CN106270479B - A kind of attapulgite-nano silver composite inorganic powder and preparation method - Google Patents
A kind of attapulgite-nano silver composite inorganic powder and preparation method Download PDFInfo
- Publication number
- CN106270479B CN106270479B CN201510262409.5A CN201510262409A CN106270479B CN 106270479 B CN106270479 B CN 106270479B CN 201510262409 A CN201510262409 A CN 201510262409A CN 106270479 B CN106270479 B CN 106270479B
- Authority
- CN
- China
- Prior art keywords
- attapulgite
- nano silver
- silver
- inorganic powder
- composite inorganic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 137
- 229960000892 attapulgite Drugs 0.000 claims abstract description 136
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000000843 powder Substances 0.000 claims abstract description 91
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000002131 composite material Substances 0.000 claims abstract description 65
- 239000000725 suspension Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 43
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 37
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 229910052709 silver Inorganic materials 0.000 claims abstract description 19
- 239000004332 silver Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004927 clay Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims description 28
- 238000012545 processing Methods 0.000 claims description 27
- 238000007725 thermal activation Methods 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 14
- 238000001694 spray drying Methods 0.000 claims description 13
- 238000011068 loading method Methods 0.000 claims description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 26
- 238000012512 characterization method Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 16
- 238000013019 agitation Methods 0.000 description 13
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 11
- 230000000844 anti-bacterial effect Effects 0.000 description 11
- 239000003638 chemical reducing agent Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000002689 soil Substances 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000003242 anti bacterial agent Substances 0.000 description 5
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 5
- 229910001958 silver carbonate Inorganic materials 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- -1 imidazole radicals Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000005118 spray pyrolysis Methods 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical class OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical class OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical class OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 206010053615 Thermal burn Diseases 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000002882 anti-plaque Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011668 ascorbic acid Chemical class 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical class OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 239000013060 biological fluid Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910010277 boron hydride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000008103 glucose Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- XRRQZKOZJFDXON-UHFFFAOYSA-N nitric acid;silver Chemical compound [Ag].O[N+]([O-])=O XRRQZKOZJFDXON-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of attapulgite-nano silver composite inorganic powder and preparation methods.The mass ratio of silver and attapulgite is 10/100-100/100 in composite powder, and the partial size of nano silver is 3-100nm.Preparation method, which includes: (1), is mixed and made into attapulgite suspension for attapulgite and water；(2) silver nitrate is added in attapulgite suspension described in step (1), is then stirred heat treatment；It (3) will treated that attapulgite suspension is spray-dried to obtain attapulgite clay compounded powder through step (2)；(4) attapulgite clay compounded powder made from step (3) is roasted, obtains the composite inorganic powder containing nano silver.Present invention process is simply, silver load capacity is big in composite powder and is firmly combined with attapulgite.
Description
Technical field
The present invention relates to composite inorganic powder fields, further say, are to be related to a kind of containing using attapulgite as carrier
The composite inorganic powder and preparation method of nano silver particles, the composite inorganic powder can be used as antibacterial additives use.
Background technique
Due to silver have many advantages, such as efficient, safety, wide sterilization spectrum, heat resistance, have no drug resistance with it is highly selective, for a long time with
Come, people begin to carry out disinfection using silverware and utensil, and silver ion has high reaction activity, and the antibacterial characteristics of silver ion are logical
The interaction for being often attributed to it and mercaptan and carboxylate, phosphate, hydroxyl, imidazole radicals, indoles, amine disturbs microorganism
Normal physiology course.But in most of practical applications, using silver ion as antibacterial agent have certain limitation, silver from
Son is easy to react and inactivate with biological fluid, and antibacterial mechanisms require certain density silver ion sustained release to come out；No
Crossing these limitations can be resolved by nano silver particles.With the emergence and development of nanosecond science and technology, nano silver start into
Enter daily life, is widely used in health care and food hygiene field now.
In medical field, such as anti-bacterial fibre and antiseptic dressing of preparation, it is widely used in burn and scald, grafting for burns, nanometer
Silver-colored stripping and slicing patch and adhesive bandage with nm silver fabric layer etc.；Antibacterial medical equipment facility such as antibacterial scalpel, tweezers, conduit of preparation etc.,
The probability of infection is reduced, antibacterial apparatus is widely used.In the living conditions, active carbon loading silver fiber applications are in drinking water
Disinfection, it had not only played the activated carbon fibre absorption property excellent to organic matter, but also increased the restraining and sterilizing bacteria of carbon fiber
Function promotes extensive use of the activated carbon fibre in drink water purifying.
So many researchers prepare nano silver as antibacterial agent, the preparation of nano silver powder can be divided into physics side
Method, chemical method and biological method.
