CN106758178A - A kind of method that carbonohydrazides complexing silver nitrate prepares antibiotic fabric product - Google Patents
A kind of method that carbonohydrazides complexing silver nitrate prepares antibiotic fabric product Download PDFInfo
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- CN106758178A CN106758178A CN201611173153.1A CN201611173153A CN106758178A CN 106758178 A CN106758178 A CN 106758178A CN 201611173153 A CN201611173153 A CN 201611173153A CN 106758178 A CN106758178 A CN 106758178A
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- Prior art keywords
- silver
- carbonohydrazides
- carbon fibe
- fabric
- silver nitrate
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- 239000004744 fabric Substances 0.000 title claims abstract description 72
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 44
- 229910001961 silver nitrate Inorganic materials 0.000 title claims abstract description 35
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical class NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 230000000536 complexating effect Effects 0.000 title claims abstract description 14
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 66
- 229910052709 silver Inorganic materials 0.000 claims abstract description 46
- 239000004332 silver Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 150000002500 ions Chemical class 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 14
- XYWUQOFFGCXNJO-UHFFFAOYSA-N NNC(=O)NN.[N+](=O)([O-])[O-].[Ag+] Chemical class NNC(=O)NN.[N+](=O)([O-])[O-].[Ag+] XYWUQOFFGCXNJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 8
- 238000009413 insulation Methods 0.000 claims abstract 2
- 238000007654 immersion Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 21
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000001994 activation Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 230000007306 turnover Effects 0.000 claims description 8
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims description 2
- 239000003651 drinking water Substances 0.000 claims description 2
- 235000020188 drinking water Nutrition 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 2
- 238000002798 spectrophotometry method Methods 0.000 claims description 2
- 238000004448 titration Methods 0.000 claims description 2
- 238000009423 ventilation Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000009467 reduction Effects 0.000 abstract description 8
- 230000002070 germicidal effect Effects 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 9
- 206010013786 Dry skin Diseases 0.000 description 7
- 239000003242 anti bacterial agent Substances 0.000 description 7
- SHOTZAAGWLBZQV-UHFFFAOYSA-N aminoazanium;carbonate Chemical compound NN.NN.OC(O)=O SHOTZAAGWLBZQV-UHFFFAOYSA-N 0.000 description 6
- 230000002421 anti-septic effect Effects 0.000 description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- RRKGBEPNZRCDAP-UHFFFAOYSA-N [C].[Ag] Chemical compound [C].[Ag] RRKGBEPNZRCDAP-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- 229910001923 silver oxide Inorganic materials 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003013 cytotoxicity Effects 0.000 description 2
- 231100000135 cytotoxicity Toxicity 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001717 pathogenic effect Effects 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
- 230000004537 potential cytotoxicity Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The present invention relates to the method that a kind of carbonohydrazides complexing silver nitrate prepares antibiotic fabric product, by with silver nitrate and carbonohydrazides complex solution, infiltrating Carbon fibe（Fabric）, by heat resolve and reduction, obtain the Carbon fibe of high stability（Fabric）Adsorption Nano Silver.It is 12 first to prepare mol ratio:5~9, Ag mass of ions concentration is 0.01~0.6% silver nitrate carbonohydrazides complex liquid；Carbon fibe（Fabric）Ratio with complex liquid is soaked 6~24 hours for 0.25~1Kg/ rises；150 360 DEG C under circulating nitrogen gas protection, insulation thermal decomposition in 0.5~6 hour；Dried after clear water washing, gained Nano Silver particle diameter is 10 ~ 60nm；0.01~0.4wt.% of silver carrying amount.Present invention reduces technological process, reaction temperature is reduced, disperse the Ag nano particles to be formed, improve the silver-colored Carbon fibe of load（Fabric）Germicidal efficiency, reduce silver-colored consumption.
Description
Technical field
Silver-colored Carbon fibe is carried the present invention relates to one kind（Fabric）Method.It is by molten with silver nitrate and carbonohydrazides complexing
Liquid, then infiltrate Carbon fibe（Fabric）, by heat resolve and reduction, using silver nitrate and the reaction heat of carbonohydrazides complex compound, obtain
Obtain the Carbon fibe of high stability（Fabric）Adsorption Nano Silver, for preparing the aspects such as efficient silver-series antibacterial agent fabric product.
