CN107699874A - A kind of nano silver fibre element composite and its preparation method and application - Google Patents
A kind of nano silver fibre element composite and its preparation method and application Download PDFInfo
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- CN107699874A CN107699874A CN201710832257.7A CN201710832257A CN107699874A CN 107699874 A CN107699874 A CN 107699874A CN 201710832257 A CN201710832257 A CN 201710832257A CN 107699874 A CN107699874 A CN 107699874A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
Abstract
The present invention provides a kind of nano silver fibre element composite and its preparation method and application, is related to field of nanocomposite materials.The present invention overcomes prepares nano silver fibre element composite by the use of chemical agent as reducing agent, oxidant or stabilizer in the prior art, so as to bring environmental pollution, improve the defects of preparing cost and subsequent treatment cost, there is provided easy, efficient, reaction condition the is controllable nano silver fibre element composite material preparation process of a kind of clean environment firendly, method.The technique mainly includes (1) and immersed cellulose membrane in the water that pH is 5 10, and concussion mixes；(2) silver salt solution is added into step (1), concussion shakes up；(3) cellulose membrane of step (2) and mixed liquor are placed in microwave reactor and carry out microwave reaction；(4) compound is dried, that is, obtains nano silver fibre element composite.Nano silver fibre element composite prepared by the method can be widely applied to the fields such as medical treatment, packaging.
Description
Technical field
The invention belongs to field of nanocomposite materials, and in particular to a kind of preparation side of Nano Silver-cellulose composite material
Method and application.
Background technology
Cellulose is the cellulose by Microbe synthesis, it be by glucose molecule by β-Isosorbide-5-Nitrae-glucosides key connection and
Into.Cellulose caused by cellulose and plant and marine alga is identical in the chemically, but cellulose is as a kind of new life
Thing material, there are many unique properties：(1) high-crystallinity and high chemical purity (2) high-tensile and modulus of elasticity.(3) very
Strong moisture holding capacity and rehydration ability.(4) splendid shape maintains ability and tear resistance.(5) good biocompatibility and
Good biodegradability.(6) during biosynthesis performance Modulatory character.Although cellulose with numerous excellent performances,
But cellulose does not have bacteriostasis in itself, and it is difficult to prevent wound by microorganism infection.
Nano Silver is a kind of broad spectrum antimicrobial agent, can not only kill Gram-negative bacteria, can also kill Gram-positive
Bacterium, and tolerant bacteria will not be produced in whole process, so Nano Silver is a kind of good antiseptic.Nano Silver is as anti-
Microbial inoculum, although the purpose of antibacterial can be reached in use, the deposition of Nano Silver may be caused, body be produced negative
Face rings.Therefore in order to avoid Nano silver deposition and the anti-microbial property of Nano Silver is realized, with regard to Nano Silver slow-release material need to be prepared
Eliminate this adverse effect.Cellulose possesses the numerous superperformance of the above, and this is provided for cellulose as composite substrate
Bigger possibility, while cellulose can make metal ion in cellulose by ionic interaction fixing metal ions
In be uniformly distributed and the sustained release of metal nanoparticle can be realized.The preparation additional reduction mostly of present nano silver composite material
Agent, such as sodium borohydride, hydrazine hydrate, formaldehyde, these reagents have higher toxicity, and are difficult to solve it after preparation terminates
Residue problem.Therefore there is an urgent need to develop a kind of method of the simple efficient synthesizing nano-silver cellulose composite material of green.
The A of Publication No. CN 102212806 patent of invention discloses a kind of " system of cellulose-nano silver composite material
Preparation Method ", the composite are prepared by following steps：After cellulose wet-coating is crushed, it is placed in silver salt solution and soaks
Stain, the cellulose for adsorbing silver ion is transferred in polyglycol solution, then ascorbic acid solution, warp is added dropwise to this mixed system
After centrifuging, wash and drying, cellulose-nano silver composite material is obtained.The present invention is under polyethylene glycol protection using anti-
Bad hematic acid reduces the method for silver ion, at the same play polyethylene glycol stabilization and ascorbic acid reaction it is gentle, nontoxic etc. excellent
Point, form the nano composite system that particle diameter is small, is evenly distributed.Cellulose-nano silver composite material can be used for medical antibacterial dressing
Deng field.But the invention is after being crushed to cellulose wet-coating, then the preparation of the composite carried out, this method undoubtedly improve
Time cost and the equipment cost for mechanical crushing input prepared by material.In addition, the process employs ascorbic acid reduction
The method of silver ion, while stabilizer polyethylene glycol is with the addition of, preparation cost is not only increased, and make preparation method complicated
Change, and after the completion of reaction, add the difficulty of reaction dissolvent post processing.
" microcrystalline cellulose/gamma-polyglutamic acid-Nano Silver is compound for the A of Publication No. CN 105236532 disclosure of the invention
The preparation method of material ", after the composite is by the way that microcrystalline cellulose is pre-processed, silver salt impregnation is added, then it is mixed to this
Reducing agent reduction is added in zoarium system, after being centrifuged, washs to neutrality, dry, then be placed in gamma-polyglutamic acid solution and soak
Stain, finally cellulosic molecule obtains after carrying out cross-linking reaction with gamma-polyglutamic acid under carbodiimides effect.The present invention is micro-
A certain amount of gamma-polyglutamic acid is crosslinked in crystalline cellulose-nano silver composite material, the bactericidal action of silver ion can be played, and
The flocculation of gamma-polyglutamic acid.Microcrystalline cellulose/gamma-polyglutamic acid-the nano silver composite material prepared can be used at water
Reason field.The invention needs to rely on crosslinked action loading nano silvery of the gamma-polyglutamic acid as crosslinking agent, and what it was additionally added goes back
Former agent and crosslinking agent, it is clear that improve the preparation cost of composite.
" a kind of silver-carrying modified cellulose base compounding function hygrometric state applies the A of Publication No. CN 102266583 disclosure of the invention
The preparation method of material ", the invention are related to a kind of preparation method of silver-carrying modified cellulose base compounding function hygrometric state dressing, including such as
Lower step：(1) cellulose after freeze-drying is placed among nitroxyl/enzyme system solution, adds oxidant reaction；(2)
Add in Diamines substance solution, heating response；(3) and then it is immersed in silver nitrate solution, obtains the silver of load containing selectivity
The cellulose of ion；Or above-mentioned cellulose is reduced to obtain the cellulose of selective loading nano silvery particle by high pressure again；
(4) combination solution is eventually adding, is taken out after being stored at room temperature, process is partially dried, packs, sterilizing, you can obtains silver-carrying modified fibre
Tie up plain base Compositional type function hygrometric state dressing.Antibacterial nano-silver, can be carried on cellulose C6 positions hydroxyl by the method for the present invention
On, and compound functional drug.Obtained dressing can treat various skin injuries, wound, empyrosis wound surface etc., have very well
Antibacterial, repairing effect.The oxidant additionally added in two above invention aoxidizes to cellulose, not only anti-to the later stage
Answer the processing of solvent to cause difficulty, environment is polluted, and the preparation cost of cellulose can be significantly improved.
The content of the invention
The present invention solves the problems, such as it is to overcome above-mentioned to prepare Nano Silver-fibre by the use of chemical agent as reducing agent or oxidant
Dimension element, there is provided a kind of methods and applications for preparing nano silver fibre element composite, the preparation method are in-situ synthesis, not only
Without doing any mechanical mashing processing to cellulose, simplify preparation technology, save the time cost and equipment cost of preparation, and
And the preparation method instead of the addition of reducing agent, oxidant and stabilizer completely, and method is simple, saves time cost
And cost of material；Efficiently, preparation efficiency is significantly improved, effectively improves nano-silver loaded rate, significantly improves the function of composite
Property；Green, preparation method is green, without adding any reducing agent, oxidant, stabilizer etc., belongs to environmentally friendly system
Standby technique；Controllable, reaction condition simplicity is controllable.
Meanwhile the nano silver fibre element prepared using this method has excellent anti-microbial property, good gas permeability, excellent
Mechanical performance and good biocompatibility, and the sustained release of nano-silver ionic can be realized.
To achieve these goals, the technical solution adopted in the present invention is：
A kind of preparation method of the cellulose composite material of loading nano silvery, including：
(1) cellulose membrane is immersed in the water that pH is 5-10, concussion mixes；
(2) silver salt solution is added into the step (1), concussion shakes up, and obtains cellulose mixed liquor；
(3) the cellulose mixed liquor for including cellulose membrane of the step (2) is placed in microwave reactor carry out it is micro-
Ripple reacts, and after reaction terminates, cellulose is washed, obtains Nano Silver-cellulose composite.
(4) step (3) Nano Silver-cellulose composite is dried, that is, obtains Nano Silver-cellulose composite wood
Material.
Further, in the step (1), the preparation method of the cellulose membrane is as follows：Glucose acetobacter xylinum is stood
After culture 2-5 days, the cellulose membrane tentatively cultivated is cut, cleaned, pure by the cellulose membrane tentatively cultivated
Change, clean again to neutrality.
Further, in the step (1), the way of purification is that the cellulose membrane is put into concentration is 0.05-
Purified in 0.2mol/L sodium hydroxide, until cellulose membrane is turned into translucent milky.
Preferably, in the step (1), pH adjusting agent is one or more of dust technology, acetic acid or sodium hydroxide.
Preferably, in the step (1), the pH of the water is 7-10.
It is highly preferred that in the step (1), the pH of the water is 8-10.
It is highly preferred that in the step (1), the pH of the water is 10.
Further, it is 15-60min by the cellulose membrane water-immersed concussion time in the step (1).
Further, in the step (2), silver salt concentrations are 0.001-0.05mol/L in silver salt solution.
Further, in the step (2), the silver salt is one kind in silver nitrate solution or silver acetate solution.
Further, in the step (2), the mass ratio of silver salt and the cellulose is in the silver salt solution of the addition
0.004:1-0.05:1。
Preferably, in the step (2), the mass ratio of silver salt and the cellulose is in the silver salt solution of the addition
0.004:1-0.009:1。
Further, in the step (2), after adding the silver salt solution, the concussion time is 15-60min.
Preferably, in the step (1) and (2), to be shaken by shaking table, shaking speed is the mode of described concussion
10-100rpm。
Further, in the step (3), the microwave reaction time is 2-30min, microwave power 200-700W.
Preferably, in the step (3), the microwave reaction time is 2-20min, microwave power 200-600W.
Further, in the step (3), the cellulose washs into cleaning solution not silver ion and cleaning solution pH value
Untill neutrality.
Further, in the step (4), the mode of the drying include vacuum freeze drying, drying, natural drying or
Machinery press dry in one kind.
It is a further object of the present invention to provide the nano silver fibre element composite prepared by above-mentioned preparation method.
Further, the particle diameter of the Nano Silver in the nano silver fibre element composite is 30-80nm.
It is a further object of the present invention to provide the application of Nano Silver-cellulose composite material.
Further, application of the Nano Silver-cellulose composite material as anti-biotic material.
Beneficial effect
(1) present invention when preparing nano silver fibre element composite without using extra addition reducing agent, oxidant and
Stabilizer, avoid because of adverse effects such as mixed liquor post processing caused by addition mentioned reagent addition is difficult, pollution environment, and
And the preparation method is simple, has significantly saved time cost and cost of material；The preparation method is green, belongs to environment friend
Good type preparation technology.
(2) preparation technology is energy-efficient, significantly improves preparation efficiency, effectively improves nano-silver loaded rate, substantially reduces
Silver salt dosage, the quality proportioning of silver salt and the cellulose can reach 0.004 in silver salt solution:1-0.09:1, it is only known skill
/ 10th of art dosage, effectively save cost, simplify wastewater treatment, environmental protection；Effectively shorten the nano-silver loaded time,
Its microwave reaction time is only 2-30min；The power of Preparation equipment is effectively reduced, microwave power is only 200-700W；Significantly carry
The feature of high composite, such as bacteriostasis rate is significantly improved, initial preparing, the pH of immersion is in 8-10 water, nanometer
The bacteriostasis rate of silver fiber element composite reaches more than 99%.
(3) preparation method is in-situ synthesis, not only without doing any mechanical mashing processing to cellulose, simplifies system
Standby technique, save the time cost and equipment cost of preparation.
(4) preparation technology is easy, controllable：Can be by controlling pH value, the ion concentration of silver salt of reaction system, Yi Jiwei
The ripple recovery time controls the content of Nano Silver and particle size.
(5) it is for example good both to have played the excellent performance of cellulose for the composite of Nano Silver-cellulose prepared by the present invention
Biocompatibility, moisture holding capacity, rehydration ability, mechanical performance, gas permeability, played the excellent bacteriostasis property of Nano Silver again,
And nano silver particles can be made to be evenly distributed in the tridimensional network of cellulose, control the particle diameter of Nano Silver in 30-
Between 80nm, the sustained release of nano-silver ionic is effectively realized, avoids the deposition of Nano Silver.
(6) microwave synthesis step reaction condition in preparation method of the present invention is gentle, preparation method is easy, condition is controllable；
Microwave penetration ability is strong, homogeneous heating, can instantaneously reach required temperature.This provides another kind for the preparation of nano metal material
Path.Have not yet to see the report that microwave is used for synthesizing nano-silver-cellulose composite material.
It should be noted that the solution have the advantages that knot that each processing step and parameter are mutually cooperateed with, interacted
Fruit, the superposition of not simple technique, effect caused by the combination of each technique is considerably beyond each single process function and effect
The superposition of fruit, there is preferably advanced and practicality.
Brief description of the drawings
Accompanying drawing 1 is X-ray diffraction (XRD) spectrogram of Nano Silver-cellulose composite material of the embodiment of the present invention 6；
Accompanying drawing 2 is the scanning electron microscope (SEM) photograph of Nano Silver-cellulose composite material of the embodiment of the present invention 4；
Accompanying drawing 3 is Nano Silver-cellulose composite material product that the present invention is prepared under the conditions of different initial pH, wherein
(a) represent and do not add silver salt solution, the natural blank control groups of pH, (b), (c), (d), (e), (f), (g), (h), (i),
(j) it is respectively the composite products prepared under the conditions of 4,5,6,7,8,9,10,11,12 to represent pH respectively；
Accompanying drawing 4 is the UV, visible light for Nano Silver-cellulose composite material that the present invention generates under the conditions of different initial pH
Spectrogram, wherein.(a) it is respectively 4,5,6,7,8,9,10,12 that, (b), (c), (d), (e), (f), (g), (h) represent pH respectively
Under the conditions of the composite for preparing.
Embodiment
The present invention is described below by specific embodiment.Unless stated otherwise, technological means used in the present invention
It is method known in those skilled in the art.In addition, embodiment is interpreted as illustrative, it is not intended to limit the present invention
Scope, the spirit and scope of the invention are limited only by the claims that follow.To those skilled in the art, without departing substantially from this
The various changes carried out on the premise of invention spirit and scope to the material component in these embodiments and dosage or change
Belong to protection scope of the present invention.
Following examples are the further explanations to the present invention, rather than the scope of the invention is limited.
The preparation of 1 Nano Silver of embodiment-cellulose composite material
(1) cellulose membrane that after glucose acetobacter xylinum quiescent culture 2-5 days, will tentatively be cultivated, by what is tentatively cultivated
Cellulose membrane is cut；Cellulose membrane surface medium is cleaned with distilled water；Purifying, cellulose membrane is put into concentration is
Purified in 0.05mol/L sodium hydroxide, until cellulose membrane is turned into translucent milky；Cleaned again with distilled water into
Property；
(2) cellulose membrane for obtaining the first step is immersed in the distilled water that pH is 5, is placed in shaking table and is shaken 15min, rotating speed
For 100rpm, it is that 0.05mol/L silver nitrate solutiones shake up then to add concentration, makes silver salt and fiber in the silver nitrate solution of addition
The mass ratio of element is 0.05:1, and be again placed in shaking 15min in shaking table, rotating speed 100rpm,.
(3) by the cellulose membrane of (2) step and mixed liquor as in microwave reactor, setting microwave power is 200w,
Reaction time is 30min.
(4) Nano Silver for obtaining step (3)-cellulose membrane distillation water washing, until not silver ion in cleaning solution
And untill the pH value of cleaning solution is neutrality, obtain Nano Silver-cellulose composite.
(5) Nano Silver for obtaining (4)-cellulose composite carries out vacuum freeze drying 24h, obtains Nano Silver-fiber
Plain composite.
The preparation of 2 Nano Silvers of embodiment-cellulose composite material
(1) cellulose membrane that after glucose acetobacter xylinum quiescent culture 2-5 days, will tentatively be cultivated, by what is tentatively cultivated
Cellulose membrane is cut, the cellulose membrane that it is 2.0 × 1.0 × 0.5 that cut growth is generous；Cellulose membrane table is cleaned with distilled water
Face culture medium；Purifying, cellulose membrane is put into the sodium hydroxide that concentration is 0.2mol/L and purified, until cellulose membrane is turned into
Translucent milky；Cleaned again with distilled water to neutrality；
(2) cellulose membrane for obtaining the first step is immersed in the distilled water that pH is 6, is placed in shaking 60min in shaking table, is turned
Speed is 10rpm, and it is that 0.001mol/L silver acetate solution shakes up then to add concentration, makes silver salt and fibre in the silver acetate solution of addition
The mass ratio of dimension element is 0.01:1, and be again placed in shaking 60min in shaking table, rotating speed 10rpm.
(3) by the cellulose membrane of (2) step and mixed liquor as in microwave reactor, setting microwave power is 700w,
Reaction time is 2min.
(4) Nano Silver for obtaining step (3)-cellulose membrane distillation water washing, until not silver ion in cleaning solution
And untill the pH value of cleaning solution is neutrality, obtain Nano Silver-cellulose composite.
(5) Nano Silver-cellulose composite progress machinery that obtains for obtaining (4) press dry, and it is multiple to obtain Nano Silver-cellulose
Condensation material.
The preparation of 3 Nano Silvers of embodiment-cellulose composite material
(1) cellulose membrane that after glucose acetobacter xylinum quiescent culture 2-5 days, will tentatively be cultivated, by what is tentatively cultivated
Cellulose membrane is cut, the cellulose membrane that it is 2.0 × 1.0 × 0.5 that cut growth is generous；Cellulose membrane table is cleaned with distilled water
Face culture medium；Purifying, cellulose membrane is put into the sodium hydroxide that concentration is 0.1mol/L and purified, until cellulose membrane is turned into
Translucent milky；Cleaned again with distilled water to neutrality；
(2) cellulose membrane for obtaining the first step is immersed in the distilled water that pH is 7, is placed in shaking 25min in shaking table, is turned
Speed is 50rpm, and it is that 0.01mol/L silver nitrate solutiones shake up then to add concentration, makes silver salt and fibre in the silver nitrate solution of addition
The mass ratio of dimension element is 0.004:1, mixed solution total system is 100ml in system, and is again placed in shaking 30min in shaking table,
Rotating speed is 50rpm.
(3) by the cellulose membrane of (2) step and mixed liquor as in microwave reactor, setting microwave power is 400w,
Reaction time is 20min.
(4) Nano Silver for obtaining step (3)-cellulose membrane distillation water washing, until not silver ion in cleaning solution
And untill the pH value of cleaning solution is neutrality, obtain Nano Silver-cellulose composite.
(5) Nano Silver for obtaining (4)-cellulose composite progress machinery press dry, and obtains Nano Silver-cellulose composite wood
Material.
The preparation of 4 Nano Silvers of embodiment-cellulose composite material
(1) cellulose membrane that after glucose acetobacter xylinum quiescent culture 2-5 days, will tentatively be cultivated, by what is tentatively cultivated
Cellulose membrane is cut；Cellulose membrane surface medium is cleaned with distilled water；Purifying, cellulose membrane is put into concentration is
Purified in 0.15mol/L sodium hydroxide, until cellulose membrane is turned into translucent milky；Cleaned again with distilled water into
Property；
(2) cellulose membrane for obtaining the first step is immersed in the distilled water that pH is 8, is placed in shaking 30min in shaking table, is turned
Speed is 60rpm, and it is that 0.02mol/L silver nitrate solutiones shake up then to add concentration, makes silver salt and fibre in the silver nitrate solution of addition
The mass ratio of dimension element is 0.006:1, and be again placed in shaking 30min in shaking table, rotating speed 60rpm.
(3) by the cellulose membrane of (2) step and mixed liquor as in microwave reactor, setting microwave power is 500w,
Reaction time is 5min.
(4) Nano Silver for obtaining step (3)-cellulose membrane distillation water washing, until not silver ion in cleaning solution
And untill the pH value of cleaning solution is neutrality, obtain Nano Silver-cellulose composite.
(5) Nano Silver-cellulose composite for obtaining (4) is dried, and obtains Nano Silver-cellulose composite material.
, can from the scanning electron microscope (SEM) photograph of the Nano Silver-cellulose composite material prepared by the embodiment referring to the drawings 4
Go out：White pointing object is nano silver particles in figure, it can be seen that Nano Silver is evenly distributed in cellulose.
It should be noted that it is experimentally confirmed, the Nano Silver-cellulose composite material prepared by embodiment 1-3,5,6
In, Nano Silver is also uniformly dispersed in cellulose.
The preparation of 5 Nano Silvers of embodiment-cellulose composite material
(1) cellulose membrane that after glucose acetobacter xylinum quiescent culture 2-5 days, will tentatively be cultivated, by what is tentatively cultivated
Cellulose membrane is cut；Cellulose membrane surface medium is cleaned with distilled water；Purifying, cellulose membrane is put into concentration is
Purified in 0.16mol/L sodium hydroxide, until cellulose membrane is turned into translucent milky；Cleaned again with distilled water into
Property；
(2) cellulose membrane for obtaining the first step is immersed in the distilled water that pH is 9, is placed in shaking 20min in shaking table, is turned
Speed is 70rpm, and it is that 0.015mol/L silver acetate solution shakes up then to add concentration, makes silver salt and fibre in the silver acetate solution of addition
The mass ratio of dimension element is 0.005:1, and be again placed in shaking 30min in shaking table, rotating speed 60rpm.
(3) by the cellulose membrane of (2) step and mixed liquor as in microwave reactor, setting microwave power is 400w,
Reaction time is 8min.
(4) Nano Silver for obtaining step (3)-cellulose membrane distillation water washing, until not silver ion in cleaning solution
And untill the pH value of cleaning solution is neutrality, obtain Nano Silver-cellulose composite.
(5) Nano Silver-cellulose composite for obtaining (4) is spontaneously dried, and obtains Nano Silver-cellulose composite wood
Material.
The preparation of 6 Nano Silvers of embodiment-cellulose composite material
(1) cellulose membrane that after glucose acetobacter xylinum quiescent culture 2-5 days, will tentatively be cultivated, by what is tentatively cultivated
Cellulose membrane is cut；Cellulose membrane surface medium is cleaned with distilled water；Purifying, cellulose membrane is put into concentration is
Purified in 0.10mol/L sodium hydroxide, until cellulose membrane is turned into translucent milky；Cleaned again with distilled water into
Property；
(2) cellulose membrane for obtaining the first step is immersed in the distilled water that pH is 10, is placed in shaking 30min in shaking table,
Rotating speed is 60rpm, and it is that 0.02mol/L silver nitrate solutiones shake up then to add concentration, make in the silver nitrate solution of addition silver salt with
The mass ratio of cellulose is 0.007:1, and be again placed in shaking 30min in shaking table, rotating speed 60rpm.
(3) by the cellulose membrane of (2) step and mixed liquor as in microwave reactor, setting microwave power is 400w,
Reaction time is 10min.
(4) Nano Silver for obtaining step (3)-cellulose membrane distillation water washing, until not silver ion in cleaning solution
And untill the pH value of cleaning solution is neutrality, obtain Nano Silver-cellulose composite.
(5) Nano Silver-cellulose composite that obtains for obtaining (4) carries out freeze-drying 12h, finally give Nano Silver-
Cellulose composite material.
1 is the composite prepared under conditions of initial pH is 10 referring to the drawings, occurs silver respectively in figure and nanometer is micro-
The characteristic peak of crystalline cellulose, non-oxidation silver characteristic peak, illustrate that product nano silver-cellulose composite is pure without other impurity, product
Degree is high.It should be noted that also it is silver oxide in the XRD of embodiment 1-5 Nano Silver-nano micro crystal cellulose compound
Characteristic peak, the Nano Silver-cellulose composite for illustrating to be prepared by embodiment 1-5 is without other impurity.
Embodiment 7
(1) cellulose membrane that after glucose acetobacter xylinum quiescent culture 2-5 days, will tentatively be cultivated, by what is tentatively cultivated
Cellulose membrane is cut；Cellulose membrane surface medium is cleaned with distilled water；Purifying, cellulose membrane is put into concentration is
Purified in 0.10-0.20mol/L sodium hydroxide, until cellulose membrane is turned into translucent milky；It is clear with distilled water again
It is washed till neutrality；
(2) cellulose membrane for obtaining the first step is immersed in the distilled water that pH is 8-10, is placed in shaking 20- in shaking table
40min, rotating speed 30-60rpm, it is that 0.001-0.02mol/L silver nitrate solutiones shake up then to add concentration, makes the nitric acid of addition
The mass ratio of silver salt and cellulose is 0.005-0.009 in silver-colored solution:1, and be again placed in shaking 20-40min in shaking table, rotating speed
For 30-60rpm.
(3) by the cellulose membrane of (2) step and mixed liquor as in microwave reactor, setting microwave power is 300-
500w, reaction time 5-10min.
(4) Nano Silver for obtaining step (3)-cellulose membrane distillation water washing, until not silver ion in cleaning solution
And untill the pH value of cleaning solution is neutrality, obtain Nano Silver-cellulose composite.
(5) Nano Silver-cellulose composite that obtains for obtaining (4) carries out freeze-drying 12h, finally give Nano Silver-
Cellulose composite material.
The composite prepared by embodiment 7, using the method for embodiment 10 determine its material to Gram-negative bacteria-
The bacteriostasis rate of Escherichia coli reaches more than 99%.And the time that composite is prepared using microwave is shorter, power is relatively low, significantly
Reduce preparation cost.
The Experimental comparison of embodiment 8
Contrast the form and color of the Nano Silver-cellulose composite material product prepared under the conditions of different initial pH.
Blank control group is：Using the preparation method of embodiment 6, keep initial pH and obtained naturally, not adding silver salt solution
Blank control set product；
Control group 1 and 2 is respectively the preparation method using embodiment 6, only changes different initial pH, is respectively in initial pH
The product prepared under conditions of 4 and 12；
Experimental group 1-6 is respectively the product prepared by embodiment 1-6.
3 it can be seen that referring to the drawings as initial pH rise, the color of product are gradually deepened, wherein control group 2, i.e.,
Under the conditions of initial pH is 11, due to silver oxide be present, therefore silver ion is prevented to enter in the tridimensional network of cellulose, thus it is multiple
When other conditions are identical, the content of the Nano Silver loaded on the contrary is reduced condensation material.And in control group 3, i.e., initial pH is 12
Under part, the color of composite becomes deeper.
The list of each product under the condition of different pH of table 1
| Group | Drawing reference numeral | Initial pH |
| Blank control group | (a) | Natural (being approximately equal to 7.5) |
| Control group 1 | (b) | 4 |
| Control group 2 | (i) | 11 |
| Control group 3 | (j) | 12 |
| Experimental group 1 | (c) | 5 |
| Experimental group 2 | (d) | 6 |
| Experimental group 3 | (e) | 7 |
| Experimental group 4 | (f) | 8 |
| Experimental group 5 | (g) | 9 |
| Experimental group 6 | (h) | 10 |
The Experimental comparison of embodiment 9
Contrast the uv-vis spectra of the Nano Silver-cellulose composite material product prepared under the conditions of different initial pH
Figure.
Control group 1,2,3 is respectively the preparation method using embodiment 6, only changes different initial pH, distinguishes in initial pH
For the product prepared under conditions of 4,12；
Experimental group 1-6 is respectively the product prepared by embodiment 1-6.
Reference picture 4 can show that experimental group 1-6 ultraviolet absorption peak is higher, illustrate its composite material nanometer silver content
It is higher, and control group 1, when initial pH is 4, i.e., in acid condition, its ultraviolet absorption peak is smaller, illustrates that its composite is received
Rice silver content is less.And in control group 2, when initial pH is 12, i.e., in alkalescence condition, its ultraviolet absorption peak is smaller, explanation
Content of nanometer silver is significantly reduced in cellulose, and when initial pH is 12, because it is strong basicity, only solvent subsequent treatment is not brought
Trouble, and pollution is also brought along to environment, meanwhile, significantly improve cost of material.
The list of each composite under the condition of different pH of table 2
| Group | Drawing reference numeral | Initial pH |
| Control group 1 | (a) | 4 |
| Control group 2 | (h) | 12 |
| Experimental group 1 | (b) | 5 |
| Experimental group 2 | (c) | 6 |
| Experimental group 3 | (d) | 7 |
| Experimental group 4 | (e) | 8 |
| Experimental group 5 | (f) | 9 |
| Experimental group 6 | (g) | 10 |
The bacteriostasis property measure of the composite of embodiment 10
Nano silver fibre element composite prepared by the present embodiment 1-6 is freeze-dried, then cut with card punch
Under a diameter of 1cm composite and it is entered standby after horizontal high voltage moist heat sterilization.Picking Escherichia coli single bacterium colony is seeded in
In 10ml LB culture mediums, diluted at 37 DEG C of 180rpm after concussion and cultivate culture 12h, it is 10 to make bacterium dense6Cfu/ml, by monolithic
Composite is put into the culture medium containing bacterium solution, 180rpm, and 37 DEG C of culture 12h carry out thalline counting.
Viable count during bacteriostasis rate=(viable count during viable count -24h during 0min)/0min.
The bacteriostasis rate of the composite of table 3
| Group | Bacteriostasis rate (%) |
| Embodiment 1 | 75.6 |
| Embodiment 2 | 85.5 |
| Embodiment 3 | 95.5 |
| Embodiment 4 | 99.0 |
| Embodiment 5 | 99.5 |
| Embodiment 6 | 99.9 |
Claims (10)
- A kind of 1. preparation method of Nano Silver-cellulose composite material, it is characterised in that：Including：(1) cellulose membrane is immersed in the water that pH is 5-10, concussion mixes；(2) silver salt solution is added into the step (1), concussion shakes up, and obtains cellulose mixed liquor；(3) the cellulose mixed liquor of the step (2) is placed in microwave reactor and carries out microwave reaction, will after reaction terminates Cellulose washs, and obtains Nano Silver-cellulose composite；(4) step (3) Nano Silver-cellulose composite is dried, that is, obtains Nano Silver-cellulose composite material.
- A kind of 2. preparation method of Nano Silver-cellulose composite material as claimed in claim 1, it is characterised in that：The step Suddenly in (1), the preparation method of the cellulose membrane is as follows：After glucose acetobacter xylinum quiescent culture 2-5 days, tentatively cultivated Cellulose membrane, the cellulose membrane tentatively cultivated is cut, cleaned, purified, cleaned again to neutrality.
- A kind of 3. preparation method of Nano Silver-cellulose composite material as claimed in claim 1, it is characterised in that：The step Suddenly the concussion time in (1) and (2) is 15-60min.
- A kind of 4. preparation method of Nano Silver-cellulose composite material as claimed in claim 1, it is characterised in that：The step Suddenly in (2), silver salt concentrations are 0.001-0.05mol/L in silver salt solution.
- A kind of 5. preparation method of Nano Silver-cellulose composite material as claimed in claim 1, it is characterised in that：It is described to add The mass ratio of silver salt and the cellulose is 0.004 in the silver salt solution entered:1-0.05:1.
- A kind of 6. preparation method of Nano Silver-cellulose composite material as claimed in claim 1, it is characterised in that：The step Suddenly in (2), the mass ratio of silver salt and the cellulose is 0.004 in the silver salt solution of the addition:1-0.009:1.
- A kind of 7. preparation method of Nano Silver-cellulose composite material as claimed in claim 1, it is characterised in that：The step Suddenly in (3), the microwave reaction time is 2-30min, microwave power 200-700W.
- A kind of 8. preparation method of Nano Silver-cellulose composite material as claimed in claim 1, it is characterised in that：The step Suddenly in (4), the mode of the drying includes one kind during vacuum freeze drying, drying, natural drying or machinery press dry.
- 9. Nano Silver-cellulose composite material that the preparation method as described in claim 1-8 any one obtains.
- 10. the application of Nano Silver-cellulose composite material as claimed in claim 9.
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