Physical method generally includes spray pyrolysis and ion sputtering process, and this method can directly be prepared from common elemental silver
Nano-Ag particles, simple process, purity is higher, but very high to equipment requirement, and time-consuming, and production cost is also higher；Such as Liu Zhi
Macro equal (micro-sized spherical silver powder prepared by spray pyrolysis and its pattern control, China YouSe Acta Metallurgica Sinica, in January, 2007 volume 17 the 1st
Phase) use spray pyrolysis to prepare silver powder, time enough is only kept in the case where being higher than 600 DEG C, silver nitrate heat could divide completely
Solution is converted into metallic silver, and silver granuel diameter is unevenly distributed, and partial size is mostly in 500nm or more；Similar, Zhang etc.
(Journal of Wuhan University of Technology-Mater.Sci.Ed.Dec.2009) passes through control nitric acid
Concentration, flow and the pressure of spray drying of silver-colored solution, the obtained average grain diameter of spray-wall interaction is under 720 DEG C of furnace temperature
The nano silver of 100nm.
Bioanalysis generates the catalyst mechanism of different enzymes by Institute of Micro-biology, carrys out reducing metal ion, prepares nano silver, still
Time-consuming low yield, the partial size and pattern of generation are not easy to control, and the source of raw material is extremely limited.
Chemical method is the most popular method for preparing nano silver at present, it mainly in the liquid phase, uses reducing agent appropriate
Such as boron hydride, hydrazine hydrate, sodium citrate, aminated compounds, glucose, ascorbic acid, hydrogen peroxide, aldehyde compound are by Ag+It is reduced into Ag0, by growing the method for obtaining nano silver.Nano silver made from this method is easy to reunite, therefore need to often be added appropriate steady
Determine agent such as polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), hydroxyethyl cellulose (HEC), dodecyl sodium sulfate, poly- second
Glycol, polyacrylamide (PAM) etc. reduce the reunion degree of Argent grain.
In order to improve the antibacterial effect and dispersibility of nano silver, usually by nano-silver loaded on different carriers, as
Antibacterial additives come using.The carrier for carrying silver is usually the inorganic mineral of meso-hole structure, including zeolite, galapectite, sepiolite, Jie
Hole silica, attapulgite etc..Wherein attapulgite is the nanoparticle of porous structure, and main component is that palygorskite is (recessed
Convex stick stone), it is a kind of aqueous rich magnesium silicate clay mineral with chain layer structure.Its skeleton structure is in 3 D stereo shape,
It is connected with each other by oxygen-octahedron and magnalium octahedron by sharing vertex, is parallel to brilliant (needle-shaped, the micro- stick of stick with numerous
Shape or fibrous monocrystal) direction arrangement tubular nanometer grade duct, total is run through in duct, from the section duct Shang Kan in big
Small equal (about 0.38nm × 0.63nm) honeycomb, belongs to natural monodimension nanometer material, has good absorption property and inexpensive,
It is ideal carrier material, therefore causes the attention of scholar and research structure.If Chinese patent CN1568703A is in table
Under the conditions of face activating agent and organic reducing agent are existing, chemically reacted using attapulgite as carrier with silver nitrate solution to be formed it is compound
Antibacterial agent；Similar, Chinese patent CN1685830A is immersed in zeolite powder in silver nitrate solution, so that silver ion is abundant
It is adsorbed in the hole of zeolite, it is nano silver that hydrazine hydrate is then added under stirring conditions silver ion reduction.
In addition to the method directly restored using reducing agent after above mixing silver nitrate and carrier, Chinese patent
CN103329893A is first modified fullerene surface with reducing agent etc., then makes modified fullerene anti-with silver nitrate
Fullerene loading nano silvery particle should be prepared；Similar Chinese patent CN103461382A is de- to covering with sulfur-containing amino acid first
Soil is modified, then silver ion is supported on modified montmorillonoid interlayer by ion exchange, turns silver ion by ultraviolet irradiation
Become nano silver, obtains silver-carrying modified montmorillonite antibacterial agent.
Chemical reduction method prepares carrying silver antimicrobials, usually has high requirements to the purity of carrier, surface nature etc., and
Also to be dispersed and be adjusted the processing of pH value before addition silver nitrate solution to carrier solution.In order to reduce between Nano silver grain
Mutually reunite, considerable amount of surfactant to be also added in reduction process, in finally also falling by continuous eccentric cleaning
The reducing agent and surfactant of face remnants, preparation process is complicated, and long preparation period limits its large-scale production application.
The content of nanometer silver of such method supported on carriers is very low, leads to antibacterial antiplaque agent effect not and be very well, remaining in antibacterial agent
Reducing agent and surfactant are applied to have a great impact.