Technical background
The invention belongs to the load silver process treatment of silver-series antibacterial agent fabric product.
Textile is one of essential product of human lives, and its daily life daily with people is closely bound up.So
And, because most of textiles itself have stronger moisture pick-up properties and larger specific surface area, so easily turning into various
The place of microbial growth.The textile for growing bacterium or other microorganisms can not only influence intensity, the color and luster of its own
With resistance to performance of waiting so long, the medium of the virus that spreads germs is will also become, harm user's is healthy.So, antiseptic of weaving
Research and development with using just increasingly turn into emphasis of concern.
Silver system textile antibacterial agent has the anti-microbial property of broad-spectrum high efficacy, and relatively broad answering is had in medicine and hygiene fieldses
With such as medical treatment such as surgical instruments, contraception apparatus, artificial limb medical equipment and operation dress, clothing of nurses, Wound dressing, bandage, mouth mask
Protective articles.Under pathogenic environmental high, the wide spectrum of silver-series antibacterial agent, efficient, safe, lasting antibacterial functions help to resist disease
Infringement of the bacterium to human body.Silver-series antibacterial agent can also be used for filter medium, silver system be added in water filtration or air filter anti-
Microbial inoculum, not only can effectively reduce bacterium in water or air, fungi and other harmful microorganisms, can also kill and remain in
Bacterium inside filter device, improves its security for using and the service life for extending filter core.
It is different according to carrier, the silver-colored silicate antiseptic of load can be divided into, silver-colored phosphate-based antiseptic, load silver Carbon fibe is carried
（Fabric）The silver-colored organic polymer antiseptic of antiseptic, load and the silver-colored photocatalyst-type anti-biotic agent of load etc..
Carry silver-colored Carbon fibe（Fabric）Preparation method be divided into front bearing silver method and rear bearing silver method.Front bearing silver method is mainly presoma
Carry silver-colored method, i.e., precursor fibre on be loaded with silver-colored source, then carry out activation charring process.The problem that front bearing silver method is present
Silver ion mainly in solution is difficult to load in precursor fibre, and after charing, activation, carbon fiber surface Argent grain point
Cloth is irregular, particle diameter is not of uniform size, and anti-microbial property is poor.
Rear bearing silver method is to load silver by the method such as physics, chemistry on the fabric for having prepared, such as dipping thermal decomposition method,
Immersion reduction method, composite spinning method, chemical deposition and physical sputtering method etc..Wherein dipping thermal decomposition method, immersion reduction method are
Relatively common load silver method：1. dipping thermal decomposition method is knitted using the film containing silver particles aqueous solution soaking such as silver nitrate, silver nitrate
Thing ,~700 DEG C are heated to after drying, and argent is obtained using silver oxide pyrolytic.It is required that calcined under inert gas shielding,
There can not be free air infiltration to enter in calcination process and temperature-fall period, once there is free air infiltration to enter, the argent for easily being formed can be oxidized to again
Silver oxide, its end product quality is difficult to control.Infusion process process is simple, low cost is pollution-free, and silver is distributed in fabric face,
Be conducive to sterilization.But the silver particles that the method is prepared mainly physical absorption, silver is easily lost in, it is impossible to reach lasting sterilization
Effect.2. immersion reduction method is to soak the fabric into a period of time in Ag-containing solution, then with a kind of reducing agent silver ion also
The former process into elemental silver.With NaBH4As a example by reduction, detailed process is fabric activation process, is soaked for a long time under the conditions of lucifuge
Stain is to AgNO3In solution, afterwards with distillation water washing until without silver ion detection in cleaning solution, NaBH is then immersed in again4Solution
In, washing removes unnecessary NaBH4, dried for a long time in cryogenic vacuum.The method can realize the good combination of fabric and Argent grain.
But reducing process process flow is long；Repeatedly washing is needed, water consumption is big, water resource requirement is high；The techniques such as lucifuge, vacuum are used, if
It is standby to require height；And Argent grain is mainly distributed in the outer surface and hole of fabric with reunion shape, the Argent grain of load than larger, and
Germicidal efficiency is not high.
