CN107398562B - The preparation method of fulvic acid nano silver gel - Google Patents

The preparation method of fulvic acid nano silver gel Download PDF

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CN107398562B
CN107398562B CN201710572471.3A CN201710572471A CN107398562B CN 107398562 B CN107398562 B CN 107398562B CN 201710572471 A CN201710572471 A CN 201710572471A CN 107398562 B CN107398562 B CN 107398562B
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fulvic acid
nano silver
gel
acid nano
silver
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CN107398562A (en
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杨宁
李维宏
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Shanxi Agricultural University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00Medicinal preparations containing inorganic active ingredients
    • A61K33/24Heavy metals; Compounds thereof
    • A61K33/38Silver; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/46Ingredients of undetermined constitution or reaction products thereof, e.g. skin, bone, milk, cotton fibre, eggshell, oxgall or plant extracts
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/0012Galenical forms characterised by the site of application
    • A61K9/0014Skin, i.e. galenical aspects of topical compositions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/06Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Abstract

The invention discloses a kind of preparation methods of fulvic acid nano silver gel, including prepare fulvic acid fine powder, prepare silver nitrate aqueous solution, prepare fulvic acid Nano silver grain compound, prepare fulvic acid nano silver gel.The present invention uses reducing agent and stabilizer of the natural fulvic acid extracting solution as Nano silver grain, using microwave-assisted synthetic method, it is simple and quick, and without adding any chemical reagents in whole preparation process, preparation process has many advantages, such as environmentally protective, convenient and efficient.The nano silver partial size of fulvic acid nano silver gel prepared by the present invention is 15-42nm, granule-morphology is uniform, favorable dispersibility, to using staphylococcus aureus as the gram-positive bacteria of representative, using Escherichia coli as the Gram-negative bacteria of representative, to using Candida albicans as the fungi of representative, all there is preferable bacteriostasis, has a broad antifungal spectrum, no cytotoxicity can be widely used in field of medicaments, and have significant advantage than common nano-silver antibacterial hydrogel.

Description

The preparation method of fulvic acid nano silver gel
Technical field
The invention belongs to technical field of nano material, are related to a kind of preparation method of nano silver gel, and in particular to a kind of Use fulvic acid as the preparation method of reducing agent and stabilizer synthesis fulvic acid nano silver gel.
Background technique
Nano particle refers to particle of the size of at least one dimension spatially between 1-100nm.Nano silver particles tool There are many such as skin effect, volume (small size) effect, quantum size effect, the macro quanta tunnel effect of nano material The special nature that macroscopic material does not have.Nano silver particles do not have drug resistance as antibacterial agent, using safe natural, as Antibiotic and sterilizing material is increasingly subject to the attention of people.Nano silver can release silver ion in the solution, and silver ion has very strong Bactericidal effect.The antibiotic property of nano-Ag particles additionally depends on its size, compared to large-sized nano-Ag particles, small size nanometer Argent grain has better antibiotic property.So obtaining, partial size is small, and the stable nanometer silver products of property are particularly critical.Currently, preparation The method of nano silver restores silver ammino solution [Ag (NH using reducing agent3 ) ]2 +, while also needing to be put into a large amount of protective agents.Institute The reducing agent of use has hydrazine hydrate, sodium borohydride, sodium hypophosphite, glucose, ascorbic acid, hydrogen peroxide, sodium citrate etc., adopts Protective agent has PVP (polyvinylpyrrolidone), PVA (polyvinyl alcohol), gelatin, chitosan polymer etc..
Humic acid is a kind of high polymer matter of macromolecule, it is obtained by organic material decomposition, especially dead Plant.It is widely present in peat, soil and other substances, by a series of closely related complexity with aromatic structure High-molecular compound composition.Humic acid is a kind of natural organic mixture matter, is divided into three classes according to the size of its molecular weight yellow rotten Acid, ulmic acid and humic acid.Wherein the degree of oxidation of fulvic acid is high, and carboxyl containing active function groups, phenolic hydroxyl group, quinonyl are more, readily soluble Yu Shui, can be absorbed by the body utilization well, physical chemistry and in terms of be better than general humic acid, be doctor A kind of best humic acid of therapeutic effect.Before thousands of years, Li Shizhen (1518-1593 A.D.) is medicinal about humic acid in Compendium of Material Medica It records, mainly to treat the diseases such as nosebleed, women's qi and blood pain, pain in the chest and abdomen.In recent years, there are many reports also to affirm Fulvic acid hemostasis, anti-inflammatory, it is antiviral, adjust immune system, antibacterial, in terms of remarkable result.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of fulvic acid nano silver gel, and this method is with green non-pollution Resource fulvic acid is not necessarily to other any chemical reagents, simple process is easy to operate, and low energy consumption, obtains as reducing agent and stabilizer The fulvic acid nano silver gel arrived, nano silver particles are uniformly dispersed, soilless sticking, yield are high.