Summary of the invention
To solve the carrying silver antimicrobials problem in the prior art, the present invention provides a kind of attapulgite-nano silvers
Composite inorganic powder and preparation method.The present inventor is had found by many experiments, is original with cheap attapulgite and silver nitrate
Material, without adding any reducing agent, will be spray-dried after powder the load can be obtained in 200-500 DEG C of calcination process
The attapulgite clay compounded inorganic powder of nano silver.Present invention process is simple, environmentally protective.It avoids and traditional prepares carrying nano silver
Attapulgite clay compounded inorganic powder need first to carry out pickling and in the suspension of silver nitrate and attapulgite to attapulgite
Complex process steps of the chemical reducing agent by silver nitrate reduction for elemental silver are added, and reduce environmental pollution.
An object of the present invention is to provide a kind of attapulgite-nano silver composite inorganic powder.
Wherein the mass ratio of silver and attapulgite is 10/100-100/100, and preferred mass ratio is 30/100-80/100, is received
The particle size range of meter Yin is 3-100nm.
The attapulgite is in rodlike or fibrous structure and with hollow nanoscale duct, the stick of attapulgite
For brilliant diameter between 30-80nm, draw ratio is generally higher than 10；There is the nano silver of partial size 3-100nm in attapulgite's surface load
Particle, for nano-Ag particles to be spherical, the mass ratio of attapulgite and nano silver is 10/100-100/100.
The second object of the present invention is to provide a kind of preparation method of attapulgite-nano silver composite inorganic powder.Include:
(1) attapulgite and water are hybridly prepared into attapulgite suspension；The attapulgite be preferably thermal activation and
The attapulgite of decentralized processing is not necessarily to acid treatment step.Method of roasting can be used in the thermal activation treatment, wherein maturing temperature
Preferably 200-450 DEG C, calcining time is preferably 5-60min；Concave convex rod soil mass concentration is in the attapulgite suspension
No more than 10%；The decentralized processing of the attapulgite can use conventional method in the prior art, such as: ultrasonic disperse,
Mechanical stirring dispersion (such as ball milling dispersion, high-speed stirred dispersion) etc..
(2) silver nitrate is added in attapulgite suspension described in step (1), is then stirred heat treatment；Institute
The mass ratio for stating silver nitrate and attapulgite is 17/100-170/100, and preferred mass ratio is 50/100-135/100；The heat
Treatment temperature is 50 DEG C or more, and preferably 50-90 DEG C, the heat treatment time is 1h or more.
It (3) will treated that attapulgite suspension is spray-dried to obtain attapulgite clay compounded powder through step (2)；
The temperature of the spray drying is preferably 150-250 DEG C, and further preferably 150-200 DEG C.
(4) attapulgite clay compounded powder made from step (3) is roasted, obtains the composite inorganic powder containing nano silver
End；Wherein, the roasting can be conventional method of roasting, such as by attapulgite clay compounded powder in Muffle kiln roasting, the roasting
Burning temperature is 200-500 DEG C；Maturing temperature is excessively high to make attapulgite duct collapse so as to cause adsorption capacity variation, and is easy
Attapulgite is caused to be reunited, temperature is too low, is unable to get nano silver simple substance.The calcining time is 5min or more, preferably 5-
180min；The partial size of nano silver particles of the roasting back loading in attapulgite's surface is 3-100nm.
After being stirred silver nitrate and attapulgite at a certain temperature in the present invention, the side by spray drying is needed
Formula obtains composite powder to be roasted.Using other such as filterings and the method dry with convection oven, it can not obtain and spray
The dry identical technical effect of mist.Without wishing to be bound by theory, inventors believe that it is recessed preparing nano silver of the invention
During convex stick soil composite powder, attapulgite suspension and silver nitrate solution are mixed and pass through heating stirring, can be promoted recessed
Carbanion in convex stick soil in carbonate, which dissolves and reacts generation silver carbonate with silver ion, is adsorbed on attapulgite's surface.?
In spray-drying process, unreacted silver nitrate solution and evenly dispersed attapulgite in the solution are in the effect for heating air-flow
Under can with further occurrence react generate silver carbonate.Simultaneously because the flash drying effect of drying process with atomizing, unreacted nitre
Sour silver solution can be evenly distributed in attapulgite's surface in solid particulate form after the drying, substantially increase connecing for the two
Contacting surface product.Silver nitrate solid particle and attapulgite institute carbonate containing can also further occurrences during subsequent baking heat
Reaction generates silver carbonate, and silver carbonate can be decomposed into silver-colored simple substance, and concave convex rod is finally equably supported in the form of nano silver
Native surface.
Then the present invention is spray-dried by the way that attapulgite and silver nitrate solution to be uniformly mixed, most laggard
Row roasting, is prepared using attapulgite as the attapulgite of carrier-nano silver composite inorganic powder.