Nano Silver is 30 × 10 in concentration-6When, with preferable antibacterial activity, but there is potential cytotoxicity；
3×10-6Under concentration, 2 grades of cytotoxicity.How to reduce its cytotoxicity problem and should give attention.At present, silver system antibacterial is reduced
The strategy of agent toxicity is mainly control, and it discharges concentration of silver ions higher than minimum inhibitory concentration, less than human body highest safe concentration.
For being applied to the silver-series antibacterial agent in the fields such as medical dressing, air and purification of water quality, it should also be noted that coming off for Argent grain is avoided,
Because the amount of coming off of Argent grain directly affects silver ion burst size, the service life and antibacterial continuation of antiseptic can be also influenceed.
The content of the invention
It is an object of the invention to provide a kind of load silver Carbon fibe with efficient, lasting bactericidal action（Fabric）Preparation side
Method.
The technical solution adopted for the present invention to solve the technical problems is that complexing and reduction using carbonohydrazides will
Silver ion is adsorbed in Carbon fibe with complex form（Fabric）Surface and micropore in, then at a lower temperature it is quick also
Former, decomposition, the load silver Carbon fibe for obtain good dispersion, not easily runing off（Fabric）.It is specific as follows：
(1) prepared by silver nitrate-carbonohydrazides complex liquid：A certain amount of silver nitrate crystal and carbonohydrazides crystal are weighed, it is water-soluble with distilling
Solution, obtains silver-colored ammonium nitrate complex liquid.Wherein, silver nitrate and the molar ratio of carbonohydrazides are 12:5~9, Ag in the aqueous solution of preparation
Mass of ion concentration is 0.01~0.6%.
(2) silver ion soaks, dries Carbon fibe（Fabric）Shaken with the silver nitrate for preparing-alanine complex liquid room temperature
Swing, soak through the Carbon fibe after charing, activation process（Fabric）, soak time is 6~24 hours；Carbon fibe during immersion（Fabric）
It is 0.25~1Kg/ liters with the ratio of complex liquid；It is filtered dry in ventilated environment, light protected environment after immersion；Then in hot blast, such as electric heating
Air dry oven, 30~70 DEG C of dryings to constant weight remove water and the crystallization water.
(3) pyrolysis：Carbon fibe after immersion is dried（Fabric）It is warming up at 120-180 DEG C, soaking time is
0.5~6 hour.Protected using dry circulating nitrogen gas during thermal decomposition, can also be protected using ammonia is decomposed when having ready conditions.Using pushing away boat
The continuous furnaces such as stove, net belt type drying oven, rotary furnace can realize continuous production.Programming rate is controlled at 0.1~2 DEG C/min,
Avoiding pyrolysis excessively acutely influences Nano Silver dispersiveness and and Carbon fibe（Fabric）The interface binding power on surface.
(4) wash：By above-mentioned Carbon fibe（Fabric）With pure water washing 2~4 times, the reactant of remnants is washed away.In order to keep away
Exempt from silver particles oxidation, the drying temperature after cleaning is controlled at 50~120 DEG C.Silver-colored remaining quantity≤the 10ppb of the water after cleaning（It is micro-
G/l), reach the standard of drinking water.
(5) detect：Sodium sulfocyanate standard liquid titration determination silver carrying amount, scanning electron microscopic observation Argent grain are used per batch
Pattern and size, and in 25 DEG C, 150 r/min, constant temperature oscillation is after 600 hours, anti-with the swollen Spectrophotometric Determination of Silver of double sulphur
Flow and failure property, turnover rate≤30% of silver, silver carrying amount receives Carbon fibe specific surface and absorption property, complex liquid silver content, soaking technology
With the influence of the parameter of thermal decomposition process, when silver carrying amount is less than 0.01 desired~0.40wt.%, repeat step（2）Silver ion
Soak, dry Carbon fibe and step（3）Pyrolysis are increasing silver carrying amount.
Silver nitrate is 12 with the mol ratio of carbonohydrazides:6~9.
Step（1）Ag mass of ions concentration is 0.01~0.1% in the aqueous solution of preparation.
Step（3）It is middle will immersion dry after Carbon fibe be warming up to 140-160 DEG C.