To achieve the above object, the invention adopts the following technical scheme.
The preparation method of fulvic acid nano silver gel of the present invention, includes the following steps:
(1) it prepares fulvic acid fine powder fulvic acid is placed in micronizer, crushes 25-35min, cross 120-160 mesh, Obtain fulvic acid fine powder;
(2) it prepares silver nitrate aqueous solution and weighs silver nitrate powder and distilled water, the silver nitrate for preparing 20-60mg/L is water-soluble Liquid, pH are adjusted to 7.0-9.0;
(3) silver nitrate aqueous solution that fulvic acid Nano silver grain compound takes (2) of certain volume to prepare is prepared in container In, fulvic acid fine powder prepared by (1) that concentration is 0.2-2g/L is added, is mixed evenly, container is then transferred to microwave In reactor, under 400~1000W power, 5~40 min is reacted, are cooled to room temperature after reaction, with distilled water, ethyl alcohol It is centrifuged respectively, after wash products 3-5 times, vacuum drying obtains fulvic acid Nano silver grain compound;
(4) fulvic acid nano silver gel is prepared by fulvic acid Nano silver grain compound, gel former and water by following Mass parts mixing: fulvic acid Nano silver grain compound 0.2%-0.5%, gel former 2%-5%, surplus is water;Mixed method It is as follows: fulvic acid Nano silver grain compound is mixed with water first and is placed in heating container, 50-80 DEG C is heated in stirring, Then constant temperature stirs, while being slowly added to gel former, then persistently constant temperature stirs 30min, cooling to receive to get having arrived fulvic acid Rice silver gel.
The pH value of the silver nitrate solution is preferably 9.0.
The reaction condition of the microwave reactor preferred 800W, 15min.
The gel former includes one of sodium alginate, xanthan gum, carbomer, guar gum and carragheen or more Kind.
The fulvic acid nano silver gel prepared using the method for the present invention, it is aobvious using X-ray diffractometer (XRD), transmitted electron Micro mirror (TEM), ultraviolet-uisible spectrophotometer (UV) carry out micromorphology analysis to product, and nano silver partial size is 15-42nm, grain Son is uniformly dispersed, soilless sticking, the result is shown in Figure 1-7.
Compared with prior art, the beneficial effects are mainly reflected as follows:
(1) reducing agent and stabilizer using natural fulvic acid extracting solution as Nano silver grain, use are microwave-assisted Synthetic method, simple and quick, and without adding any chemical reagents in whole preparation process, preparation process has green ring The advantages that guarantor, convenient and efficient.Huang is made by carrier of fulvic acid during preparation in fulvic acid nano silver gel of the invention Rotten acid nano-ag composite, dispersing agent and protective agent of the fulvic acid as nano silver make nano silver is uniform and stable to be distributed in water In gel rubber system.It is right using X-ray diffractometer (XRD), transmission electron microscope (TEM), ultraviolet-uisible spectrophotometer (UV) Prepared Nano silver grain carries out micromorphology analysis, and nano silver partial size is 15-42nm, and granule-morphology is uniform, and dispersibility is good It is good.
(2) fulvic acid nano silver gel of the invention is to using staphylococcus aureus as the gram-positive bacteria of representative, with Escherichia coli are the Gram-negative bacteria of representative, to using Candida albicans as the fungi of representative, all have preferable bacteriostasis, Has a broad antifungal spectrum, no cytotoxicity can be widely used in field of medicaments, and have than common nano-silver antibacterial hydrogel and show The advantage of work.