Following technical scheme specifically can be used in the present invention:
(1) attapulgite and water are mixed and made into attapulgite suspension；
(2) silver nitrate is added in attapulgite suspension described in step (1), is then stirred heat treatment；
It (3) will treated that attapulgite suspension is spray-dried to obtain attapulgite clay compounded powder through step (2)；
(4) by attapulgite clay compounded powder made from step (3) in Muffle kiln roasting, the compound nothing containing nano silver is obtained
Machine powder；
Attapulgite described in step (1) is preferably the attapulgite of thermal activation and decentralized processing, the thermal activation treatment
Roasting method can be used, maturing temperature is 200-450 DEG C, calcining time 5-60min；Concave convex rod in the attapulgite suspension
The mass concentration of soil is no more than 10%；The decentralized approach of the attapulgite can use common side in the prior art
Method, such as: ultrasonic wave dispersion, mechanical stirring dispersion (such as ball milling dispersion, high-speed stirred dispersion) etc..Nitre described in step (2)
The mass ratio of sour silver and attapulgite is 17/100-170/100；The heat treatment temperature is 50-90 DEG C, when the heat treatment
Between be 1h or more.
The temperature of spray drying described in step (3) is 150-250 DEG C, preferably 150-200 DEG C；
Step (4) the middle Muffle furnace maturing temperature is 200-500 DEG C；The calcining time is 5-180min；The roasting
Burning back loading in the nano silver particles partial size of attapulgite's surface is 3-100nm.
Compared with prior art, advantages of the present invention is embodied in:
Attapulgite is natural monodimension nanometer material, has very big specific surface area, absorption property and chemical reactivity
Equal nano effects, allow the nano silver formed after roasting to be firmly adsorbed on attapulgite's surface, in this way in attapulgite
Surface forms equally distributed nanoscale Argent grain.It can also be with although being decomposed silver nitrate by the method that directly heats calcining
Nano silver simple substance is obtained, but its decomposition temperature is high, energy consumption is high, and the nano silver particles of preparation are easy to happen reunion, and partial size compares
Greatly.By heating stirring, then then spray drying exists so that carbonate contained by inside silver nitrate and attapulgite sufficiently reacts
It can be prepared by nano silver lower than roasting under silver nitrate decomposition temperature, not only avoid using reducing agent or other chemical reaction bands
The environmental pollution come, and the decomposition temperature of silver carbonate is relatively low, and roasting produces silver-colored simple substance at relatively low temperatures,
Silver-colored simple substance is uniformly adsorbed on attapulgite's surface in the form of nano silver, and this nano silver for being adsorbed on attapulgite's surface is living
Property is very big, can slowly release the silver ion with antibacterial effect, and nano-Ag particles are firmly combined with attapulgite.
Detailed description of the invention
Fig. 1: attapulgite-nano silver composite inorganic powder transmission electron microscope photo prepared by embodiment 10.
Fig. 2: attapulgite-nano silver composite inorganic powder XRD spectra prepared by embodiment 10.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated.
In embodiment it is raw materials used be it is commercially available, in embodiment attapulgite draw ratio used is greater than 10, and single stick is brilliant
Diameter is between 30-80nm.
The present invention is by using X-ray diffraction analysis (XRD) and transmission electron microscope (TEM) to prepared concave convex rod
Soil-nano silver composite inorganic powder is characterized.
Attapulgite thermal activation and decentralized processing are as follows:
A certain amount of attapulgite is put into Muffle furnace, roasts 30min at 400 DEG C；By above-mentioned roasting bumps
Stick soil is put into ball mill, at 500 rpm ball milling 3h；The attapulgite of a certain amount of above-mentioned processing is weighed, is matched after distilled water is added
The suspension that attapulgite mass concentration is 5%, first mechanical stirring 1h, then ultrasonication 30min is made；Then it will handle well
Suspension be centrifuged at 12000r/min by centrifuge；Finally discard supernatant liquor to get thermal activation and dispersion at
The attapulgite of reason.
Embodiment 1
The a certain amount of attapulgite (AT) through thermal activation and decentralized processing is weighed, being configured to attapulgite mass concentration is
1% water slurry, then by silver nitrate solution (AgNO3/ AT=17/100) it is added in attapulgite suspension, at 50 DEG C
Under, magnetic agitation 1h, then attapulgite suspension is spray-dried at 200 DEG C, it collects spray-dried obtained multiple
Powder is closed, it is multiple to get attapulgite-nano silver that obtained composite powder is finally roasted to 30min in Muffle furnace at 500 DEG C
Close inorganic powder.
Composite powder obtained after above-mentioned spray-dried composite powder obtained and roasting is subjected to X-ray diffraction respectively
(XRD) it characterizes, is as a result listed in table 1, the particle size range of nano silver is 3-100nm.
Embodiment 2
In addition to the temperature of magnetic agitation is adjusted to 70 DEG C after mix silver nitrate solution and attapulgite suspension, Qi Tagong
Skill step is same as Example 1, and characterization result is listed in table 1, and the particle size range of nano silver is 3-100nm.
