CN106818867B - Environment-friendly biomass nano-antibacterial ornament materials and preparation method thereof - Google Patents
Environment-friendly biomass nano-antibacterial ornament materials and preparation method thereof Download PDFInfo
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- CN106818867B CN106818867B CN201710081251.0A CN201710081251A CN106818867B CN 106818867 B CN106818867 B CN 106818867B CN 201710081251 A CN201710081251 A CN 201710081251A CN 106818867 B CN106818867 B CN 106818867B
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- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
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- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
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- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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Abstract
Environment-friendly biomass nano-antibacterial ornament materials and preparation method thereof, belongs to decoration material field.All it is indoor antibacterial environment protection coating on the market now, environmentally protective requirement cannot be fully achieved.The present invention is made of zinc acetate, distilled water, cellulose, plant polyphenol, its parts by weight is respectively 1~70 part of zinc acetate, 10~500 parts of distilled water A, 5~15 parts of cellulose, 50~100 parts of distilled water B, 1~10 part of plant polyphenol, 10~100 parts of distilled water C.Cellulose of the present invention is bacteria cellulose, cellulose acetate, carboxymethyl cellulose, microcrystalline cellulose, cotton fiber, non-woven fabrics, paper, broadleaf, softwood, cellulose ether, methylcellulose, hydroxypropyl methyl cellulose, at least one of hydroxyethyl cellulose.The present invention can kill the bacterium in air, and zinc oxide is nontoxic, and required Zn-ef ficiency can be also provided for human body, environmentally protective, can recycle.
Description
Technical field
The invention belongs to decoration material fields；More particularly to a kind of environment-friendly biomass nano-antibacterial ornament materials and its system
Preparation Method.
Background technique
Spring is the season that influenza virus is most easily propagated, based on influenza is directly propagated with airborne droplet, one sound of flu victims
Cough, can propagate there are about 100,000 germs, a sneeze about contains 1,000,000 germs, and a sneeze can make droplet with 167 kilometers
Speed per hour, the place other than 6 meters is ejected into one second.The virus propagation unscrupulous in air that flu victims carry, and children
Resistance it is generally lower, it is easier to influenza.Therefore, the bacterium in air can be killed and the material nontoxic to body
By the concern of domestic and international personage.
It left floating bulky grain in haze weather air, hundreds of Atmospheric particulates can be directly entered and be attached on human body or more
In respiratory tract and the lobe of the lung, and it can largely be sucked by human body.Secondly, haze weather causes surface layer ultraviolet light to weaken, it is easy
So that in air germ increased activity, fine particle meeting " with " bacterium, virus come the depths of respiratory system, cause to feel
Dye.Particulate pollutant in haze day can not only cause myocardial infarction, also will cause myocardial ischemia or damage, be also easy to induce the heart
The acute attack of vascular diseases.Therefore, can adsorb the bulky grain in air but also kill the material of bacterium is domestic and foreign scholars
The emphasis of concern.
What is had on the market now is all indoor antibacterial environment protection coating, and general silver-doped is as a kind of antibacterial inside coating
Agent, nano-Ag particles more because that can be directly entered thallus in conjunction with oxygen metabolism enzyme, make thallus be choked to death, can kill and connect with it
The microorganisms such as the most of bacteriums, fungi, mould, the spore that touch, but environmentally protective requirement cannot be fully achieved in coating itself,
And price is higher.
Summary of the invention
It is an object of the present invention to provide a kind of environment-friendly biomass nano-antibacterial ornament materials and preparation method thereof, can both kill
The bacterium gone out in air, can provide required Zn-ef ficiency also for human body, environmentally protective.
The invention is realized by the following technical scheme:
A kind of environment-friendly biomass nano-antibacterial ornament materials, the environment-friendly biomass nano-antibacterial ornament materials master
If being made of zinc acetate, distilled water, cellulose, plant polyphenol, parts by weight be respectively 1~70 part zinc acetate, 10~
500 parts of distilled water A, 5~15 parts of cellulose, 50~100 parts of distilled water B, 1~10 part of plant polyphenol, 10~100 parts
Distilled water C.