(3) fulvic acid nano silver gel of the invention not only has nanometer silver antimicrobial, also has both fulvic acid and sterilizes, is disease-resistant It is thin can to form layer of gel in wound surface after uniformly spraying fulvic acid nano silver gel for poison, erosion prevention and muscle growing etc. effect Film, bacteriostasis persistently, gas permeability and hygroscopicity it is good, effectively facilitate wound healing, have hemostasis, analgesic, anti-inflammatory sterilization work With.It can be used for burning, scald, the irregular wound of large area such as wound, it can also be used to bedsore, skin ulcer, tinea of feet and hands, Nv Xingyin Other scytitis such as road inflammation, cervicitis, cervical erosion.The antibacterial effect of simple nano silver is significantly improved, to promotion wound Growth reduces scar generation and has certain effect, and the silver nano-grain of this method synthesis has in fields such as biology, pharmacy, catalysis Applications well prospect.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram that the method for the present invention prepares gained nano silver.
Fig. 2 is prepared ultraviolet-visible absorbance phenogram of gained nano silver by the embodiment of the present invention 1.
Fig. 3 is prepared the TEM figure of gained nano silver by the embodiment of the present invention 1.
Fig. 4 is prepared ultraviolet-visible absorbance phenogram of gained nano silver by the embodiment of the present invention 2.
Fig. 5 is prepared the TEM figure of gained nano silver by the embodiment of the present invention 2.
Fig. 6 is prepared ultraviolet-visible absorbance phenogram of gained nano silver by the embodiment of the present invention 3.
Fig. 7 is prepared the TEM figure of gained nano silver by the embodiment of the present invention 3.
Specific embodiment
The method for preparing fulvic acid nano silver gel with the method for the present invention is exemplified below.
Embodiment 1
The method for preparing fulvic acid nano silver gel, includes the following steps:
(1) it prepares fulvic acid fine powder fulvic acid is placed in micronizer, crushes 30min, cross 140 meshes, obtain yellow corruption Sour fine powder;
(2) it prepares silver nitrate aqueous solution and weighs silver nitrate powder and distilled water, prepare the silver nitrate aqueous solution of 40mg/L, pH It is adjusted to 9.0;
(3) silver nitrate aqueous solution that fulvic acid Nano silver grain compound takes (2) of certain volume to prepare is prepared in container In, fulvic acid fine powder prepared by (1) that concentration is 1.0g/L is added, is mixed evenly, it is anti-that container is then transferred to microwave It answers in device, under 800W power, reacts 15min, be cooled to room temperature after reaction, be centrifuged, cleaned respectively with distilled water, ethyl alcohol After product 4 times, vacuum drying obtains fulvic acid Nano silver grain compound;
(4) fulvic acid nano silver gel is prepared by fulvic acid Nano silver grain compound, gel former and water by following Mass parts mixing: fulvic acid Nano silver grain compound 0.3%, alginate 2%, xanthan gum 2%, surplus is water;Mixed method is such as Under: fulvic acid Nano silver grain compound is mixed with water first and is placed in heating container, 50 DEG C are heated in stirring, it is then permanent Temperature stirring, while being slowly added to alginate and xanthan gum, then persistently constant temperature stirs 30min, cooling to receive to get having arrived fulvic acid Rice silver gel.
Fulvic acid nano silver gel X-ray diffraction (XRD) characterization result of synthesis is as shown in Figure 1, ultraviolet-visible absorbance Spectrum (UV-vis) characterization result is as shown in Fig. 2, transmission electron microscope (TEM) characterization result is as shown in Figure 3.Transmission electron microscope is seen Examine, the results showed that, the nano-Ag particles of synthesis are mostly almost spherical, and nano silver partial size is 15nm, size uniformity, good dispersion, It is not easy to reunite.
Embodiment 2
The method for preparing fulvic acid nano silver gel, includes the following steps:
(1) it prepares fulvic acid fine powder fulvic acid is placed in micronizer, crushes 35min, cross 160 meshes, obtain yellow corruption Sour fine powder;
(2) it prepares silver nitrate aqueous solution and weighs silver nitrate powder and distilled water, prepare the silver nitrate aqueous solution of 60mg/L, pH It is adjusted to 8.0;
(3) silver nitrate aqueous solution that fulvic acid Nano silver grain compound takes (2) of certain volume to prepare is prepared in container In, fulvic acid fine powder prepared by (1) that concentration is 2g/L is added, is mixed evenly, container is then transferred to microwave reaction In device, under 1000W power, 5 min is reacted, is cooled to room temperature after reaction, is centrifuged, is cleaned respectively with distilled water, ethyl alcohol After product 5 times, vacuum drying obtains fulvic acid Nano silver grain compound;
(4) fulvic acid nano silver gel is prepared by fulvic acid Nano silver grain compound, gel former and water by following Mass parts mixing: fulvic acid Nano silver grain compound 0.5%, carbomer 3% and carragheen 2%, surplus are water;Mixed method is such as Under: fulvic acid Nano silver grain compound is mixed with water first and is placed in heating container, 50 DEG C are heated in stirring, it is then permanent Temperature stirring, while it being slowly added to carbomer and carragheen, then persistently constant temperature stirs 30min, it is cooling to get fulvic acid nanometer has been arrived Silver gel.