Embodiment 3
In addition to the temperature of magnetic agitation is adjusted to 90 DEG C after mix silver nitrate solution and attapulgite suspension, Qi Tagong
Skill step and characterizing method are same as Example 1, and characterization result is listed in table 1, and the particle size range of nano silver is 3-100nm.
Comparative example 1
In addition to the temperature of magnetic agitation is adjusted to room temperature after mix silver nitrate solution and attapulgite suspension, Qi Tagong
Skill step and characterizing method are same as Example 1, and characterization result is listed in table 1.
Composite powder characterization result prepared by composite powder prepared by embodiment 1-3 and comparative example 1 is listed in table 1.
Table 1
From table 1 it follows that attapulgite suspension is mixed only with silver nitrate solution under conditions of being higher than room temperature
It carries out, the composite powder containing simple-substance nano silvery can just be prepared.
Embodiment 4
The a certain amount of attapulgite through thermal activation and decentralized processing is weighed, it is dense that addition distilled water is configured to attapulgite quality
The suspension that degree is 10%, then silver nitrate solution (AgNO3/ AT=170/100) it is added in attapulgite suspension, 60
At DEG C, 1h is stirred, then attapulgite suspension is spray-dried in 150 DEG C, collects spray-dried composite powder obtained
End, finally by obtained composite powder in 200 DEG C of roasting 10min to get attapulgite-nano silver composite inorganic powder.
Composite powder obtained after above-mentioned spray-dried composite powder obtained and roasting is carried out X-ray respectively to spread out
(XRD) characterization is penetrated, table 2 is as a result listed in, the particle size range of nano silver is 3-100nm.
Embodiment 5
In addition to the time of magnetic agitation is adjusted to 2h after mix silver nitrate solution and attapulgite suspension, other techniques
Step is same as Example 4 with characterizing method, and characterization result is listed in table 2, and the particle size range of nano silver is 3-100nm.
Comparative example 2
Except by silver nitrate solution and attapulgite suspension, after mixing without heating magnetic agitation, Direct spraying is dry
Dry outer, other processing steps and characterizing method are same as Example 4, and characterization result is listed in table 2.
Comparative example 3
It is other in addition to the time of magnetic agitation is adjusted to 30min after mix silver nitrate solution and attapulgite suspension
Processing step is same as Example 4 with characterizing method, and characterization result is listed in table 2.
Composite powder characterization result prepared by embodiment 4-5 and comparative example 2-3 is listed in table 2.
Table 2
From Table 2, it can be seen that if other conditions are the same, mixing time is more than that 1h can guarantee finally to prepare
Obtain the composite powder containing nano silver.
Embodiment 6
The a certain amount of attapulgite through thermal activation and decentralized processing is weighed, is configured to attapulgite quality after distilled water is added
The suspension that concentration is 5%, then silver nitrate solution (AgNO3/ AT=135/100) it is added in attapulgite suspension,
At 90 DEG C, magnetic agitation 3h, then attapulgite suspension is spray-dried in 170 DEG C, it collects spray-dried obtained
Composite powder, finally by obtained composite powder in 200 DEG C of roasting 15min to get attapulgite-nano silver composite inorganic powder
End.
Composite powder obtained after above-mentioned spray-dried composite powder obtained and roasting is carried out X-ray respectively to spread out
(XRD) characterization is penetrated, table 3 is as a result listed in, the particle size range of nano silver is 3-100nm.
Embodiment 7
Except will spray drying after powder maturing temperature be adjusted to 300 DEG C in addition to, other processing steps are same as Example 6；
Characterizing method is same as Example 1, is as a result listed in table 3, and the particle size range of nano silver is 3-100nm.
Embodiment 8
Except will spray drying after powder maturing temperature be adjusted to 400 DEG C in addition to, other processing steps are same as Example 6；
Characterizing method is same as Example 1, is as a result listed in table 3, and the particle size range of nano silver is 3-100nm.
Embodiment 9
Except will spray drying after powder maturing temperature be adjusted to 500 DEG C in addition to, other processing steps are same as Example 6,
Characterization result is listed in table 3；Characterizing method is same as Example 1, is as a result listed in table 3, and the particle size range of nano silver is 3-100nm.
Comparative example 4
Except will spray drying after powder maturing temperature be adjusted to 150 DEG C in addition to, other processing steps are same as Example 6；
Characterizing method is same as Example 1, is as a result listed in table 3.
Composite inorganic Powder characterization result prepared by embodiment 6-8 and comparative example 4 is listed in table 3.
Table 3
From table 3 it is observed that if other conditions are the same, maturing temperature, which reaches 200 DEG C or more, to be made
It is standby to obtain nano silver composite powder of the invention.
