CN106142243B - 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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- CN106142243B CN106142243B CN201610523053.0A CN201610523053A CN106142243B CN 106142243 B CN106142243 B CN 106142243B CN 201610523053 A CN201610523053 A CN 201610523053A CN 106142243 B CN106142243 B CN 106142243B
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- 239000011425 bamboo Substances 0.000 title claims abstract description 177
- 235000017166 Bambusa arundinacea Nutrition 0.000 title claims abstract description 163
- 235000017491 Bambusa tulda Nutrition 0.000 title claims abstract description 163
- 241001330002 Bambuseae Species 0.000 title claims abstract description 163
- 235000015334 Phyllostachys viridis Nutrition 0.000 title claims abstract description 163
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000000845 anti-microbial effect Effects 0.000 title description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 128
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 79
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000002023 wood Substances 0.000 claims abstract description 63
- 239000000463 material Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000004381 surface treatment Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 40
- 239000011701 zinc Substances 0.000 claims description 33
- 229910052725 zinc Inorganic materials 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 150000003751 zinc Chemical class 0.000 claims description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 18
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 206010013786 Dry skin Diseases 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 claims description 5
- 244000137852 Petrea volubilis Species 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 150000001243 acetic acids Chemical class 0.000 claims description 3
- 240000007880 Phyllostachys bambusoides Species 0.000 claims description 2
- 235000001550 Phyllostachys bambusoides Nutrition 0.000 claims description 2
- 240000005827 Phyllostachys nigra Species 0.000 claims description 2
- 235000010717 Phyllostachys nigra Nutrition 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 230000001788 irregular Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 240000003096 Chimonobambusa quadrangularis Species 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000005498 polishing Methods 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 52
- 239000011787 zinc oxide Substances 0.000 abstract description 25
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 21
- 230000001408 fungistatic effect Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000003115 biocidal effect Effects 0.000 abstract description 4
- 239000004480 active ingredient Substances 0.000 abstract description 2
- -1 graphene oxide/modified zinc oxide Chemical class 0.000 abstract description 2
- 238000002203 pretreatment Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 26
- 241000588724 Escherichia coli Species 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 6
- 230000005764 inhibitory process Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 210000000170 cell membrane Anatomy 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 240000007833 Dracaena angustifolia Species 0.000 description 1
- 235000009262 Dracaena angustifolia Nutrition 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical class [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Forests & Forestry (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The invention discloses a kind of preparation method of stannic oxide/graphene nano piece/zinc oxide/bamboo composite, zinc oxide and stannic oxide/graphene nano piece are in depth incorporated in inside bamboo wood by methods described by hydro-thermal reaction, so as to obtain the stannic oxide/graphene nano piece/zinc oxide/bamboo composite with good fungistatic effect.The method according to the invention technique is simple, green and cost is low, the surface treatment method being modified different from 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 set to penetrate into material internal, active ingredient not easily runs off, good anti-bacterial effect and persistently.Bamboo wood can also keep preferable antibiotic property in the secondary operation in later stage.
Description
Technical field
The invention belongs to field of compound material, and in particular to a kind of bamboo composite and preparation side with antibiotic property
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 features such as high and renewable, it can be widely applied to the multiple fields such as building, building materials, household.China's bamboo timber resource enriches, and rationally opens
Hair can alleviate the problems such as domestic timber resources is in short supply using bamboo wood, have very high economic value and the ecological value.Especially building
In terms of building materials application, bamboo structure has in light weight, good toughness, deforms many advantages, such as small and intensity is high, can make truss
Solve the problems, such as the large span in building, be a kind of high-quality low energy building material, accorded with by the use of bamboo wood as modern architecture material
Close the requirement of sustainable development.However, natural bamboo is because the compositions such as aqueous, starch, protein, lignin are easily by bacterium and mould
The erosion of bacterium, so as to cause bamboo wood is easily mouldy to rot, make it be not easy to store after processing, be unfavorable for the large-scale comprehensive profit of bamboo wood
With.Although the characteristics of bamboo structure itself makes bamboo wood be easy to regularization and standardization, the problems such as fresh bamboo wood storage is difficult is limited to,
Large-scale standardization and industrialization is still not implemented in the building matching component of bamboo wood at present.Therefore, anti-corrosive antibacterial is carried out to bamboo wood
Processing, extend bamboo wood storage and service life, value and product function for improving bamboo wood, promote bamboo wood in Building wood
Large-scale application in terms of material has important practical significance.
