite dispersion mode of ultrasonic-stirring-ultrasonic to obtain the mixed liquid 4, which specifically includes the following steps,
- the silver particles can be uniformly dispersed through the composite dispersion mode of ultrasonic-stirring-ultrasonic.
- step S4 the rotational speed of the centrifuge is 4000-7000r/min, preferably 6000r/min, and the centrifugation time is 10-15min, preferably 15min.
- the preparation method of silver colloid provided by the present invention can be used to prepare colloids such as gold colloid and zinc colloid.
- the embodiment of the present invention also provides a silver colloid prepared by the aforementioned method for preparing silver colloid.
- the reagents used in the following examples are all commercially available, among which the silver powder is purchased from the China Metallurgical Research Institute, the particle size of the silver powder is 80 ⁇ 20nm, the specific surface area is ⁇ 3.0m 3 /g, and the purity is 99.9%.
- the bottom precipitate after centrifugation is basically nano-silver powder.
- the bottom silver powder is collected, dried and weighed. The weight is 4mg, so the concentration of silver in the prepared silver colloid is 60ppm.
- Figure 1 is a TEM image of silver colloid. It can be seen that the size and location of silver particles are relatively uniform.
- Figure 2 is a TEM image of a single silver particle. It can be seen that the size of a single silver particle is about 80nm. This figure shows that silver colloid successful preparation.
- the peak position of the silver colloid prepared in this embodiment is around 425 nm, which is due to the larger diameter of the silver particles and the wider particle size distribution range of the silver particles.
- the silver colloid prepared in this example has good stability, and the silver colloid will not change after being placed for two months. There will be a little precipitation of the silver colloid after more than two months, and a uniform silver colloid can be obtained by shaking it manually.
- the peak position of the silver colloid prepared in this embodiment is around 425 nm, which is due to the larger diameter of the silver particles and the wider particle size distribution range of the silver particles.
- the intensity of the characteristic absorption peak of the silver colloid prepared in this example is higher than that of the silver colloid prepared in Example 1.
- the silver colloid prepared in this example has good stability, and the silver colloid will not change after being placed for two months. There will be a little precipitation of the silver colloid after more than two months, and a uniform silver colloid can be obtained by shaking it manually.
- the peak position of the silver colloid prepared in this embodiment is around 425 nm, which is due to the larger diameter of the silver particles and the wider particle size distribution range of the silver particles.
- the intensity of the characteristic absorption peak of the silver colloid prepared in this example is higher than that of the silver colloid prepared in Example 2.
- the silver colloid prepared in this example has good stability, and the silver colloid will not change after being placed for two months. There will be a little precipitation of the silver colloid after more than two months, and a uniform silver colloid can be obtained by shaking it manually.
- an aerosol-assisted atmospheric pressure plasma deposition device provided by patent CN202122332358.2 is selected for preparation:
- Plasma is generated after argon gas is introduced, and the cotton surface is treated with plasma.
- the power frequency is 20kHz
- the voltage is 14kV
- the time is 30s
- the current is 8.5mA
- the power density of the plasma is 16.48W/cm 3 .
- Example 3 Put the silver colloid prepared in Example 1 into an ultrasonic nebulizer, the liquid consumption rate of the nebulizer is 3mL/min, and the particle size of the mist generated: 1-5 ⁇ m; Nano-silver particles can be used to obtain nano-antibacterial cotton, the power frequency is 20kHz, the voltage is 14kV, the current is 8.5mA, the power density of the plasma is 16.48W/cm 3 , and the time is 10min.