Embodiment 10
The a certain amount of attapulgite through thermal activation and decentralized processing is weighed, is configured to attapulgite quality after distilled water is added
The suspension that concentration is 3%, then silver nitrate solution (AgNO3/ AT=50/100) it is added in attapulgite suspension, 70
At DEG C, magnetic agitation 2h, then attapulgite suspension is spray-dried at 170 DEG C, after collection is spray-dried
Obtained composite powder is roasted 5min at 350 DEG C finally to get attapulgite-nano silver composite inorganic powder by composite powder
End.
Composite powder obtained after above-mentioned spray-dried composite powder obtained and roasting is subjected to transmitted electron respectively
Microscope (TEM) characterizes (as shown in Figure 1) and X-ray diffraction (XRD) characterization (as shown in Figure 2), is as a result listed in table 4, nano silver
Particle size range be 3-100nm.
Embodiment 11
Except will it is spray-dried after powder calcining time be adjusted to 20min in addition to, other processing steps and characterizing method are equal
Same as in Example 10, characterization result is listed in table 4, and the particle size range of nano silver is 3-100nm.
Embodiment 12
Except will it is spray-dried after powder calcining time be adjusted to 60min in addition to, other processing steps and characterizing method are equal
Same as in Example 10, characterization result is listed in table 4, and the particle size range of nano silver is 3-100nm.
Embodiment 13
Except will it is spray-dried after powder calcining time be adjusted to 180min in addition to, other processing steps and characterizing method are equal
Same as in Example 10, characterization result is listed in table 4, and the particle size range of nano silver is 3-100nm.
Comparative example 5
Except will it is spray-dried after powder calcining time be adjusted to 2min in addition to, other processing steps and characterizing method with
Embodiment 10 is identical, and characterization result is listed in table 4.
Composite powder characterization result prepared by embodiment 10-13 and comparative example 5 is listed in table 4.
Table 4
As can be seen from Table 4, calcining time is more than that nano silver composite powder of the invention can be obtained in 5min.
Embodiment 14
In addition to silver nitrate and attapulgite mass ratio are adjusted to 135:100, other processing steps and characterizing method are equal
Same as Example 1, characterization result is listed in table 5, and the particle size range of nano silver is 3-100nm.
Comparative example 6
The a certain amount of attapulgite through thermal activation and decentralized processing is weighed, is configured to attapulgite quality after distilled water is added
The suspension that concentration is 1%, is then added to certain density hydrochloric acid solution in above-mentioned attapulgite suspension, room temperature magnetic force
Stir 1h, it is ensured that the carbonate contained by inside attapulgite is by hydrochloric acid fully reacting, by the concave convex rod after above-mentioned HCl treatment
Attapulgite is configured to the suspension that mass concentration is 1% after soil deionized water eccentric cleaning, then by silver nitrate (AgNO3/
AT=17/100) solution is added drop-wise in attapulgite solution, at 50 DEG C, magnetic agitation 1h, then by attapulgite suspension
It is spray-dried at 200 DEG C, the composite powder after being spray-dried is collected, finally by obtained composite powder 500
30min is roasted at DEG C.
Composite powder obtained after above-mentioned spray-dried composite powder obtained and roasting is carried out X-ray respectively to spread out
(XRD) characterization is penetrated, table 5 is as a result listed in.
Comparative example 7
Except will it is spray-dried after powder maturing temperature be adjusted to 300 DEG C in addition to, other processing steps and characterizing method are equal
Identical as comparative example 6, characterization result is listed in table 5.
Composite powder characterization result prepared by embodiment 14 and comparative example 6-7 is listed in table 5.
Table 5
As can be seen from Table 5, if the attapulgite in the present invention carried out at traditional thermal activation, dispersion and pickling
Reason, it will the chemical composition for changing attapulgite, it is compound that nano silver is prepared in the preparation method for leading to not through the invention
Powder.
Embodiment 15
The a certain amount of attapulgite through thermal activation and decentralized processing is weighed, is configured to attapulgite quality after distilled water is added
The suspension that concentration is 5%, then silver nitrate solution (AgNO3/ AT=135/100) it is added in attapulgite suspension,
At 90 DEG C, magnetic agitation 3h, then attapulgite suspension is spray-dried at 170 DEG C, after collection obtains spray drying
Composite powder, obtained composite powder is finally roasted into 30min at 500 DEG C.
Composite powder obtained after above-mentioned spray-dried composite powder obtained and roasting is carried out X-ray respectively to spread out
(XRD) characterization is penetrated, table 6 is as a result listed in, the particle size range of nano silver is 3-100nm.
Comparative example 8
In addition to directly being roasted after drying the attapulgite suspension after magnetic agitation in 80 DEG C of baking oven,
Its processing step and characterizing method are identical as embodiment 15, and characterization result is listed in table 6.