By silver nitrate (AgNO3) as oxidant, carbonic acid hydrazine (CH6N4O) as complexing reducing agent, it is configured to the aqueous solution；Will
Solution gradually evaporates can form gel.Carbonic acid hydrazine fusing point only has 153 DEG C, and silver nitrate just can be rapid at 120 DEG C with carbonic acid hydrazine gel
React, release a large amount of gases and heat, can obtain scattered nano level superfine silver powder.Carbon is there occurs during this first
, there is NH in the decomposition reaction of sour hydrazine4 +.With the carrying out of heating, water evaporation, the NH in solution4 +And NO3 -Ion is then with NH4NO3It is brilliant
The form of body is separated out, and finally gives AgOH, Ag2O and NH4NO3The mixture of crystal.Above-mentioned mixed crystal is further heated,
The decomposition reaction of complexity can occur, Nano Silver and CO is obtained2、H2O、N2O、N2Deng gas.
When silver nitrate and carbonic acid hydrazine are in molar ratio 12:Reaction equation when 5 is as follows：
12AgNO3+5CH6N4O→12Ag+5CO2+15H2O+16N2O
When silver nitrate and carbonic acid hydrazine are in molar ratio 4:Reaction equation when 3 is as follows：
4AgNO3+3CH6N4O→4Ag+3CO2+9H2O+8N2
When silver nitrate is excessive, reaction occurs the oxide of silver；When reducing agent carbonic acid hydrazine is further excessive, it is necessary to oxygen is joined
With reaction, or ammonia is discharged.
The present invention carries silver-colored Carbon fibe for producing（Fabric）, with reaction temperature is low and the characteristics of efficiency high, generally 120
Between~180 DEG C, the heat promotion reaction of decomposition reaction release is carried out.Compared with conventional dipping and thermal decomposition process, shorten
Technological process, is reduced reaction temperature, avoids the occurrence of the Ag particles caused due to pyroreaction and combined loosely with carbon surface
Easily there is the problem of silver oxide.Compared with conventional reduction method, dipping time is reduced, and due to network of the present invention
Close Ag compounds and decompose a large amount of gas such as NH of generation3、H2O、CO2、N2, N2O etc., disperses the Ag nano particles to be formed, and overcomes
General N aBH4The Ag particle agglomeration phenomenons for preparing are reduced, high silver supported Carbon fibe is carried（Fabric）Germicidal efficiency, reduce silver-colored consumption.
Present invention process process is simple, easily operated, yield is high, be easy to industrialized production, with clean, environmental protection and
Characteristics of energy saving.Gained Nano Silver particle diameter is 8 ~ 50nm；0.01~0.42wt.% of silver carrying amount；Argent grain and Carbon fibe（Fabric）Knot
High with joint efforts, 150r/min vibrates in 25 DEG C of thermostatted waters, after 600 hours, turnover rate≤20% of silver；Argent grain good dispersion, kill
Bacterium efficiency high.
Specific embodiment
The present invention is elaborated below by way of specific embodiment.
Embodiment 1
(1) prepared by silver nitrate-carbonohydrazides complex liquid：17g silver nitrates and 6.75g carbonohydrazides are weighed, with distillation water dissolves, is obtained
100 liters of silver-colored ammonium nitrate complex liquids.Wherein, silver nitrate and the molar ratio of carbonohydrazides are 4:3, Ag ions matter in the aqueous solution of preparation
Amount concentration is about 0.01%.
(2) silver ion soaks, dries Carbon fibe（Fabric）：By through the Carbon fibe after charing, activation process（Fabric）With steaming
Distilled water is cleaned, dries, cooled.It is 4 to be about 0.01%, molar ratio with Ag mass of ion concentration:3 silver nitrate-carbonohydrazides complexing
Liquid shaken at room temperature, immersion Carbon fibe（Fabric）, soak time is 6 hours；Carbon fibe during immersion（Fabric）With the ratio of complex liquid
It is 1Kg/ liters；It is filtered dry in ventilated environment, light protected environment after immersion；In electric drying oven with forced convection, 30 DEG C of dryings to constant weight remove water
And the crystallization water.
(3) pyrolysis：Carbon fibe after immersion is dried（Fabric）It is warming up at 120 DEG C, soaking time is 6 hours.
Using being dried in dry circulating nitrogen gas protection tube furnace during thermal decomposition, programming rate is 2 DEG C/min.
(4) wash：By above-mentioned Carbon fibe（Fabric）With pure water washing 2 times, the reactant of remnants is washed away.After cleaning
Electric drying oven with forced convection, 50 DEG C of dryings to constant weight.