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Abstract
本发明属于胶体化学技术领域,具体涉及一种银胶体及制备方法,该方法包括将分散剂加入水中溶解,得到溶液一;将银粉与水分散均匀得到混合液二;将混合液二滴入溶液一中,得到混合液三;将混合液三在密封状态下分散均匀得到混合液四;将混合液四离心,得到的上层清液即为银胶体。本发明所提供的银胶体的制备方法,原料简单、工艺简单、成本低,制备出的银胶体中仅含纳米银颗粒和分散剂;且制备的银胶体稳定性好,能够长时间储存不变质。
Description
本发明属于胶体化学技术领域,具体涉及一种银胶体及制备方法。
在纳米材料研究领域中,纳米银是近年来研究较多的金属纳米材料之一。纳米银由于自身具有小尺寸效应、量子尺寸效应、表面效应和宏观量子隧道效应,因而展现出许多特有性能。当银的粒径达到纳米级时,由于呈现出表面效应和量子效应,其抗菌性能将增大至数千倍。25纳米以下的纳米银,其粒径比细菌、病毒的尺寸还小,因而它可以穿透细胞壁与它们用于呼吸的基酶结合,使细菌、病毒窒息而死,不留下改变基因的可能性。所以,纳米银具有高效广谱杀菌、渗透性强、无耐药性、修复再生、抗菌持久、安全无毒等特点,在塑料玩具、家居用品、水果保鲜、空气净化、医用材料等领域具有十分广阔的应用前景。
在较多的情况下,银胶体作为目标产物,具有更为广阔的工业和商业应用。由于纳米银其粒径较小,表面能较高,具有极强的团聚倾向。现有的银胶体的制备过程,主要从银的盐溶液出发,通过还原剂与银盐生成银颗粒,同时为了银颗粒在溶液中的稳定性,溶液中必不可少的需要加入大量添加剂,如专利CN201210258492.5提供了一种银胶体及其制备方法,制备出的胶体中,除银盐和还原剂以外,还含有分散剂、保护剂、pH调节剂等。大量添加剂的存在不仅会提升银胶体的成本。
发明内容
为解决现有技术的不足,本发明的目的是提供一种银胶体的制备方法,原料简单、工艺简单、成本低,制备出的银胶体中仅含纳米银颗粒和分散剂。
本发明的另一目的是提供一种仅含纳米银颗粒和分散剂的银胶体。
为解决现有技术的不足,本发明提供的技术方案为:
一种银胶体的制备方法,包括,
S1:将分散剂加入水中溶解,得到溶液一;将银粉与水分散均匀得到混合液二;
S2:将所述混合液二滴入所述溶液一中,得到混合液三;
S3:将所述混合液三在密封状态下分散均匀得到混合液四;
S4:将所述混合液四离心,得到的上层清液即为银胶体。
优选的,所述步骤S1中,所述银粉与水通过超声分散均匀,超声时间为15~20min。
优选的,所述混合液二中银粉的浓度为0.05~0.75g/L,银粉中银颗粒的粒径为80±20nm。
优选的,所述步骤S2中,所述混合液二以3~5mL/min的速度逐滴滴入溶液一中。
优选的,所述混合液三中,所述分散剂与所述银粉的质量比为10:1~20:1;所述银粉的质 量浓度为0.01~0.15g/L。
优选的,所述将混合液三在密封状态下分散均匀得到混合液四,包括,
S31:密封状态下,对混合液三进行超声分散;
S32:密封状态下,对超声分散后的混合液三进行搅拌;
S32:密封状态下,将搅拌后的混合液三进行超声分散得到混合液四。
优选的,所述步骤S31中,超声分散时间为3.5~4.5h;
所述步骤S32中,搅拌时间为24~48h;
所述步骤S33中,超声分散时间为3.5~4.5h。
优选的,所述步骤S31中,超声分散时间为4h;
所述步骤S32中,搅拌时间为36h;
所述步骤S33中,超声分散时间为4h。
优选的,所述步骤S4中,离心转速为4000~7000r/min,离心时间为10~15min。
一种银胶体,由前述的银胶体的制备方法制备而成。
本发明的有益效果:
1)本发明所提供的银胶体的制备方法,原料简单、工艺简单、成本低,制备出的银胶体中仅含纳米银颗粒和分散剂;且制备的银胶体稳定性好,能够长时间储存不变质;
2)采用本发明所提供的银胶体制备的纳米抗菌棉具有良好的杀菌效果。
图1为实施例一制备的银胶体的TEM图;
图2为实施例一制备的银胶体的TEM放大图;
图3为实施例一、实施例二、实施例三制备的银胶体的紫外吸收光谱图;
图4为7k倍率下,实施例四制备的纳米抗菌棉表面的大肠杆菌SEM照片;
图5为10k倍率下,实施例四制备的纳米抗菌棉表面的大肠杆菌SEM照片。
下面结合实施方式对本发明作进一步描述。以下实施方式仅用于更加清楚地说明本发明的技术方案,而不能以此来限制本发明的保护范围。
本发明实施例提供一种银胶体的制备方法,包括以下步骤:
S1:将分散剂加入水中溶解,得到溶液一;将银粉加入水中,分散均匀得到混合液二;