Comparative example 9
In addition to directly being roasted after drying the attapulgite suspension after magnetic agitation in 170 DEG C of baking oven,
Other processing steps and characterizing method are identical as embodiment 15, and characterization result is listed in table 6.
Composite powder acquired results prepared by embodiment 15 and comparative example 8-9 are listed in table 6.
Table 6
As can be seen from Table 6, it without spray drying, and after directly mixed solution is dried in an oven, is prepared into
Into nano silver composite powder also containing a large amount of unconverted nitric acid silver components, silver nitrate is soluble easily in water, is difficult in the application
It is attached together with attapulgite, is easily lost, to influence final application effect.Therefore, in preparation method of the invention
Drying process with atomizing be vital for nano silver composite powder is finally prepared.
Claims (7)
1. a kind of attapulgite-nano silver composite inorganic powder preparation method, which is characterized in that the described method includes:
(1) attapulgite and water are mixed and made into attapulgite suspension；The matter of attapulgite in the attapulgite suspension
Measuring concentration is no more than 10%；
(2) silver nitrate is added in attapulgite suspension described in step (1), is then stirred heat treatment；The nitre
The mass ratio of sour silver and attapulgite is 50/100-135/100；The heat treatment temperature is 50 DEG C or more, when the heat treatment
Between be 1h or more；
It (3) will treated that attapulgite suspension is spray-dried to obtain attapulgite clay compounded powder through step (2)；
(4) attapulgite clay compounded powder made from step (3) is roasted, obtains the composite inorganic powder containing nano silver；Its
In, maturing temperature is 200-500 DEG C, and calcining time is 5min or more；Nanometer of the roasting back loading in attapulgite's surface
The partial size of silver particles is 3-100nm.
2. attapulgite as described in claim 1-nano silver composite inorganic powder preparation method, it is characterised in that: step
(1) in, the attapulgite is the attapulgite by thermal activation and decentralized processing.
3. attapulgite as claimed in claim 2-nano silver composite inorganic powder preparation method, it is characterised in that: step
(1) in, the thermal activation uses method of roasting, wherein maturing temperature is 200-450 DEG C, calcining time 5-60min.
4. attapulgite as described in claim 1-nano silver composite inorganic powder preparation method, it is characterised in that: described
Heat treatment temperature is 50-90 DEG C.
5. attapulgite as described in claim 1-nano silver composite inorganic powder preparation method, it is characterised in that: described
The temperature of spray drying is 150-250 DEG C.
6. attapulgite as described in claim 1-nano silver composite inorganic powder preparation method, it is characterised in that: described
The calcining time of step (4) is 5-180min.
7. attapulgite made from the preparation method as described in any one of claim 1-6-nano silver composite inorganic powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510262409.5A CN106270479B (en) | 2015-05-21 | 2015-05-21 | A kind of attapulgite-nano silver composite inorganic powder and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510262409.5A CN106270479B (en) | 2015-05-21 | 2015-05-21 | A kind of attapulgite-nano silver composite inorganic powder and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106270479A CN106270479A (en) | 2017-01-04 |
| CN106270479B true CN106270479B (en) | 2018-12-28 |
Family
ID=57633611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510262409.5A Active CN106270479B (en) | 2015-05-21 | 2015-05-21 | A kind of attapulgite-nano silver composite inorganic powder and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106270479B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106862585A (en) * | 2017-01-22 | 2017-06-20 | 泉州师范学院 | It is a kind of to prepare CaCO by template of egg-shell meal3The method of Ag composites |
| CN107488274A (en) * | 2017-09-20 | 2017-12-19 | 界首市希捷仿真花卉有限公司 | A kind of preparation method of emulating plastics flower filler |
| CN108987698A (en) * | 2018-07-12 | 2018-12-11 | 东华大学 | A kind of preparation method of silver-carrying concave-convex stick soil matrix lithium ion battery negative material |
| CN110278962A (en) * | 2019-06-26 | 2019-09-27 | 广东工业大学 | A kind of attapulgite nanometer material and the preparation method and application thereof |
| CN111670913A (en) * | 2020-03-12 | 2020-09-18 | 华东理工大学 | Mesoporous iron oxide single crystal loaded with Ag nanoparticles, preparation method and its application in the field of antibacterial and antiviral |
| CN114698648B (en) * | 2022-03-29 | 2024-03-22 | 浙江恒达新材料股份有限公司 | Preparation method of nano silver loaded antibacterial fiber nano particles |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08133919A (en) * | 1994-11-10 | 1996-05-28 | Toto Ltd | Solid substance having antimicrobial action, its production and antimicrobial action on liquid and its flow channel |