Traditional bamboo and wood material anti-biotic material mainly uses organic bactericide, such as pentachlorophenol, there is that toxicity is big, the term of validity
It is short, chemical stability is poor and only has the shortcomings that bacteriostasis to part strain.Due to good anti-bacterial effect, heat endurance it is good, no
It is long and the advantages that to humans and animals nontoxicity to be also easy to produce drug resistance, effect, the inorganic antibacterial material using titanium dioxide as representative
Extensive concern is received in recent years.Such as it is remaining use normal temperature dipping and Low Temperature Heat Treatment method be combined prepare it is nano zinc oxide modified
Bamboo and wood material, the antimildew and antibacterial performance [application for a patent for invention number of bamboo and wood material can be improved:200910093088.5].Mineral-modified bamboo
Timber in wood surface frequently with covering with paint, lacquer, colour wash, etc. various coating or to prepare bamboo and wood material/inorganic matter with impregnation inorganic matter presoma multiple
Condensation material.But though semar technique plays a protective role, top layer is easily peeled off, and the problems such as yellowing, loss of gloss be present；And impregnate
Method by most of inorganic deposition or can only be filled in bamboo wood top layer, and the heat endurance, antibacterial effect to bamboo wood are particularly long-acting
The improvement of property is limited.
The 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, using the method that supersonic oscillations and negative pressure of vacuum are combined by before inorganic matter
Drive body to impregnate inside bamboo wood, stannic oxide/graphene nano piece/zinc oxide/bamboo wood compound material is then prepared using hydro-thermal process method
Material, it is simple for process, green, cost is cheap, and stannic oxide/graphene nano piece and nano zine oxide are easily inside bamboo wood
Growth, can obviously improve the heat endurance and anti-microbial property of bamboo wood.
The preparation method of stannic oxide/graphene nano piece/zinc oxide/bamboo composite according to the present invention is included such as
Lower step：
1) bamboo material is pre-processed, the surface of bamboo material handled first, such as scraper can be utilized
Or sand paper etc. carries out the surface treatment such as polish to the surface of bamboo material, then successively with deionized water, ethanol vacuum ultrasonic 30
Minute purged of impurities, 40 DEG C of dryings；
2) bamboo material by step 1) processing is totally submerged in the zinc salt mixed liquor for being dispersed with stannic oxide/graphene nano piece
In, below 0.01MPa is evacuated to, being ultrasonically treated makes zinc salt and graphene oxide fill as far as possible inside bamboo material for 10 minutes,
Stand 24h；
3) solution ph is adjusted to 10 toward 1mol/L monoethanolamine solutions are added dropwise in step 2) mixed liquor, take out again true
It is empty that after being ultrasonically treated 10 minutes, bamboo material is taken out after impregnating 24h to below 0.01MPa, with deionized water by the miscellaneous of its surface
Matter cleans up, 60 DEG C of dryings；
4) suspension for 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, ultrasound 30 minutes mix
Uniformly, the monoethanolamine solution that concentration is 1mol/L is added dropwise and adjusts pH value of solution=10, stirring 1h is allowed to well mixed；
5) mixed liquor obtained by step 4) is moved on in water heating kettle, the bamboo material added after the dipping obtained by step 3), bamboo wood
It is 1 with maceration extract volume ratio:3 to 1:20, it is heated to 60~200 DEG C, preferably 70~130 DEG C under hydrothermal reaction condition, insulation 1~
96 hours, preferably 2~12 hours, cooling, bamboo wood is taken out, is washed with water 3 to 5 times, dried, that is, obtain graphene/zinc oxide/bamboo
Material composite.