(5) detect：Gained Nano Silver particle diameter is 8nm；Silver carrying amount 0.01%；Argent grain and Carbon fibe（Fabric）Adhesion
Height, 150r/min vibrates in 25 DEG C of thermostatted waters, and after 600 hours, the turnover rate of silver is 6%.
Embodiment 2
(1) prepared by silver nitrate-carbonohydrazides complex liquid：17g silver nitrates and 6.75g carbonohydrazides are weighed, with distillation water dissolves, is obtained
18 liters of silver-colored ammonium nitrate complex liquids.Wherein, silver nitrate and the molar ratio of carbonohydrazides are 4:3, Ag ions matter in the aqueous solution of preparation
Amount concentration is about 0.6%.
(2) silver ion soaks, dries Carbon fibe（Fabric）：By through the Carbon fibe after charing, activation process（Fabric）With steaming
Distilled water is cleaned, dries, cooled.It is about 0.6% with Ag mass of ion concentration, molar ratio is 4:3 silver nitrate-carbonohydrazides complexing
Liquid shaken at room temperature, immersion Carbon fibe（Fabric）, soak time is 24 hours；Carbon fibe during immersion（Fabric）With the ratio of complex liquid
It is 1Kg/ liters；It is filtered dry in ventilated environment, light protected environment after immersion；In electric drying oven with forced convection, 70 DEG C of dryings to constant weight remove water
And the crystallization water.
(3) pyrolysis：Carbon fibe after immersion is dried（Fabric）It is warming up at 180 DEG C, soaking time is 0.5 small
When.Protected using dry circulating nitrogen gas at 0.1 DEG C/min using net belt type drying oven, programming rate control during thermal decomposition.
(4) wash：By above-mentioned Carbon fibe（Fabric）With pure water washing 4 times, the reactant of remnants is washed away.Used after cleaning
In net belt type drying oven, 120 DEG C of dryings to constant weight.
(5) detect：Gained Nano Silver particle diameter is 48nm；Silver carrying amount 0.42%；Argent grain and Carbon fibe（Fabric）Adhesion
Height, 150r/min vibrates in 25 DEG C of thermostatted waters, and after 600 hours, the turnover rate of silver is 19%.
Embodiment 3
(1) prepared by silver nitrate-carbonohydrazides complex liquid：17g silver nitrates and 3.75g carbonohydrazides are weighed, with distillation water dissolves, is obtained
18 liters of silver-colored ammonium nitrate complex liquids.Wherein, silver nitrate and the molar ratio of carbonohydrazides are 12:5, Ag ions matter in the aqueous solution of preparation
Amount concentration is about 0.6%.
(2) silver ion soaks, dries Carbon fibe（Fabric）：By through the Carbon fibe after charing, activation process（Fabric）With steaming
Distilled water is cleaned, dries, cooled.It is about 0.6% with Ag mass of ion concentration, molar ratio is 12:5 silver nitrate-carbonohydrazides complexing
Liquid shaken at room temperature, immersion Carbon fibe（Fabric）, soak time is 12 hours；Carbon fibe during immersion（Fabric）With the ratio of complex liquid
It is 0.25Kg/ liters；It is filtered dry in ventilated environment, light protected environment after immersion；Dried to constant weight in 60 DEG C of heated-air dryings cylinder, removing water and
The crystallization water.
(3) pyrolysis：Carbon fibe after immersion is dried（Fabric）It is warming up at 140 DEG C, soaking time is 3 hours.
Boat drying oven, programming rate control are pushed away at 0.5 DEG C/min using automatic during thermal decomposition, are protected using dry circulating nitrogen gas.
(4) wash：By above-mentioned Carbon fibe（Fabric）With pure water washing 3 times, the reactant of remnants is washed away.Used after cleaning
Automatically boat drying oven, 110 DEG C of dryings to constant weight are being pushed away.
(5) detect：Gained Nano Silver particle diameter is 30nm；Silver carrying amount 0.16%；Argent grain and Carbon fibe（Fabric）Adhesion
Height, 150r/min vibrates in 25 DEG C of thermostatted waters, and after 600 hours, the turnover rate of silver is 10%.
Embodiment 4
(1) prepared by silver nitrate-carbonohydrazides complex liquid：17g silver nitrates and 6.0g carbonohydrazides are weighed, with distillation water dissolves, 36 is obtained
Rise silver-colored ammonium nitrate complex liquid.Wherein, silver nitrate and the molar ratio of carbonohydrazides are 3:2, Ag mass of ions in the aqueous solution of preparation
Concentration is about 0.3%.
(2) silver ion soaks, dries Carbon fibe（Fabric）：By through the Carbon fibe after charing, activation process（Fabric）With steaming
Distilled water is cleaned, dries, cooled.It is about 0.3% with Ag mass of ion concentration, molar ratio is 3:2 silver nitrate-carbonohydrazides complexing
Liquid shaken at room temperature, immersion Carbon fibe（Fabric）, soak time is 12 hours；Carbon fibe during immersion（Fabric）With the ratio of complex liquid
It is 0.5Kg/ liters；It is filtered dry in ventilated environment, light protected environment after immersion；Dried to constant weight in 60 DEG C of heated-air dryings cylinder, removing water and
The crystallization water.
(3) pyrolysis：Carbon fibe after immersion is dried（Fabric）It is warming up at 160 DEG C, soaking time is 3 hours.
Boat drying oven, programming rate control are pushed away at 0.5 DEG C/min using automatic during thermal decomposition, are protected using dry circulating nitrogen gas.
(4) wash：By above-mentioned Carbon fibe（Fabric）With pure water washing 2 times, the reactant of remnants is washed away.Used after cleaning
Automatically boat drying oven, 120 DEG C of dryings to constant weight are being pushed away.
(5) detect：Gained Nano Silver particle diameter is 33nm；Silver carrying amount 0.3%；Argent grain and Carbon fibe（Fabric）Adhesion
Height, 150r/min vibrates in 25 DEG C of thermostatted waters, and after 600 hours, the turnover rate of silver is 15%.
Embodiment 5
(1) prepared by silver nitrate-carbonohydrazides complex liquid：8.5g silver nitrates and 2.63g carbonohydrazides are weighed, with distillation water dissolves, is obtained
36 liters of silver-colored ammonium nitrate complex liquids.Wherein, silver nitrate and the molar ratio of carbonohydrazides are 12:7, Ag ions matter in the aqueous solution of preparation
Amount concentration is about 0.15%.
(2) silver ion soaks, dries Carbon fibe（Fabric）：By through the Carbon fibe after charing, activation process（Fabric）With steaming
Distilled water is cleaned, dries, cooled.It is about 0.15% with Ag mass of ion concentration, molar ratio is 12:7 silver nitrate-carbonohydrazides network
Close liquid shaken at room temperature, immersion Carbon fibe（Fabric）, soak time is 9 hours；Carbon fibe during immersion（Fabric）With the ratio of complex liquid
Example is 0.25Kg/ liters；It is filtered dry in ventilated environment, light protected environment after immersion；Dried to constant weight in 50 DEG C of heated-air drying cylinders, remove water
And the crystallization water.
(3) pyrolysis：Carbon fibe after immersion is dried（Fabric）It is warming up at 150 DEG C, soaking time is 2 hours.
Tube furnace, programming rate is protected to control at 1 DEG C/min using dry circulating nitrogen gas during thermal decomposition.
(4) wash：By above-mentioned Carbon fibe（Fabric）With pure water washing 2 times, the reactant of remnants is washed away.With 90 after cleaning
DEG C air dry oven drying is to constant weight.
(5) detect：Gained Nano Silver particle diameter is 20nm；Silver carrying amount 0.03%；Argent grain and Carbon fibe（Fabric）Adhesion
Height, 150r/min vibrates in 25 DEG C of thermostatted waters, and after 600 hours, the turnover rate of silver is 12%.
Claims (4)
1. a kind of method that carbonohydrazides complexing silver nitrate prepares antibiotic fabric product, it is characterised in that comprise the following steps：
(1) prepared by silver nitrate-carbonohydrazides complex liquid：Silver nitrate crystal and carbonohydrazides crystal are weighed, with distillation water dissolves, is obtained
Silver-colored ammonium nitrate complex liquid, silver nitrate is 12 with the mol ratio of carbonohydrazides:5~9, Ag mass of ions concentration is in the aqueous solution of preparation
0.01~0.6%；
(2) silver ion soaks, dries Carbon fibe：With the silver nitrate for preparing-alanine complex liquid shaken at room temperature, immersion warp
Carbon fibe after charing, activation process, soak time is 6~24 hours；The ratio of Carbon fibe and complex liquid is 0.25 during immersion
~1Kg/ liters；It is filtered dry in ventilation, light protected environment after immersion；Then dried to constant weight in 30~70 DEG C of hot blast, removing water and
The crystallization water；
(3) pyrolysis：Carbon fibe is warming up at 120-180 DEG C after immersion is dried, and insulation carries out heat in 0.5~6 hour
Decompose, protected using dry circulating nitrogen gas during thermal decomposition, or protected using ammonia is decomposed；Using pushing away boat stove, net belt type drying oven
Or rotary furnace continuous furnace, realize continuous production；Programming rate is controlled at 0.1~2 DEG C/min；
(4) wash：By above-mentioned Carbon fibe pure water washing 2~4 times, the reactant of remnants is washed away；In order to avoid silver particles oxygen
Change, the drying temperature after cleaning is controlled at 50~120 DEG C, and the silver-colored remaining quantity≤10ppb of the water after cleaning reaches the mark of drinking water
It is accurate；
(5) detect：Sodium sulfocyanate standard liquid titration determination silver carrying amount, scanning electron microscopic observation Argent grain pattern are used per batch
And size, and in 25 DEG C, 150 r/min, constant temperature oscillation is lost after 600 hours with the anti-current of the swollen Spectrophotometric Determination of Silver of double sulphur
Performance, turnover rate≤30% of silver, silver carrying amount receives Carbon fibe specific surface and absorption property, complex liquid silver content, soaking technology and heat
The influence of the parameter of decomposition technique, when silver carrying amount is less than 0.01 desired~0.40wt.%, repeat step（2）Silver ion soaks
Steep, dry Carbon fibe and step（3）Pyrolysis are increasing silver carrying amount.
2. the method that carbonohydrazides complexing silver nitrate as claimed in claim 1 prepares antibiotic fabric product, it is characterised in that：Silver nitrate
It is 12 with the mol ratio of carbonohydrazides:6~9.
3. the method that carbonohydrazides complexing silver nitrate as claimed in claim 1 prepares antibiotic fabric product, it is characterised in that：Step
（1）Ag mass of ions concentration is 0.01~0.1% in the aqueous solution of preparation.
4. the method that carbonohydrazides complexing silver nitrate as claimed in claim 1 prepares antibiotic fabric product, it is characterised in that：Step
（3）It is middle will immersion dry after Carbon fibe be warming up to 140-160 DEG C.
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| CN114989596A (en) * | 2022-06-21 | 2022-09-02 | 佛山市三水日邦化工有限公司 | Antibacterial polyurethane film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006014965A (en) * | 2004-07-02 | 2006-01-19 | Suzutora:Kk | Deodorant fiber sheet |
| CN103451920A (en) * | 2013-08-16 | 2013-12-18 | 北京林业大学 | Preparation method of silver-loaded active wood carbon fiber |
| WO2016057816A1 (en) * | 2014-10-08 | 2016-04-14 | University Of South Alabama | Modification of fibers with nanostructures using reactive dye chemistry |
| CN105887474A (en) * | 2016-06-07 | 2016-08-24 | 北京中船经济技术开发有限公司 | Graphene purification and sterilization cloth |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006014965A (en) * | 2004-07-02 | 2006-01-19 | Suzutora:Kk | Deodorant fiber sheet |
| CN103451920A (en) * | 2013-08-16 | 2013-12-18 | 北京林业大学 | Preparation method of silver-loaded active wood carbon fiber |
| WO2016057816A1 (en) * | 2014-10-08 | 2016-04-14 | University Of South Alabama | Modification of fibers with nanostructures using reactive dye chemistry |
| CN105887474A (en) * | 2016-06-07 | 2016-08-24 | 北京中船经济技术开发有限公司 | Graphene purification and sterilization cloth |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114989596A (en) * | 2022-06-21 | 2022-09-02 | 佛山市三水日邦化工有限公司 | Antibacterial polyurethane film and preparation method thereof |
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