| JPH09249511A (en) * | 1996-03-13 | 1997-09-22 | Miyoshi Oil & Fat Co Ltd | Antimicrobial agent and its production |
| CN1568703A (en) * | 2003-07-24 | 2005-01-26 | 合肥工业大学 | Attapulgite-argentum nanometer composite antibiotic material and preparation method thereof |
| CN101300981A (en) * | 2008-05-15 | 2008-11-12 | 兰州大学 | Nano silver-loaded attapulgite antibacterial agent and preparation method thereof |
| CN102071570A (en) * | 2010-06-25 | 2011-05-25 | 淮阴工学院 | Method for preparing rodlike ultrafine silver powder by carrying out chemical silvering on surfaces of attapulgite nanofibers |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1281126C (en) * | 2004-02-13 | 2006-10-25 | 黄德欢 | Nanometer silver antiseptic powder preparation method |
| CN100364408C (en) * | 2006-03-16 | 2008-01-30 | 上海师范大学 | Nano mesoporous silver-loaded antibacterial agent and preparation method thereof |
-
2015
- 2015-05-21 CN CN201510262409.5A patent/CN106270479B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08133919A (en) * | 1994-11-10 | 1996-05-28 | Toto Ltd | Solid substance having antimicrobial action, its production and antimicrobial action on liquid and its flow channel |
| JPH09249511A (en) * | 1996-03-13 | 1997-09-22 | Miyoshi Oil & Fat Co Ltd | Antimicrobial agent and its production |
| CN1568703A (en) * | 2003-07-24 | 2005-01-26 | 合肥工业大学 | Attapulgite-argentum nanometer composite antibiotic material and preparation method thereof |
| CN101300981A (en) * | 2008-05-15 | 2008-11-12 | 兰州大学 | Nano silver-loaded attapulgite antibacterial agent and preparation method thereof |
| CN102071570A (en) * | 2010-06-25 | 2011-05-25 | 淮阴工学院 | Method for preparing rodlike ultrafine silver powder by carrying out chemical silvering on surfaces of attapulgite nanofibers |
Non-Patent Citations (1)
| Title |
|---|
| 凹凸棒石抗菌复合材料制备及其抗菌试验研究;李宏伟;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20050615;第B020-10页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106270479A (en) | 2017-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106270479B (en) | A kind of attapulgite-nano silver composite inorganic powder and preparation method | |
| Karthik et al. | Acalypha indica–mediated green synthesis of ZnO nanostructures under differential thermal treatment: Effect on textile coating, hydrophobicity, UV resistance, and antibacterial activity | |
| CN100450677C (en) | Plant reduction method for preparing silver Nano granules and gold Nano granules | |
| CN106633364B (en) | A kind of antibacterial polypropylene and preparation method thereof | |
| CN105080526B (en) | A kind of titanium dioxide-diatom ooze composite process of indoor formaldehyde degradation by photocatalytic oxidation process prepared by biological template | |
| CN105623002B (en) | A kind of latex containing graphene and its preparation method and application | |
| CN103039521B (en) | Method for preparing antibacterial powder loaded with monodisperse silver nanometer mesoporous silica | |
| CN108477213A (en) | Nano zine oxide@carbon quantum dot complex antimicrobials and its preparation method and application | |
| CN101912976A (en) | Method for preparing silver nanoparticles by reduction of plant extract | |
| CN107413329A (en) | A kind of metal oxide-loaded method for preparation of active carbon | |
| CN102125056A (en) | Method for preparing silver/graphene antimicrobial composite material | |
| CN105887227B (en) | The preparation method of antibacterial and deodouring viscose rayon | |
| CN104525966B (en) | A kind of xanthan gum-argentum nano composite material and preparation method thereof | |
| Ermokhina et al. | Synthesis of large-pore mesoporous nanocrystalline TiO2 microspheres | |
| Nazir et al. | Photo-assisted inactivation of highly drug resistant bacteria and DPPH scavenging activities of zinc oxide graphted Pd-MCM-41 synthesized by new hydrothermal method | |
| CN1861095A (en) | Load type super-fine copper-powder copper-complementary agent, its prepn. method and use | |
| CN103146758A (en) | Method for preparing nano silver particles through microbial surface reduction | |
| CN107675292B (en) | A kind of nano-silver bamboo charcoal fiber and its Bactericidal underwear product | |
| CN100364549C (en) | Iron supplement for loaded superfine iron powder, preparation method and application | |
| KR100698342B1 (en) | Composite functional nano bio-ceramic composition and preparation method thereof | |
| CN106882791B (en) | The preparation method and applications of water dispersible carbon nano-onions | |
| CN101444726B (en) | Method of preparing high-performance TiO2 nanometer photocatalystic material | |
| CN101836660B (en) | Preparation method of composite nano-antibacterial, as well as antibacterial NL latex and antibacterial TPI rubber | |
| CN105665733A (en) | A green method for preparing graphite-like phase C3N4/nano-silver antibacterial composite material | |
| Xu et al. | Precise phase adjustment and antibacterial property of copper sulfide particles in confined mesoporous silica nanoreactor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |