CN106142243A - A kind of antimicrobial form bamboo composite and preparation method - Google Patents
A kind of antimicrobial form bamboo composite and preparation method Download PDFInfo
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- CN106142243A CN106142243A CN201610523053.0A CN201610523053A CN106142243A CN 106142243 A CN106142243 A CN 106142243A CN 201610523053 A CN201610523053 A CN 201610523053A CN 106142243 A CN106142243 A CN 106142243A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27J—MECHANICAL WORKING OF CANE, CORK, OR SIMILAR MATERIALS
- B27J1/00—Mechanical working of cane or the like
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K9/00—Chemical or physical treatment of reed, straw, or similar material
- B27K9/002—Cane, bamboo
Abstract
The invention discloses the preparation method of a kind of stannic oxide/graphene nano piece/zinc oxide/bamboo composite, zinc oxide and stannic oxide/graphene nano piece are in depth combined inside bamboo wood by described method by hydro-thermal reaction, thus obtain the stannic oxide/graphene nano piece/zinc oxide/bamboo composite with good fungistatic effect.The method according to the invention technique is simple, environmental protection and low cost, it is different from the modified surface treatment method of traditional nano-inorganic substance, the method being combined by pre-treatment and hydro-thermal method prepares the bamboo composite of graphene oxide/modified zinc oxide, graphene oxide and zinc oxide is made to penetrate into material internal, active ingredient not easily runs off, good anti-bacterial effect and persistently.Bamboo wood also can keep preferable antibiotic property when the secondary operations in later stage.
Description
Technical field
The invention belongs to field of compound material, be specifically related to a kind of bamboo composite with antibiotic property and preparation side
Method.
Background technology
Bamboo is a kind of natural fast-growing material and the important forest reserves.Bamboo wood has that growth cycle is short, yield is high, intensity
The feature such as high and renewable, can be widely applied to multiple fields such as building, building materials, household.China's bamboo timber resource enriches, and rationally opens
Sending out utilizes bamboo wood can alleviate the problems such as domestic timber resources is in short supply, has very high economic worth and the ecological value.Building especially
Building materials application aspect, bamboo structure has that lightweight, good toughness, deformation be little and the plurality of advantages such as intensity is high, can make truss
Solve the large span problem in building, be the low energy building material of a kind of high-quality, utilize bamboo wood to accord with as modern architecture material
Close the requirement of sustainable development.But, natural bamboo due to the composition such as aqueous, starch, protein, lignin easily by bacterium and mould
The erosion of bacterium, thus cause bamboo wood easy to be mouldy rotten so that it is it is difficult to storage after processing, be unfavorable for the large-scale comprehensive profit of bamboo wood
With.Although the feature of bamboo structure itself makes bamboo wood be easy to regularization and standardization, but is limited to fresh bamboo wood and stores the problems such as difficult,
The building matching component still unrealized large-scale standardization and industrialization of current bamboo wood.Therefore, anti-corrosive antibacterial is carried out to bamboo wood
Process, extend bamboo wood and store and service life, for the value improving bamboo wood and product function, promote bamboo wood at Building wood
Large-scale application in terms of material has important practical significance.
Traditional bamboo timber anti-biotic material mainly uses organic bactericide, such as pentachlorophenol, has that toxicity is big, the term of validity
Short, chemical stability is poor and only has the shortcomings such as bacteriostasis to part bacterial classification.Due to good anti-bacterial effect, Heat stability is good, no
It is easily generated drug resistance, effect length and to the advantages such as humans and animals is non-toxic, the inorganic antibacterial material with titanium dioxide as representative
Receive extensive concern in recent years.As remaining etc. use normal temperature dipping and Low Temperature Heat Treatment method combine prepare nano zinc oxide modified
Bamboo timber, can improve the antimildew and antibacterial performance [application for a patent for invention number: 200910093088.5] of bamboo timber.Mineral-modified bamboo
Timber covers with paint, lacquer, colour wash, etc. various coating or to prepare bamboo timber/inorganic matter with impregnation process inorganic matter presoma multiple frequently with at wood surface
Condensation material.Though but semar technique plays a protective role, but top layer is easily peeled off, and there is the problem such as yellowing, loss of gloss；And impregnate
Method can only be particularly long-acting to heat endurance, the antibacterial effect of bamboo wood by major part inorganic deposition or be filled in bamboo wood top layer
The improvement of property is limited.
Content of the invention
For above-mentioned the problems of the prior art, it is an object of the invention to provide a kind of stannic oxide/graphene nano piece/oxygen
Change the preparation method of zinc/bamboo composite, use the method that supersonic oscillations and negative pressure of vacuum combine by before inorganic matter
Drive body and impregnate inside bamboo wood, then use hydro-thermal facture to prepare stannic oxide/graphene nano piece/zinc oxide/bamboo wood compound material
Material, simple for process, environmental protection, with low cost, and stannic oxide/graphene nano piece and nano zine oxide are easily inside bamboo wood
Growth, can obviously improve heat endurance and the anti-microbial property of bamboo wood.
The preparation method of stannic oxide/graphene nano piece/zinc oxide/bamboo composite according to the present invention include as
Lower step:
1) bamboo material is pre-processed, first the surface of bamboo material is processed, for example, can utilize scraper
Or the surface that sand paper etc. is to bamboo material carries out the surface treatments such as polishing, then use deionized water, ethanol vacuum ultrasonic 30 successively
Minute purged of impurities, 40 DEG C of dryings；
2) by step 1) bamboo material that processes is totally submerged in the zinc salt mixed liquor being dispersed with stannic oxide/graphene nano piece
In, it is evacuated to below 0.01MPa, within ultrasonically treated 10 minutes, make zinc salt and graphene oxide try one's best and fill inside bamboo material,
Stand 24h；
3) toward step 2) mixed liquor is added dropwise over 1mol/L monoethanolamine solution regulation solution ph to 10, again take out true
Empty to below 0.01MPa, after ultrasonically treated 10 minutes, after dipping 24h, take out bamboo material, with miscellaneous by its surface of deionized water
Matter cleans up, 60 DEG C of dryings；
4) suspension being dispersed with stannic oxide/graphene nano piece is added in zinc solution, wherein stannic oxide/graphene nano piece
Concentration be 0.02～3g/L, preferably 0.2～1g/L, zinc solution concentration is 0.005～2mol/L, ultrasonic 30 minutes mixing
Uniformly, being added dropwise over monoethanolamine solution regulation pH value of solution=10 that concentration is 1mol/L, stirring 1h is allowed to mix；
5) step 4) gained mixed liquor moves on in water heating kettle, adds step 3) bamboo material after the dipping of gained, bamboo wood
Be 1:3 to 1:20 with maceration extract volume ratio, under hydrothermal reaction condition, be heated to 60～200 DEG C, preferably 70～130 DEG C, insulation 1～
96 hours, preferably 2～12 hours, cooling, take out bamboo wood, wash with water 3 to 5 times, be dried, i.e. obtain Graphene/zinc oxide/bamboo
Material composite.
Wherein, step 1) described bamboo material can be for justifying bamboo, bamboo chip, Bamboo veneer, bamboo silk, bamboo fibre, bamboo particle etc.；Bag
Containing bamboo kinds such as mao bamboon, black bamboo, firm bamboo, phyllostachys bambusoides or Fang Zhu, there is no particular restriction for the shape of described bamboo material, can be irregular
Shape or regular shape, it is preferable that for example can be the square shape of 1cm × 1cm × 1cm or diameter 4cm × length
The round bamboo section of 10cm.
Step 2) described in zinc salt be zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, the one in zinc dihydrogen phosphate or
Multiple, zinc salt concentration is 0.5～3mol/L, preferably 2～3mol/L, and graphene oxide water solution concentration is 0.5～10g/L, excellent
Select 2～5g/L；
Step 4) described in zinc salt be zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, the one in zinc dihydrogen phosphate or
Multiple, concentration is 0.005～2mol/L, preferably 0.01～0.5mol/L.
According to an aspect of the invention, it is provided a kind of stannic oxide/graphene nano piece/zinc oxide/bamboo composite
Preparation method, it comprises the steps:
Bamboo block (1cm × 1cm × 1cm) scraper is scraped off very thin one layer in surface, about about 1～2mm, then spend from
Sub-water, 30 minutes purged of impurities of ethanol vacuum ultrasonic, after 40 DEG C of dryings, be totally submerged in 20mL saturated acetic acid zinc and oxidation stone
Ink alkene nanometer sheet (1.5g/L) mixed liquor, at vacuum condition ultrasonically treated 10 minutes, is added dropwise over the mono-second of 1mol/L after standing 24h
Alkanolamine solution regulation solution ph, to 10, at vacuum condition ultrasonically treated 10 minutes, is taken out bamboo block after dipping 24h, is used deionization
The impurity on surface is rinsed well by water, 60 DEG C of dryings；
The stannic oxide/graphene nano piece aqueous solution that the concentration of 1.5mL is 10g/L is added the concentration of 20mL is 0.05mol/L
Zinc nitrate solution in, within ultrasonic 30 minutes, mix, be added dropwise over monoethanolamine solution (1mol/L) to pH value of solution=10, stir
Mixing 1h to be allowed to mix, then moving on in water heating kettle, the bamboo block (1cm × 1cm × 1cm) after addition process, 120 DEG C of hydro-thermals
Process 3h, cooling, take out bamboo block, wash with water 5 times, be dried, i.e. obtain stannic oxide/graphene nano piece/zinc oxide/bamboo wood and be combined
Material.
According to an aspect of the invention, it is provided a kind of stannic oxide/graphene nano piece/zinc oxide/bamboo composite,
Described stannic oxide/graphene nano piece/zinc oxide/bamboo composite is by stannic oxide/graphene nano piece/oxygen according to the present invention
The preparation method changing zinc/bamboo composite prepares.
Beneficial effect
The present invention compared with prior art has the advantage that
1st, the present invention utilizes ultrasonic and negative pressure of vacuum auxiliary to impregnate composite material precursor, can at utmost make oxygen-containingization
The aqueous solution depth of penetration of zinc precursor and stannic oxide/graphene nano piece is in bamboo wood inside, with bamboo wood in hydrothermal treatment process
Cell membrane hydroxyl forms the chemical bond of stable combination, makes zinc oxide and stannic oxide/graphene nano piece be firmly secured to cell membrane
On.
2nd, the method technique of the present invention is simple, environmental protection and low cost, is different from traditional nano-inorganic substance modified
Surface treatment method, the method being combined by pre-treatment and hydro-thermal method prepares stannic oxide/graphene nano piece/modified zinc oxide
Bamboo composite, makes stannic oxide/graphene nano piece and zinc oxide penetrate into material internal, and active ingredient not easily runs off, antibacterial effect
Fruit is good and lasting.Bamboo wood also can keep preferable antibiotic property when the secondary operations in later stage.
3rd, the present invention uses nano zine oxide and stannic oxide/graphene nano piece modified bamboo wood jointly antibacterial to improve it first
Performance.Collaborative antibacterial effect, nano zine oxide and oxidation stone is there is between nano zine oxide and stannic oxide/graphene nano piece
The fungistatic effect of ink alkene nanosheet composite material is far above nano zinc oxide modified bamboo wood or the bamboo wood of graphene oxide modification.
Brief description
Fig. 1 is for according to embodiments of the invention 1 (d), comparative example 1 (c), comparative example 2 (b) and comparative example
The SEM photograph of modified bamboo block prepared by 3 (a)；
Fig. 2 is for according to embodiments of the invention 1 (a), comparative example 1 (b), comparative example 2 (c) and comparative example
The XRD result figure of modified bamboo block prepared by 3 (d)；
Fig. 3 is for according to embodiments of the invention 1 (a), comparative example 1 (b), comparative example 2 (c) and comparative example
The TG result figure of modified bamboo block prepared by 3 (d)；
Fig. 4 is changing of preparing according to embodiments of the invention the 1st, comparative example the 1st, comparative example 2 and comparative example 3
The Bactericidal test result figure of property bamboo block.
Detailed description of the invention
Preparation in accordance with the present invention, in step 1) in bamboo material is pre-processed, for example can utilize scraper
Or the surface that sand paper etc. is to bamboo material carries out the surface treatments such as polishing, on the one hand ensure bamboo material surfacing, the opposing party
Face ensures bamboo material surface not by outside contamination.
In step 2) in through step 1) process after bamboo material carry out impregnation process, will its be totally submerged in point
Dissipate in the zinc salt mixed liquor having graphene oxide nanometer sheet, and by being evacuated to below 0.01MPa, ultrasonically treated 10 minutes
Make zinc salt and stannic oxide/graphene nano piece try one's best to fill inside bamboo material.Wherein in order to make zinc salt immerse bamboo material as far as possible
Inside, in solution, the concentration of zinc salt is higher as far as possible, for example, can use the zinc solution of saturated concentration, simultaneously ultrasonic place
Reason improves the permeability of bamboo wood pit membrane by utilizing ultrasonication effect, greatly accelerates circulation speed on pit for the moisture
Degree, so that zinc solution is more easy to infiltrate into inside bamboo wood；And vacuumize and contribute to discharging the air within bamboo material, enter
And the immersion of beneficially zinc solution.Therefore described zinc salt can be able to be for example zinc chloride, sulphur with the big zinc salt of Selective dissolution degree
Acid zinc, zinc nitrate, zinc acetate, one or more in zinc dihydrogen phosphate, described zinc salt concentration is 0.5～3mol/L, preferably 2
～3mol/L.Based on same reason, the concentration of described stannic oxide/graphene nano piece is preferably 0.5～10g/L, further preferably
It is 2～5g/L.
In step 5) in hydro-thermal process carried out to the bamboo material after processing, but the concentration of zinc salt in this hydrothermal process
Should control in the range of 0.005～2mol/L (step 4)).As zinc salt concentration too low (such as less than 0.005mol/L), bamboo wood
The nano zine oxide amount of interior generation is less；And as zinc salt concentration too high (such as larger than 2mol/L), the zinc oxide of generation during hydro-thermal
Being more likely formed bulky grain, blocking bamboo wood duct, make zinc oxide content decline, antibacterial effect also reduces on the contrary.Therefore rate-determining steps
5) scope of zinc salt concentration in, has a major impact to the anti-microbial property of final products.
Hereinafter, will be described in detail the present invention.Before doing so, it should be appreciated that in this specification and appended
Claims in the term that uses should not be construed as and be limited to general sense and dictionary meanings, and inventor should allowed
On the basis of suitably definition term is to carry out the principle of best interpretations, according to implication corresponding with the technical elements of the present invention and generally
Thought explains.Therefore, description presented herein is merely for the sake of the preferred embodiment illustrating purpose, is not intended to limit this
The scope of invention, it will thus be appreciated that in the case of without departing from the spirit and scope of the present invention, can be obtained it by it
His equivalents or improved procedure.
Following example are enumerated only as the example of embodiment of the present invention, do not constitute any limit to the present invention
System, it will be appreciated by those skilled in the art that the modification in the range of essence without departing from the present invention is with design each falls within the present invention
Protection domain.
Hereinafter, the disclosure is described with reference to the accompanying drawings in detail preferred embodiment.Before described, it should
The term that solution uses in specification and appended, and should not be interpreted as limited to general and dictionary meaning, but should
When the principle that the explanation best based on permission inventor suitably defines term, based on the meaning corresponding to the technology of the present invention aspect
Justice and concept explain.Therefore, the preferred embodiment describing only for illustration purpose in this, and not refer to limit the present invention
Scope, it is therefore to be understood that, can be made other under without departing from the spirit and scope of the present invention and equivalent implement and repair
Change.
Embodiment
Material characterization instrument:
SEM: model is S-4800Hitachi, manufacturer is Hitachi Hitachi, Ltd
X-ray diffractometer: model is D8Advance, manufacturer is Bruker company of Germany
Thermogravimetric analyzer: model is Q600, manufacturer is TA company of the U.S.
The stannic oxide/graphene nano piece aqueous solution is purchased from Qingdao Hua Gaomo alkene Science and Technology Co., Ltd.
Embodiment 1:
Bamboo block (1cm × 1cm × 1cm) scraper is scraped off very thin one layer in surface, about about 1～2mm, then spend from
Sub-water, 30 minutes purged of impurities of ethanol vacuum ultrasonic, after 40 DEG C of dryings, be totally submerged in 20mL saturated acetic acid zinc and oxidation stone
Ink alkene nanometer sheet (2g/L) mixed liquor, at vacuum condition ultrasonically treated 10 minutes, is added dropwise over 1mol/L monoethanol after standing 24h
Amine aqueous solution regulation solution ph, to 10, at vacuum condition ultrasonically treated 10 minutes, is taken out bamboo block after dipping 24h, is used deionized water
The impurity on surface is rinsed well, 60 DEG C of dryings；
The stannic oxide/graphene nano piece aqueous solution that the concentration of 1.5mL is 10g/L is added the concentration of 20mL is 0.05mol/L
Zinc nitrate solution in, within ultrasonic 30 minutes, mix, be added dropwise over monoethanolamine solution (1mol/L) to pH value of solution=10, stir
Mixing 1h to be allowed to mix, then moving on in water heating kettle, the bamboo block (1cm × 1cm × 1cm) after addition process, 120 DEG C of hydro-thermals
Process 3h, cooling, take out bamboo block, wash with water 5 times, be dried, i.e. obtain stannic oxide/graphene nano piece/zinc oxide/bamboo wood and be combined
Material (ZGB).
Intercept one piece with the modified circle bamboo that the present embodiment is prepared by blade, top layer cut about 2～3mm, after in centre
One piece of thin slice is cut at position, carries out SEM sign to it.Fig. 1 d is the SEM photograph of modified bamboo block prepared according to the present embodiment, by shining
Piece it can be seen that in the composite prepared according to the present embodiment, by the method for this method prepare material modified, nano oxygen
Change zinc and stannic oxide/graphene nano piece major part in bamboo block growth inside.XRD result shows (see Fig. 2 a), and 2 θ are 15 ° and 22 °
Diffraction maximum is respectively belonging to cellulose (110) and (002) crystal face；2 θ are the characteristic peak that the diffraction maximum of 11.3 ° is graphene oxide,
Belong to its (001) crystal face；2 θ are that 32.1 °, 34.8 °, 36.6 °, 47.8 ° and 56.8 ° are respectively belonging to wurtzite-type zinc oxide
(100), (002), (101), (102) and (110) crystal face, this result explanation nano zine oxide and stannic oxide/graphene nano piece
It is all deposited in bamboo wood.Thermal gravimetric analysis results shows (see Fig. 3), modified through nano zine oxide and stannic oxide/graphene nano piece
Bamboo wood heat endurance is better than unmodified sample.
Comparative example 1:
It is totally submerged the bamboo block (1cm × 1cm × 1cm) after surface preparation as in Example 1 cleaning in 20mL
In stannic oxide/graphene nano piece (2g/L) solution, at vacuum condition ultrasonically treated 10 minutes, take out bamboo block after dipping 24h, spend
The impurity on surface is rinsed well by ionized water, 60 DEG C of dryings；
Adding the 1.5mL stannic oxide/graphene nano piece aqueous solution (10g/L) in 20mL water, 1mol/L monoethanolamine solution is adjusted
Joint solution ph, to 10, at vacuum condition ultrasonically treated 10 minutes, then moves on in water heating kettle, addition process after bamboo block,
120 DEG C of hydro-thermals process 3h, cooling, take out bamboo block, wash with water repeatedly, are dried, i.e. obtain graphene oxide/bamboo composite
(GB)。
Comparative example 2:
It is totally submerged the bamboo block (1cm × 1cm × 1cm) after surface preparation as in Example 1 cleaning in 20mL
Saturated acetic acid zinc solution, at vacuum condition ultrasonically treated 10 minutes, stands 24h, is added dropwise over 1mol/L monoethanolamine solution and adjusts
Joint solution ph, to 10, at vacuum condition ultrasonically treated 10 minutes, takes out bamboo block, by deionized water by surface after dipping 24h
Impurity is rinsed well, 60 DEG C of dryings；
It is added dropwise over monoethanolamine solution (1mol/L) toward 20mL zinc nitrate (0.05mol/L) to pH value of solution=10, stirring
1h is allowed to mix, and then moves on in water heating kettle, the bamboo block after addition process, processes 3h, cooling 120 DEG C of hydro-thermals, takes out
Bamboo block, washes with water repeatedly, is dried, i.e. obtains zinc oxide/bamboo composite (ZB).
Comparative example 3:
By surface preparation bamboo block (1cm × 1cm × 1cm) deionized water, ethanol vacuum ultrasonic 30 as in Example 1
Minute purged of impurities, then 40 DEG C are drying to obtain unmodified bamboo wood (OB).
EXPERIMENTAL EXAMPLE 1:
Use inhibition zone method to carry out bacteriostatic test to sample, may determine that sample according to the size of inhibition zone around antibacterial substance
The quality of product antimildew and antibacterial.Escherichia coli are carried out to the modified bamboo block prepared in embodiment 1 and comparative example 1 to 3 antibacterial
Performance test, specific operation process is: prepare the culture medium needed for antibacterial experiment: weigh yeast extract powder 2.5g, albumen respectively
Peptone 5g, NaCl 5g, agar powder 7.5g pour in conical flask, add 500ml deionized water, utilize 1mol/L NaOH regulation pH extremely
7.4, stirring 20min is placed in 120 DEG C of autoclave sterilizers sterilizing 20min, then moves in super-clean bench by nutrient solution, point
Install in sterile petri dish, treat that its natural coagulation becomes solid medium, take the Escherichia coli after dilution twice and be applied to culture medium, so
After by fixing for sample in the medium, be placed in constant incubator 37 DEG C and cultivate 24h.Fig. 4 is for according to embodiments of the invention the 1st,
The Bactericidal test result figure of the modified bamboo block of comparative example the 1st, comparative example 2 and comparative example 3 preparation.Upper left in figure
OB is the design sketch of the unmodified bamboo block of comparative example 3, it can be seen that does not has inhibition zone, illustrates do not have fungistatic effect；Right
Upper ZB is the zinc oxide/bamboo block of comparative example 2, the stannic oxide/graphene nano piece/bamboo block of lower-left GB comparative example 1 and bottom right
ZGB be the stannic oxide/graphene nano piece/zinc oxide/bamboo block of embodiment 1 colibacillary inhibition zone is respectively 1.25cm, 1cm,
2.15cm.This result illustrate, unmodified bamboo wood anti-microbial property is very poor, almost without fungistatic effect, and nano zine oxide and
The composite modified bamboo wood of stannic oxide/graphene nano piece has excellent fungistatic effect, and its bacteriostasis property uses oxidation far above independent
Zinc or the bamboo wood of stannic oxide/graphene nano piece modification.This illustrates to there is collaborative pressing down between nano zine oxide and graphene oxide
The effect of bacterium, nano zine oxide immobilized on bamboo culm wall can promote the formation of peroxide, effectively decomposes and destroys bacterium
Structure, thus bacteria growing inhibiting, reach sterilizing and antibacterial effect；And stannic oxide/graphene nano piece can be come by machine cuts
Destroy Bacillus coli cells film, reach purpose, the carbonyl on stannic oxide/graphene nano piece and the hydroxyl on bamboo cell membrane of sterilizing
Between formed hydrogen bond also effectively strengthen its antibacterial stability；Additionally, nano zine oxide and the zinc ion concentration being released are in oxidation
On graphene nanometer sheet surface, substantially increasing bacterium and the chance of zinc contact, this is probably zinc oxide and graphene oxide
The composite modified main cause with collaborative inhibitory effect.
EXPERIMENTAL EXAMPLE 2:
According to the method described in embodiment 1, surface treatment is carried out to bamboo wood (1cm × 1cm × 1cm), then it is being contained
The nano zine oxide (being purchased from Chemical Reagent Co., Ltd., Sinopharm Group) of 2g/L and the aqueous solution of 2g/L stannic oxide/graphene nano piece
Middle dipping 12h, takes out bamboo wood water and cleans, is dried, and it is antibacterial that by the identical technique of EXPERIMENTAL EXAMPLE 1, it is carried out Escherichia coli
Performance test, it is 1.5cm to colibacillary inhibition zone.
EXPERIMENTAL EXAMPLE 3:
Enter with the surface to the bamboo wood of preparation in the bamboo wood prepared in embodiment 1 and EXPERIMENTAL EXAMPLE 2 such as scraper or sand paper
Row is processed, and wipes top layer about 2～3mm respectively off, carries out Escherichia coli anti-microbial property survey by the identical technique of EXPERIMENTAL EXAMPLE 1
Examination, it is respectively 2cm and 0.8cm to colibacillary inhibition zone.This explanation bamboo wood in use as surface is worn or
When secondary operations causes top layer to be destroyed, the bamboo wood being prepared by the method for the present invention still has good antibacterial effect, explanation
Zinc oxide and stannic oxide/graphene nano piece are deeper into the inside of bamboo wood and are securely joined with.
EXPERIMENTAL EXAMPLE 4:
It is in 90% high humidity closed environment by being placed on relative humidity according to the sample of embodiment the 1st, comparative example 1 to 3,
It appeared that the unmodified bamboo wood of comparative example 3 starts mildew occur for about 1 day, and after placing 30 days, comparative example 1
The modified bamboo wood of graphene oxide a small amount of mildew, after placing 90 days, the bamboo wood of the modified zinc oxide of comparative example 2 occur
A small amount of mildew also occurs, but the bamboo wood of the zinc oxide of embodiment 1 and the modification of stannic oxide/graphene nano piece is still without fungus growth, this
Nano zine oxide and the composite modified fungicidal properties that bamboo wood is greatly improved of graphene oxide are described.
Claims (9)
1. a preparation method for stannic oxide/graphene nano piece/zinc oxide/bamboo composite, described method includes walking as follows
Rapid:
1) bamboo material is pre-processed, first the surface of bamboo material is processed, for example, can utilize scraper or sand
The surface to bamboo material such as paper carries out the surface treatments such as polishing, then uses deionized water, ethanol vacuum ultrasonic 30 minutes successively
Purged of impurities, 40 DEG C of dryings；
2) by step 1) bamboo material that processes is totally submerged in the zinc salt mixed liquor being dispersed with stannic oxide/graphene nano piece, takes out
Vacuum, to below 0.01MPa, makes zinc salt and graphene oxide try one's best for ultrasonically treated 10 minutes and fills inside bamboo material, stand
24h；
3) toward step 2) mixed liquor is added dropwise over 1mol/L monoethanolamine solution regulation solution ph to 10, it again is evacuated to
Below 0.01MPa, after ultrasonically treated 10 minutes, takes out bamboo material after dipping 24h, by deionized water by clear for the impurity on its surface
Wash clean, 60 DEG C of dryings；
4) adding the suspension being dispersed with stannic oxide/graphene nano piece in zinc solution, wherein stannic oxide/graphene nano piece is dense
Degree is 0.02～3g/L, preferably 0.2～1g/L, and zinc solution concentration is 0.005～2mol/L, and mixing in ultrasonic 30 minutes is all
Even, it is added dropwise over monoethanolamine solution regulation pH value of solution=10 that concentration is 1mol/L, stirring 1h is allowed to mix；
5) by step 4) gained mixed liquor moves on in water heating kettle, adds step 3) bamboo material after the dipping of gained, bamboo wood with
Maceration extract volume ratio is 1:3 to 1:20, is heated to 60～200 DEG C under hydrothermal reaction condition, preferably 70～130 DEG C, is incubated 1～96
Hour, preferably 2～12 hours, cooling, take out bamboo wood, wash with water 3 to 5 times, be dried, i.e. obtain Graphene/zinc oxide/bamboo wood
Composite.
2. the preparation method of stannic oxide/graphene nano piece/zinc oxide/bamboo composite according to claim 1, it is special
Levy and be, step 1) described bamboo material can be circle bamboo, bamboo chip, Bamboo veneer, bamboo silk, bamboo fibre, bamboo particle etc., comprise hair
The bamboo kinds such as bamboo, black bamboo, firm bamboo, phyllostachys bambusoides or Fang Zhu, the shape of described bamboo material can be irregular shape or regular shape.
3. the preparation method of stannic oxide/graphene nano piece/zinc oxide/bamboo composite according to claim 2, it is special
Levy and be, the round bamboo section of the square shape being shaped as 1cm × 1cm × 1cm of described bamboo material or diameter 4cm × long 10cm.
4. the preparation method of stannic oxide/graphene nano piece/zinc oxide/bamboo composite according to claim 1, it is special
Levy and be, step 2) described in zinc salt be zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, the one in zinc dihydrogen phosphate or many
Kind, zinc salt concentration is 0.5～3mol/L, and stannic oxide/graphene nano piece concentration of aqueous solution is 0.5～10g/L.
5. the preparation method of stannic oxide/graphene nano piece/zinc oxide/bamboo composite according to claim 4, it is special
Levy and be, step 2) described in zinc salt concentration be 2～3mol/L, stannic oxide/graphene nano piece concentration of aqueous solution is 2～5g/L.
6. the preparation method of stannic oxide/graphene nano piece/zinc oxide/bamboo composite according to claim 1, it is special
Levy and be, step 4) described in zinc salt be zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, the one in zinc dihydrogen phosphate or many
Kind, concentration is 0.005～2mol/L.
7. the preparation method of stannic oxide/graphene nano piece/zinc oxide/bamboo composite according to claim 6, it is special
Levying and being, stating zinc salt concentration is 0.01～0.5mol/L.
8. a preparation method for stannic oxide/graphene nano piece/zinc oxide/bamboo composite, it comprises the steps:
The bamboo block scraper of 1cm × 1cm × 1cm shape is scraped off very thin one layer in surface, about about 1～2mm, then spend from
Sub-water, 30 minutes purged of impurities of ethanol vacuum ultrasonic, after 40 DEG C of dryings, be totally submerged in 20mL saturated acetic acid zinc and 1.5g/L
The stannic oxide/graphene nano piece mixed liquor of concentration, at vacuum condition ultrasonically treated 10 minutes, is added dropwise over 1mol/L after standing 24h
Monoethanolamine solution regulation solution ph, to 10, at vacuum condition ultrasonically treated 10 minutes, is taken out bamboo block after dipping 24h, is spent
The impurity on surface is rinsed well by ionized water, 60 DEG C of dryings；
The nitre adding the concentration of 20mL to be 0.05mol/L the stannic oxide/graphene nano piece aqueous solution that the concentration of 1.5mL is 10g/L
In acid zinc solution, within ultrasonic 30 minutes, mix, be added dropwise over the monoethanolamine solution of concentration 1mol/L to pH value of solution=10, stir
Mixing 1h to be allowed to mix, then moving on in water heating kettle, the bamboo block of the 1cm × 1cm × 1cm shape after addition process, at 120 DEG C
Hydro-thermal processes 3h, cooling, takes out bamboo block, washes with water 5 times, is dried, i.e. obtains stannic oxide/graphene nano piece/zinc oxide/bamboo wood
Composite.
9. stannic oxide/graphene nano piece/zinc oxide/bamboo composite, described stannic oxide/graphene nano piece/zinc oxide/bamboo
Material composite is combined by stannic oxide/graphene nano piece/zinc oxide/bamboo wood as claimed in any of claims 1 to 8
The preparation method of material prepares.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792581A (en) * | 2005-11-14 | 2006-06-28 | 深圳清华大学研究院 | Method for mfg. sterilizing nano plates |
| CN101659751A (en) * | 2009-09-21 | 2010-03-03 | 国际竹藤网络中心 | Natural lignocellulose material with modified zinc oxide and preparation method thereof |
| CN103283781A (en) * | 2013-06-21 | 2013-09-11 | 中山大学 | Graphene oxide loaded nanometer zinc oxide antibacterial agent, preparation method and applications thereof |
| CN103535376A (en) * | 2013-09-15 | 2014-01-29 | 浙江理工大学 | Preparation method of nanometer zinc oxide-bamboo charcoal composite particle with antibacterial and adsorption functions |
| CN103734188A (en) * | 2014-01-02 | 2014-04-23 | 上海大学 | Preparation method and applications of zinc oxide-graphene oxide composite nanomaterial |
| CN104068058A (en) * | 2014-07-01 | 2014-10-01 | 南京林业大学 | Preparation method for graphene oxide bacteria-inhibiting composite material |
| CN104264259A (en) * | 2014-10-15 | 2015-01-07 | 钱景 | Graphene and salix psammophila regenerated cellulose blended fiber and preparation method thereof |
| CN105498689A (en) * | 2015-12-09 | 2016-04-20 | 唐山冀东石墨烯科技发展有限公司 | Graphene loaded nano ZnO/Ag composite material and preparation method thereof |
-
2016
- 2016-07-05 CN CN201610523053.0A patent/CN106142243B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792581A (en) * | 2005-11-14 | 2006-06-28 | 深圳清华大学研究院 | Method for mfg. sterilizing nano plates |
| CN101659751A (en) * | 2009-09-21 | 2010-03-03 | 国际竹藤网络中心 | Natural lignocellulose material with modified zinc oxide and preparation method thereof |
| CN103283781A (en) * | 2013-06-21 | 2013-09-11 | 中山大学 | Graphene oxide loaded nanometer zinc oxide antibacterial agent, preparation method and applications thereof |
| CN103535376A (en) * | 2013-09-15 | 2014-01-29 | 浙江理工大学 | Preparation method of nanometer zinc oxide-bamboo charcoal composite particle with antibacterial and adsorption functions |
| CN103734188A (en) * | 2014-01-02 | 2014-04-23 | 上海大学 | Preparation method and applications of zinc oxide-graphene oxide composite nanomaterial |
| CN104068058A (en) * | 2014-07-01 | 2014-10-01 | 南京林业大学 | Preparation method for graphene oxide bacteria-inhibiting composite material |
| CN104264259A (en) * | 2014-10-15 | 2015-01-07 | 钱景 | Graphene and salix psammophila regenerated cellulose blended fiber and preparation method thereof |
| CN105498689A (en) * | 2015-12-09 | 2016-04-20 | 唐山冀东石墨烯科技发展有限公司 | Graphene loaded nano ZnO/Ag composite material and preparation method thereof |
Cited By (16)
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|---|---|---|---|---|
| CN106863507A (en) * | 2016-12-30 | 2017-06-20 | 亚振家具股份有限公司 | A kind of method that timber hydrophobicity and stability are improved based on nano titanium oxide |
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| CN106799259A (en) * | 2017-01-18 | 2017-06-06 | 浙江省林业科学研究院 | A kind of preparation method of the bamboo matter composite for loading graphene oxide/nano-silver layer |
| CN106824266B (en) * | 2017-01-18 | 2019-04-19 | 浙江农林大学 | A kind of preparation method loading graphene oxide/nano titania layer bamboo matter composite material |
| CN106799259B (en) * | 2017-01-18 | 2019-05-03 | 浙江省林业科学研究院 | A kind of preparation method loading graphene oxide/nano-silver layer bamboo matter composite material |
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| CN111958744B (en) * | 2020-07-01 | 2022-07-08 | 阜阳大可新材料股份有限公司 | Production method of environment-friendly moisture-proof high-density fiberboard with thickness of 1mm |
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