Ultraviolet-visible absorption spectra (UV-vis) characterization result of the fulvic acid nano silver gel of synthesis as shown in figure 4, Transmission electron microscope (TEM) characterization result is as shown in Figure 5.Transmission electron microscope observing, the results showed that, the nano-Ag particles of synthesis are more For almost spherical, nano silver partial size is 42nm, size uniformity, good dispersion, not easy to reunite.
Embodiment 3
The method for preparing fulvic acid nano silver gel, includes the following steps:
(1) it prepares fulvic acid fine powder fulvic acid is placed in micronizer, crushes 25min, cross 120 meshes, obtain yellow corruption Sour fine powder;
(2) it prepares silver nitrate aqueous solution and weighs silver nitrate powder and distilled water, prepare the silver nitrate aqueous solution of 20mg/L, pH It is adjusted to 7.0;
(3) silver nitrate aqueous solution that fulvic acid Nano silver grain compound takes (2) of certain volume to prepare is prepared in container In, fulvic acid fine powder prepared by (1) that concentration is 0.2g/L is added, is mixed evenly, it is anti-that container is then transferred to microwave It answers in device, under 400W power, reacts 40 min, be cooled to room temperature after reaction, be centrifuged respectively with distilled water, ethyl alcohol, be clear After washing product 3 times, vacuum drying obtains fulvic acid Nano silver grain compound;
(4) fulvic acid nano silver gel is prepared by fulvic acid Nano silver grain compound, gel former and water by following Mass parts mixing: fulvic acid Nano silver grain compound 0.2%, guar gum 1% and carragheen 1%, surplus are water;Mixed method is such as Under: fulvic acid Nano silver grain compound is mixed with water first and is placed in heating container, 50 DEG C are heated in stirring, it is then permanent Temperature stirring, while it being slowly added to guar gum and carragheen, then persistently constant temperature stirs 30min, it is cooling to get fulvic acid nanometer has been arrived Silver gel.
Ultraviolet-visible absorption spectra (UV-vis) characterization result of the fulvic acid nano silver gel of synthesis as shown in fig. 6, Transmission electron microscope (TEM) characterization result is as shown in Figure 7.Transmission electron microscope observing, the results showed that, the nano-Ag particles of synthesis are more For almost spherical, nano silver partial size is 25nm, size uniformity, good dispersion, not easy to reunite.
With the fungistatic effect test of fulvic acid nano silver gel prepared by embodiment
1. test method
Using the nano-silver water gel of the present embodiment fulvic acid nano silver gel being prepared and prior art preparation into The test of row fungistatic effect.Strain include to staphylococcus aureus (Staphylococcus aureus) be representative leather it is blue Family name's positive bacteria, with Escherichia coli (Escherichia coli) for the Gram-negative bacteria of representative and with Candida albicans (Moniliaalbican) be representative fungi.Above-mentioned strain is the preservation of Microbiological Lab, Agricultural University Of Shanxi.
Bacteriostatic test is carried out using Odontothrips loti.It will be for examination strain point with beef-protein medium and sabouraud culture medium It is not inoculated into the test tube equipped with culture medium, cultivates for 24 hours, expand culture at 37 DEG C.Activated strain inclined plane is taken, with life It manages saline and contains 10 at every milliliter6~107The bacteria suspension of CFU, it is spare.Sterilized culture medium is heated to melt completely, It is poured in culture dish, about 20 mL of every ware, solidifies.Invisible spectro lawn is washed down with physiology salt and is diluted.Draw 1 mL bacterium solution Planar surface is poured into, is coated with bacterium solution uniformly with spreader.Oxford cup is placed, the novel fulvic acid nanometer of synthesis is added in cup Silver-colored solution, fills.It is put into 37 DEG C of incubators and cultivates 24 h, with vernier caliper measurement antibacterial circle diameter.Made with Nano silver solution Control.Operation is same as above.It is analyzed using SPSS v11 .5 software statistics, data are indicated with mean ± standard deviation (x ± S).