S2:将混合液二滴入溶液一中,得到混合液三;
S3:将混合液三在密封状态下分散均匀得到混合液四;
S4:将混合液四放入离心机中离心,得到的上层清液即为银胶体。
在本发明可选实施例中,分散剂为十二烷基硫酸钠(SDS),分散剂在溶液一中的浓度为2.5g/L。SDS作为纳米银分散剂,可有效防止纳米银颗粒团聚。
在本发明可选实施例中,混合液二中银粉的浓度为0.05~0.75g/L,银粉中银颗粒的粒径为80±20nm,比表面积≥3.0m
3/g。
在本发明可选实施例中,步骤S1中,银粉与水通过超声或搅拌分散均匀得到混合液二。优选通过超声分散均匀,超声时间为15~20min。
在本发明可选实施例中,步骤S2中,混合液二以3~5mL/min的速度逐滴滴入溶液一中,优选滴加速度为4mL/min。
在本发明可选实施例中,混合液三中,分散剂与银粉的质量比为10:1~20:1,优选20:1。
在本发明可选实施例中,混合液三中,银粉的质量浓度为0.01~0.15g/L,优选0.1g/L。
在本发明可选实施例中,将混合液三在密封状态下,通过超声-搅拌-超声的复合分散模式将混合液三分散均匀得到混合液四,具体包括以下步骤,
S31:密封状态下,对混合液三进行超声分散,超声时间为3.5~4.5h,优选4h;
S32:密封状态下,对超声分散后的混合液三进行搅拌,搅拌时间为24~48h,优选36h;
S32:密封状态下,将搅拌后的混合液三进行超声分散-得到混合液四,超声时间为3.5~4.5h,优选4h。
由于纳米颗粒容易团聚,通过超声-搅拌-超声的复合分散模式才能使银颗粒分散均匀。
在本发明可选实施例中,步骤S4中,离心机的转速为4000~7000r/min,优选6000r/min,离心时间为10~15min,优选15min。
本发明所提供的银胶体的制备方法可用于制备金胶体、锌胶体等胶体。
本发明实施例还提供一种银胶体,由前述的银胶体的制备方法制备而成。
下述实施例所用试剂均为市售,其中银粉购自中国冶金研究总院,银粉粒径80±20nm,比表面积≥3.0m
3/g,纯度为99.9%。
实施例一
制备纳米银胶体
1)将200mg的十二烷基硫酸钠(SDS)放入80ml去离子水中溶解,得到溶液一;
2)将10mg纳米银粉放入20ml去离子水中,然后通过超声进行分散15min得到混合液二;
3)将混合液二逐滴滴入溶液一中得到混合液三,控制速度4mL/min;
4)将混合液三密封,防止水分挥发,已经经过超声分散4h、磁力搅拌24h、超声分散4h得到混合液四;
5)将混合液四放入离心机中,6000r/min离心10min,取上层清液,上层清液即为银胶体。银胶体呈亮黄色透明状,亮黄色为纳米级的银颗粒折射的光芒。
由于SDS极易溶于水不会沉淀,因此离心之后底部沉淀的基本都是纳米银粉,将底部银粉收集烘干称量,重量为4mg,因此制得的银胶体中银的浓度为60ppm。
图1为银胶体的TEM图,可看出银颗粒尺寸及银颗粒位置分布较为均匀,图2为单个银颗粒的TEM图,可看出单个银颗粒大小约在80nm上下,此图表明银胶体的成功制备。
从图3可以看出,本实施例制备的银胶体的峰位在425nm附近,这是由于银颗粒的直径较大,银颗粒的粒度分布范围较广。
本实施例制备的银胶体稳定性好,放置两个月银胶体也不会发生变化,两个月以上银胶体会有少许沉淀,手动摇匀即可得到均一的银胶体。
实施例二
制备纳米银胶体
1)将200mg的十二烷基硫酸钠(SDS)放入80ml去离子水中溶解,得到溶液一;
2)将13mg纳米银粉放入20ml去离子水中,然后通过超声进行分散15min得到混合液二;
3)将混合液二逐滴滴入溶液一中得到混合液三,控制速度4mL/min;
4)将混合液三密封,防止水分挥发,已经经过超声分散4h、磁力搅拌24h、超声分散4h得到混合液四;
5)将混合液四放入离心机中,6000r/min离心10min,取上层清液,上层清液即为银胶体。银胶体呈亮黄色透明状,制得的银胶体中银的浓度为90ppm。
从图3可以看出,本实施例制备的银胶体的峰位在425nm附近,这是由于银颗粒的直径较大,银颗粒的粒度分布范围较广。同时,本实施例制备的银胶体的特征吸收峰的强度高于实施例一制备的银胶体的特征吸收峰强度。
本实施例制备的银胶体稳定性好,放置两个月银胶体也不会发生变化,两个月以上银胶体会有少许沉淀,手动摇匀即可得到均一的银胶体。
实施例三
制备纳米银胶体
1)将200mg的十二烷基硫酸钠(SDS)放入80ml去离子水中溶解,得到溶液一;
2)将15mg纳米银粉放入20ml去离子水中,然后通过超声进行分散15min得到混合液二;
3)将混合液二逐滴滴入溶液一中得到混合液三,控制速度4mL/min;
4)将混合液三密封,防止水分挥发,已经经过超声分散4h、磁力搅拌24h、超声分散4h得到混合液四;
5)将混合液四放入离心机中,6000r/min离心10min,取上层清液,上层清液即为银胶体。银胶体呈亮黄色透明状,制得的银胶体中银的浓度为130ppm。
从图3可以看出,本实施例制备的银胶体的峰位在425nm附近,这是由于银颗粒的直径较大,银颗粒的粒度分布范围较广。同时,本实施例制备的银胶体的特征吸收峰的强度高于实施例二制备的银胶体的特征吸收峰强度。
本实施例制备的银胶体稳定性好,放置两个月银胶体也不会发生变化,两个月以上银胶体会有少许沉淀,手动摇匀即可得到均一的银胶体。
实施例四
制备纳米抗菌棉,选用专利CN202122332358.2提供的一种气溶胶辅助大气压等离子体沉积装置制备:
1)选取优质长绒棉,压平后放置于升降操作台之上;
2)通入氩气后产生等离子体,并用等离子体处理棉花表面,电源频率为20kHz,电压为14kV,时间30s,电流为8.5mA,等离子体的功率密度为16.48W/cm
3。经过等离子体处理后,棉纤维表面结构被破坏,化学键断裂,更利于纳米颗粒的沉积;
3)将实施例一制备的银胶体放入超声波雾化器中,雾化器液体消耗速率3mL/min,产生雾粒径:1-5μm;雾化气通入等离子体中,通过等离子体沉积纳米银颗粒即可得到纳米抗菌棉,电源频率为20kHz,电压为14kV,电流为8.5mA,等离子体的功率密度为16.48W/cm
3,时间10min。
纳米抗菌棉抗菌性能测试:
将纳米抗菌棉浸泡在大肠杆菌培养液之中(细菌浓度2×10
5/cm
3),在37℃下恒温培养24小时,之后取少量菌液,通过分光光度计(620nm)测试菌液吸光度,结果表明培养24小时后,大肠杆菌数量下降90%以上。从培养液中取出纳米抗菌棉,通过戊二醛固定液将表面的大肠杆菌固定,之后通过扫描电镜观察纳米抗菌棉表面大肠杆菌的生存状态,从图4和图5中可以看出,大肠杆菌基本全部处于扭曲或已破损的状态,旁边还有已破损的细胞膜,未观察到棉纤维表面存在圆润健康的个体,证明制备的纳米抗菌棉对大肠杆菌有强烈的抗菌能力,可以有效杀死停留在表面的大肠杆菌,同时可以抑制周边的细菌生长。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和变形,这些改进和变形也应视为本发明的保护范围。
Claims (10)
- 一种银胶体的制备方法,其特征在于,包括,S1:将分散剂加入水中溶解,得到溶液一;将银粉与水分散均匀得到混合液二;S2:将所述混合液二滴入所述溶液一中,得到混合液三;S3:将所述混合液三在密封状态下分散均匀得到混合液四;S4:将所述混合液四离心,得到的上层清液即为银胶体。
- 根据权利要求1所述的一种银胶体的制备方法,其特征在于,所述步骤S1中,所述银粉与水通过超声分散均匀,超声时间为15~20min。
- 根据权利要求1所述的一种银胶体的制备方法,其特征在于,所述混合液二中银粉的浓度为0.05~0.75g/L,银粉中银颗粒的粒径为80±20nm。
- 根据权利要求1所述的一种银胶体的制备方法,其特征在于,所述步骤S2中,所述混合液二以3~5mL/min的速度逐滴滴入溶液一中。
- 根据权利要求1所述的一种银胶体的制备方法,其特征在于,所述混合液三中,所述分散剂与所述银粉的质量比为10:1~20:1;所述银粉的质量浓度为0.01~0.15g/L。
- 根据权利要求1所述的一种银胶体的制备方法,其特征在于,所述将混合液三在密封状态下分散均匀得到混合液四,包括,S31:密封状态下,对混合液三进行超声分散;S32:密封状态下,对超声分散后的混合液三进行搅拌;S32:密封状态下,将搅拌后的混合液三进行超声分散得到混合液四。
- 根据权利要求6所述的一种银胶体的制备方法,其特征在于,所述步骤S31中,超声分散时间为3.5~4.5h;所述步骤S32中,搅拌时间为24~48h;所述步骤S33中,超声分散时间为3.5~4.5h。
- 根据权利要求7所述的一种银胶体的制备方法,其特征在于,所述步骤S31中,超声分散时间为4h;所述步骤S32中,搅拌时间为36h;所述步骤S33中,超声分散时间为4h。
- 根据权利要求1所述的一种银胶体的制备方法,其特征在于,所述步骤S4中,离心转速为4000~7000r/min,离心时间为10~15min。
- 一种银胶体,其特征在于,由权利要求1~9中任意一项权利要求所述的银胶体的制备方法制备而成。
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