Environment-friendly biomass nano-antibacterial ornament materials of the present invention, the cellulose are bacteria cellulose, vinegar
Acid cellulose, carboxymethyl cellulose, microcrystalline cellulose, cotton fiber, non-woven fabrics, paper, broadleaf, softwood, cellulose ether, methyl
At least one of cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose.
Environment-friendly biomass nano-antibacterial ornament materials of the present invention, the plant polyphenol are tea polyphenols, grape
At least one of polyphenol, apple polyphenol.
The preparation method of environment-friendly biomass nano-antibacterial ornament materials of the present invention, includes the following steps:
The preparation of step 1, nano-ZnO solution: zinc acetate, the distilled water A of certain mass are weighed according to parts by weight, will be claimed
Measured zinc acetate is poured into distilled water A and is stirred, until the complete clear of solution, with NaOH solution adjust pH value 7~
In 12 ranges, for use；
Step 2, cellulose mix the preparation of nano oxidized zinc solution: weighing the fiber of certain mass according to parts by weight
Element, distilled water B, load weighted cellulose is poured into distilled water B and is stirred, is stirring evenly and then adding into made from step 1 and receives
Rice ZnO solution, continues stand-by after mixing evenly；
The preparation of step 3, cellulose mixing nano zinc oxide material: cellulose prepared by step 2 mixes nano oxidized
Zinc solution pours into and carries out hydro-thermal reaction in hydrothermal reaction kettle, and 80~220 DEG C of reaction temperature, 10~16h of reaction time, end of reaction
It is stand-by after the product natural cooling, distillation water washing and the filtering that obtain afterwards；
The synthesis of step 4, environment-friendly biomass nano-antibacterial ornament materials: the plant of certain mass is weighed according to parts by weight
Object polyphenol, distilled water C, load weighted plant polyphenol is poured into distilled water C and is stirred, and is stirring evenly and then adding into step 3 system
The cellulose mixing nano zinc oxide material obtained, stirs 30min, and 200~500rpm of agitator speed is put into ultrasonic wave after stirring
Middle progress ultrasonic vibration 20min, ultrasonic power are set as 500~1500W, and the product after ultrasound is put into 80 DEG C of thermostatic drying chambers
Environment-friendly biomass nano-antibacterial ornament materials is made in middle drying.
The preparation method of environment-friendly biomass nano-antibacterial ornament materials of the present invention, NaOH solution in step 1
Concentration is 1mol/l.
The preparation method of environment-friendly biomass nano-antibacterial ornament materials of the present invention, the mixing time in step 2
It is 1~5h.
The preparation method of environment-friendly biomass nano-antibacterial ornament materials of the present invention, hydrothermal reaction kettle in step 3
The volume that middle cellulose mixes nano oxidized zinc solution accounts for the 80% of reaction kettle volume.
The preparation method of environment-friendly biomass nano-antibacterial ornament materials of the present invention, product is naturally cold in step 3
But time is 10~72h.
The preparation method of environment-friendly biomass nano-antibacterial ornament materials of the present invention, constant temperature drying in step 4
Time is 10~72h.
Compound effective component in the present invention in plant polyphenol can be with a variety of pairs of human bodies such as formaldehyde in indoor air, VOC
Poisonous and hazardous pollutant is chemically reacted, and the pollutant in room air is effectively removed, until the special role of purification.Example
If tea polyphenols main component is flavanol compound, anthocyan, anthoxanthins, contracting acid and depside composition, molecule is in space
The recombination of structure and chelating, generate molecule structure change and generate active oxygen, can effectively stable free electron, so that electronics is left original
Position, forms the hydrogen bond of intramolecular, the activated state of formation can with the pollutant reactions such as formaldehyde in indoor air, to remove first
Aldehyde.
Environment-friendly biomass nano-antibacterial decorative material surface of the present invention is enriched ZnO particle, high surface activity,
The anti-microbial property of the common strain such as Escherichia coli, staphylococcus aureus is had excellent performance than existing anti-biotic material, antibacterial ring size
Width is 11.9mm.
The present invention uses the environment-friendly biomass nano-antibacterial ornament materials of hydrothermal synthesis method synthesis, can kill in air
Bacterium, zinc oxide is nontoxic, and required Zn-ef ficiency can be also provided for human body, environmentally protective, can recycle.Environment-friendly type
Biomass nano antibacterial decorative material may be used as fancy goods, books paper, wallpaper, calligraphy paintings, mask filter layer, food
Packaging etc..Environment-friendly biomass nano-antibacterial ornament materials prepared by the present invention is low in cost and antibiotic property with higher
Can, it is the critical material for making upholstery.
The method of the present invention simple process, equipment requirement is not high, and the low in raw material price such as cellulose are easy to get, and are easy to back
It receives, therefore production cost is low, it can large-scale industrial production；The cellulose used is natural products, environmental-friendly, pollution-free.
Zinc oxide partial size in environment-friendly biomass nano-antibacterial ornament materials of the present invention is on a 10nm~2 μm left side
The right side, regular appearance, basic soilless sticking, good dispersion.
Detailed description of the invention
Fig. 1 is the SEM photograph of environment-friendly biomass nano-antibacterial ornament materials prepared by specific embodiment one；
Fig. 2 is the SEM photograph for the contrast material that specific embodiment one is not added with zinc acetate；
Fig. 3 is the XRD spectra of environment-friendly biomass nano-antibacterial ornament materials prepared by specific embodiment one；
Fig. 4 is the photo of environment-friendly biomass nano-antibacterial ornament materials sample prepared by specific embodiment one；
Fig. 5 is the antibacterial of environment-friendly biomass nano-antibacterial ornament materials sample prepared by specific embodiment one to contrasting
Piece；
Fig. 6 is the ANTIMICROBIAL DATA column of environment-friendly biomass nano-antibacterial ornament materials prepared by specific embodiment one
Figure；
Fig. 7 is the SEM photograph of environment-friendly biomass nano-antibacterial ornament materials prepared by specific embodiment two.
Specific embodiment
Specific embodiment 1:
A kind of environment-friendly biomass nano-antibacterial ornament materials, the environment-friendly biomass nano-antibacterial ornament materials master
If being made of zinc acetate, distilled water, cellulose, plant polyphenol, parts by weight be respectively 30 parts zinc acetate, 250 parts
Distilled water A, 10 parts of cellulose, 100 parts of distilled water B, 5 parts of plant polyphenol, 50 parts of distilled water C.
Environment-friendly biomass nano-antibacterial ornament materials described in present embodiment, the cellulose are filter paper；It is described
Plant polyphenol be tea polyphenols.
The preparation method of environment-friendly biomass nano-antibacterial ornament materials, includes the following steps: described in present embodiment
The preparation of step 1, nano-ZnO solution: zinc acetate, the distilled water A of certain mass are weighed according to parts by weight, will be claimed
Measured zinc acetate is poured into distilled water A and is stirred, until the complete clear of solution, adjusting pH value with NaOH solution is 10,
For use；
Step 2, cellulose mix the preparation of nano oxidized zinc solution: weighing the fiber of certain mass according to parts by weight
Element, distilled water B, load weighted cellulose is poured into distilled water B and is stirred, mixing time 2 hours, is stirring evenly and then adding into
Nano-ZnO solution made from step 1 continues to stir 1h, after mixing evenly for use；
The preparation of step 3, cellulose mixing nano zinc oxide material: cellulose prepared by step 2 mixes nano oxidized
Zinc solution pours into and carries out hydro-thermal reaction in hydrothermal reaction kettle, and 100 DEG C of reaction temperature, reaction time 10h is obtained after completion of the reaction
It is stand-by after product natural cooling, distillation water washing and filtering；
The synthesis of step 4, environment-friendly biomass nano-antibacterial ornament materials: the plant of certain mass is weighed according to parts by weight
Object polyphenol, distilled water C, load weighted plant polyphenol is poured into distilled water C and is stirred, and is stirring evenly and then adding into step 3 system
Cellulose mixing nano zinc oxide material, stirring 30min, agitator speed 200rpm, be put into after stirring in ultrasonic wave into
Row ultrasonic vibration 20min, ultrasonic power are set as 500W, and the product after ultrasound, which is put into 80 DEG C of thermostatic drying chambers, dries, and make
Obtain environment-friendly biomass nano-antibacterial ornament materials.
The preparation method of environment-friendly biomass nano-antibacterial ornament materials described in present embodiment, NaOH is molten in step 1
The concentration of liquid is 1mol/l；The volume that cellulose mixes nano oxidized zinc solution in hydrothermal reaction kettle in step 3 accounts for reaction kettle body
Long-pending 80%；The time of product natural cooling is 10h in step 3；The time of constant temperature drying is 10h in step 4.
Hydrothermal reaction kettle is the hydrothermal reaction kettle of polytetrafluoroethylsubstrate substrate in present embodiment.
The SEM picture of environment-friendly biomass nano-antibacterial ornament materials described in present embodiment is as shown in Figure 1, XRD is composed
Figure as shown in figure 3, comparison be not added zinc acetate scanning electron microscope diagram piece it is as shown in Figure 2.
It is zinc oxide little particle regular appearance it can be seen from Fig. 1, uniform, the short grained partial size of zinc oxide is about 10~
20nm or so, above small particles random distribution biggish Zinc oxide particles, diameter be about 100nm, long is about 500nm left
It is right.
From the XRD spectrum of Fig. 3 it can be seen that diffraction maximum is very sharp, illustrate that crystallinity is very high, and do not occur impurity peaks, explanation
Purity is very high.Fig. 2 is the scanning electron microscope diagram piece that zinc acetate is not added, and as seen from the figure, filter paper is beaten into ultra-fine fibre
Dimension, average diameter are 100nm or so.
The anti-microbial property of environment-friendly biomass nano-antibacterial ornament materials described in present embodiment is with golden yellow grape
Coccus (S.aureus) and Escherichia coli (E.coli) are template, pass through the size of measurement antibacterial ring size using Drug sensitivity test
Come what is determined.The bacterium of one pipe fresh cultured is used to match bacteria suspension, and concentration is about 108CFU/ml.150 μ l are pipetted with liquid-transfering gun
Diluted bacteria suspension is placed on training in bacterium solution on culture medium, to be uniformly coated on to the surface of culture medium with spreading rod, then by sample
The centre of base, labelled paper are supported, inverted plate cultivates 18h at 37 DEG C in constant incubator.After culture, around sample
It was found that there is transparent antibacterial ring size to occur, the size of antibacterial ring size, each plate amount 3 times are measured with ruler, and be averaged each sample
The inhibition zone diameter of product measures in three times, is averaged, and also measurement repeatedly, guarantees the repeatability of data to every group of sample.
The print photo of environment-friendly biomass nano-antibacterial ornament materials described in present embodiment, antimicrobial sample comparison photo and antibacterial
Histogram is as shown in Fig. 4, Fig. 5, Fig. 6.
Environment-friendly biomass nano-antibacterial ornament materials anti-microbial property described in present embodiment is good.By that can be seen in Fig. 6
The anti-microbial property of staphylococcus aureus is better than Escherichia coli out, and with the increase of acetic acid Zn content, antibacterial ring width also exists
Increase.The sample that the acetic acid Zn content of pH 9 is 3g is to the antibacterial ring width of Escherichia coli and staphylococcus aureus
10.25mm and 11.9mm.
Specific embodiment 2:
A kind of environment-friendly biomass nano-antibacterial ornament materials, the environment-friendly biomass nano-antibacterial ornament materials master
If being made of zinc acetate, distilled water, cellulose, plant polyphenol, parts by weight be respectively 35 parts zinc acetate, 300 parts
Distilled water A, 10 parts of cellulose, 100 parts of distilled water B, 1 part of plant polyphenol, 10 parts of distilled water C.
Environment-friendly biomass nano-antibacterial ornament materials described in present embodiment, the cellulose are filter paper；It is described
Plant polyphenol be tea polyphenols.
The preparation method of environment-friendly biomass nano-antibacterial ornament materials, includes the following steps: described in present embodiment
The preparation of step 1, nano-ZnO solution: zinc acetate, the distilled water A of certain mass are weighed according to parts by weight, will be claimed
Measured zinc acetate is poured into distilled water A and is stirred, until the complete clear of solution, adjusting pH value with NaOH solution is 12,
For use；
Step 2, cellulose mix the preparation of nano oxidized zinc solution: weighing the fiber of certain mass according to parts by weight
Element, distilled water B, load weighted cellulose is poured into distilled water B and is stirred, mixing time 2 hours, is stirring evenly and then adding into
Nano-ZnO solution made from step 1 continues to stir 1h, after mixing evenly for use；
The preparation of step 3, cellulose mixing nano zinc oxide material: cellulose prepared by step 2 mixes nano oxidized
Zinc solution pours into and carries out hydro-thermal reaction in hydrothermal reaction kettle, and 180 DEG C of reaction temperature, reaction time 10h is obtained after completion of the reaction
It is stand-by after product natural cooling, distillation water washing and filtering；
The synthesis of step 4, environment-friendly biomass nano-antibacterial ornament materials: the plant of certain mass is weighed according to parts by weight
Object polyphenol, distilled water C, load weighted plant polyphenol is poured into distilled water C and is stirred, and is stirring evenly and then adding into step 3 system
Cellulose mixing nano zinc oxide material, stirring 30min, agitator speed 200rpm, be put into after stirring in ultrasonic wave into
Row ultrasonic vibration 20min, ultrasonic power are set as 500W, and the product after ultrasound, which is put into 80 DEG C of thermostatic drying chambers, dries, and make
Obtain environment-friendly biomass nano-antibacterial ornament materials.
The preparation method of environment-friendly biomass nano-antibacterial ornament materials described in present embodiment, NaOH is molten in step 1
The concentration of liquid is 1mol/l；The volume that cellulose mixes nano oxidized zinc solution in hydrothermal reaction kettle in step 3 accounts for reaction kettle body
Long-pending 80%；The time of product natural cooling is 10h in step 3；The time of constant temperature drying is 10h in step 4.
The SEM picture of environment-friendly biomass nano-antibacterial ornament materials described in present embodiment is as shown in Figure 7.
It in cellulose surface growth is acicular type zinc oxide that a length of 1 μm of width is 100nm or so it can be seen from Fig. 7,
Cellulose fibre outer surface is oxidized zinc and wraps.
Environment-friendly biomass nano-antibacterial ornament materials described in present embodiment is easy to use, and preparation is simple, using wide
It is general, ZnO and cellulose, plant polyphenol are carried out compound, using the antibiotic property of ZnO and the low cost of cellulose, easy moulding and made
The advantages of type malleable, manufactured product is portable, and price is low, and moulding can change with the appreciation level and mood of consumer
Become, and can also be recycled after it repeatedly folds aesthetics decline, is processed again.
Claims (7)
1. a kind of environment-friendly biomass nano-antibacterial ornament materials, it is characterised in that: the environment-friendly biomass nano-antibacterial
Ornament materials is mainly made of zinc acetate, distilled water, cellulose, plant polyphenol, and parts by weight are respectively 1~70 part of second
Sour zinc, 10~500 parts of distilled water A, 5~15 parts of cellulose, 50~100 parts of distilled water B, 1~10 part of plant polyphenol,
10~100 parts of distilled water C；
The cellulose is filter paper；
The plant polyphenol is tea polyphenols；
A kind of environment-friendly biomass nano-antibacterial ornament materials, to common bacterias such as Escherichia coli, staphylococcus aureuses
The anti-microbial property of kind is had excellent performance than existing anti-biotic material, and antibacterial ring width is 11.9mm；
A kind of preparation method of environment-friendly biomass nano-antibacterial ornament materials, includes the following steps:
The preparation of step 1, nano-ZnO solution: zinc acetate, the distilled water A of certain mass are weighed according to parts by weight, will be weighed
Zinc acetate pour into distilled water A and be stirred, until the complete clear of solution, adjusts pH value in 7~12 models with NaOH solution
In enclosing, for use；
Step 2, cellulose mix the preparation of nano oxidized zinc solution: weighing the cellulose of certain mass according to parts by weight, steam
Load weighted cellulose is poured into distilled water B and is stirred by distilled water B, is stirring evenly and then adding into nano-ZnO made from step 1
Solution continues stand-by after mixing evenly；
The preparation of step 3, cellulose mixing nano zinc oxide material: cellulose mixing nano zine oxide prepared by step 2 is molten
Liquid pours into and carries out hydro-thermal reaction in hydrothermal reaction kettle, and 80~220 DEG C of reaction temperature, 10~16h of reaction time, after completion of the reaction
It is stand-by after product natural cooling, distillation water washing and the filtering arrived；
The synthesis of step 4, environment-friendly biomass nano-antibacterial ornament materials: the plant for weighing certain mass according to parts by weight is more
Phenol, distilled water C, load weighted plant polyphenol is poured into distilled water C and is stirred, is stirring evenly and then adding into made from step 3
Cellulose mixing nano zinc oxide material, stir 30min, 200~500rpm of agitator speed, be put into after stirring in ultrasonic wave into
Row ultrasonic vibration 20min, ultrasonic power are set as 500~1500W, and the product after ultrasound, which is put into 80 DEG C of thermostatic drying chambers, to be dried
It is dry, environment-friendly biomass nano-antibacterial ornament materials is made.
2. a kind of preparation method of environment-friendly biomass nano-antibacterial ornament materials described in claim 1, it is characterised in that: packet
Include following steps:
The preparation of step 1, nano-ZnO solution: zinc acetate, the distilled water A of certain mass are weighed according to parts by weight, will be weighed
Zinc acetate pour into distilled water A and be stirred, until the complete clear of solution, adjusts pH value in 7~12 models with NaOH solution
In enclosing, for use；
Step 2, cellulose mix the preparation of nano oxidized zinc solution: weighing the cellulose of certain mass according to parts by weight, steam
Load weighted cellulose is poured into distilled water B and is stirred by distilled water B, is stirring evenly and then adding into nano-ZnO made from step 1
Solution continues stand-by after mixing evenly；
The preparation of step 3, cellulose mixing nano zinc oxide material: cellulose mixing nano zine oxide prepared by step 2 is molten
Liquid pours into and carries out hydro-thermal reaction in hydrothermal reaction kettle, and 80~220 DEG C of reaction temperature, 10~16h of reaction time, after completion of the reaction
It is stand-by after product natural cooling, distillation water washing and the filtering arrived；
The synthesis of step 4, environment-friendly biomass nano-antibacterial ornament materials: the plant for weighing certain mass according to parts by weight is more
Phenol, distilled water C, load weighted plant polyphenol is poured into distilled water C and is stirred, is stirring evenly and then adding into made from step 3
Cellulose mixing nano zinc oxide material, stir 30min, 200~500rpm of agitator speed, be put into after stirring in ultrasonic wave into
Row ultrasonic vibration 20min, ultrasonic power are set as 500~1500W, and the product after ultrasound, which is put into 80 DEG C of thermostatic drying chambers, to be dried
It is dry, environment-friendly biomass nano-antibacterial ornament materials is made.
3. the preparation method of environment-friendly biomass nano-antibacterial ornament materials according to claim 2, it is characterised in that: step
The concentration of NaOH solution is 1mol/l in rapid 1.
4. the preparation method of environment-friendly biomass nano-antibacterial ornament materials according to claim 2, it is characterised in that: step
Mixing time in rapid 2 is 1~5h.
5. the preparation method of environment-friendly biomass nano-antibacterial ornament materials according to claim 2, it is characterised in that: step
The volume that cellulose mixes nano oxidized zinc solution in hydrothermal reaction kettle in rapid 3 accounts for the 80% of reaction kettle volume.
6. the preparation method of environment-friendly biomass nano-antibacterial ornament materials according to claim 2, it is characterised in that: step
The time of product natural cooling is 10~72h in rapid 3.
7. the preparation method of environment-friendly biomass nano-antibacterial ornament materials according to claim 2, it is characterised in that: step
The time of constant temperature drying is 10~72h in rapid 4.
Priority Applications (1)
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