2, test result
Test result is shown in Table 1.
The antibacterial result of fulvic acid nano silver gel of 1 the method for the present invention of table preparation
Bacteriostatic experiment result is shown by table 1: fulvic acid nano silver gel and simple nanometer using the method for the present invention preparation Silver-colored hydrogel all has and preferably contacts bacteriostasis, and the contact surface of sample and culture medium is without bacterial growth.But in fulvic acid In nano silver gel and nano-silver water gel comparative test, then the antibacterial effect for the fulvic acid nano silver gel that prepared by three embodiments Fruit is significantly better than nano-silver water gel (p < 0.05), illustrates that fulvic acid enhances the bacteriostasis of nano-silver water gel.Wherein The fungistatic effect of fulvic acid nano silver gel prepared by best approach embodiment 1 is significantly better than embodiment 2 and 3 again.
In conclusion novel fulvic acid nano-silver antibacterial hydrogel is to using staphylococcus aureus as the gram of representative sun Property bacterium preferably connects to using Escherichia coli as the Gram-negative bacteria of representative to having using Candida albicans as the fungi of representative Touch bacteriostasis.The bacteriostasis of the novel fulvic acid nanometer silver antimicrobial temperature-sensitive hydrogel of the present invention is substantially better than other simple nanometers The bacteriostasis of silver-colored hydrogel, fulvic acid enhance the bacteriostasis of hydrogel.So the novel fulvic acid nano silver of the present invention is anti- Bacterium hydrogel is more significant than other hydrogel (such as simple nano-silver water gel) fungistatic effects, is worth clinical expansion.
Embodiment is the optimal specific embodiment of the present invention, is not intended to restrict the invention, although referring to before Stating embodiment, invention is explained in detail, for those skilled in the art, still can be to aforementioned each Technical solution documented by embodiment is modified or equivalent replacement of some of the technical features.It is all in the present invention Spirit and principle within, any modification, equivalent replacement, improvement and so on, should be included in protection scope of the present invention it It is interior.

Claims (4)

1. the preparation method of fulvic acid nano silver gel, includes the following steps:
(1) it prepares fulvic acid fine powder fulvic acid is placed in micronizer, crushes 25-35min, cross 120-160 mesh, obtain Fulvic acid fine powder;
(2) it prepares silver nitrate aqueous solution and weighs silver nitrate powder and distilled water, prepare the silver nitrate aqueous solution of 20-60mg/L, pH It is adjusted to 7.0-9.0;
(3) silver nitrate aqueous solution that fulvic acid Nano silver grain compound takes (2) of certain volume to prepare is prepared in container, Fulvic acid fine powder prepared by (1) that concentration is 0.2-2g/L is added, is mixed evenly, container is then transferred to microwave reaction In device, under 400~1000W power, 5~40 min are reacted, are cooled to room temperature after reaction, distinguished with distilled water, ethyl alcohol It is centrifuged, after wash products 3-5 times, vacuum drying obtains fulvic acid Nano silver grain compound;
(4) fulvic acid nano silver gel is prepared by fulvic acid Nano silver grain compound, gel former and water by following quality Part mixing: fulvic acid Nano silver grain compound 0.2%-0.5%, gel former 2%-5%, surplus is water;Mixed method is as follows: Fulvic acid Nano silver grain compound is mixed with water first and is placed in heating container, 50-80 DEG C is heated in stirring, it is then permanent Temperature stirring, while it being slowly added to gel former, then persistently constant temperature stirs 30min, it is cooling solidifying to get fulvic acid nano silver has been arrived Glue.
2. the preparation method of fulvic acid nano silver gel according to claim 1, which is characterized in that the silver nitrate is molten The pH value of liquid is preferably 9.0.
3. the preparation method of fulvic acid nano silver gel according to claim 1, which is characterized in that the microwave reaction The reaction condition of device preferred 800W, 15min.
4. the preparation method of fulvic acid nano silver gel according to claim 1, which is characterized in that the gel-forming Agent includes one of sodium alginate, xanthan gum, carbomer, guar gum and carragheen or a variety of.
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CN111375784B (en) * 2020-05-21 2022-07-12 宁夏师范学院 Method for preparing stable nano-silver gel
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