Wherein, the step 1) bamboo material can be circle 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 1cm × 1cm × 1cm square shape or diameter 4cm × length
10cm circle bamboo section.
Zinc salt described in step 2) be zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, one kind in zinc dihydrogen phosphate or
A variety of, 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；
Zinc salt described in step 4) be zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, one kind in zinc dihydrogen phosphate or
A variety of, concentration is 0.005~2mol/L, preferably 0.01~0.5mol/L.
According to an aspect of the invention, there is provided a kind of stannic oxide/graphene nano piece/zinc oxide/bamboo composite
Preparation method, it comprises the following steps：
Bamboo block (1cm × 1cm × 1cm) is scraped off into very thin one layer in surface with scraper, about 1~2mm or so, then spend from
30 minutes sub- water, ethanol vacuum ultrasonic purged of impurities, after 40 DEG C of dryings, it is totally submerged in 20mL saturated acetic acids zinc and oxidation stone
Black alkene nanometer sheet (1.5g/L) mixed liquor, it is ultrasonically treated 10 minutes in vacuum condition, the mono- second of 1mol/L is added dropwise after standing 24h
Alkanolamine solution adjusts solution ph to 10, is ultrasonically treated 10 minutes in vacuum condition, takes out bamboo block after impregnating 24h, use deionization
Water rinses the impurity on surface well, 60 DEG C of dryings；
It is 0.05mol/L by the concentration that the stannic oxide/graphene nano piece aqueous solution that 1.5mL concentration is 10g/L adds 20mL
Zinc nitrate solution in, ultrasound 30 minutes is well mixed, and monoethanolamine solution (1mol/L) is added dropwise to pH value of solution=10, stirs
Mix 1h and be allowed to well mixed, then move on in water heating kettle, the bamboo block (1cm × 1cm × 1cm) after addition processing, in 120 DEG C of hydro-thermals
3h is handled, cooling, bamboo block is taken out, is washed with water 5 times, dries, that is, it is compound to obtain stannic oxide/graphene nano piece/zinc oxide/bamboo wood
Material.
According to an aspect of the invention, there is provided a kind of stannic oxide/graphene nano piece/zinc oxide/bamboo composite,
Stannic oxide/graphene nano piece/zinc oxide/the bamboo composite is by stannic oxide/graphene nano piece/oxygen according to the present invention
The preparation method for changing zinc/bamboo composite is prepared.
Beneficial effect
The present invention has following advantage compared with prior art：
1st, the present invention impregnates composite material precursor using ultrasound and negative pressure of vacuum auxiliary, can at utmost make containing oxidation
The aqueous solution depth of penetration of zinc precursor and stannic oxide/graphene nano piece into bamboo wood inside, in hydrothermal treatment process with bamboo wood
Cell membrane hydroxyl forms the chemical bond of stable combination, zinc oxide and stannic oxide/graphene nano piece is firmly secured to cell membrane
On.
2nd, method technique of the invention is simple, green and cost is low, is modified different from traditional nano-inorganic substance
Surface treatment method, the method being combined by pre-treatment and hydro-thermal method prepare stannic oxide/graphene nano piece/modified zinc oxide
Bamboo composite, stannic oxide/graphene nano piece and zinc oxide is set to penetrate into material internal, active ingredient not easily runs off, antibacterial effect
Fruit is good and lasting.Bamboo wood can also keep preferable antibiotic property in the secondary operation in later stage.
3rd, the present invention is modified bamboo wood to improve its antibacterial jointly using nano zine oxide and stannic oxide/graphene nano piece first
Performance.There is cooperate with antibacterial effect, nano zine oxide and oxidation stone between nano zine oxide and stannic oxide/graphene nano piece
The fungistatic effect of black alkene nanosheet composite material is far above the bamboo wood that nano zinc oxide modified bamboo wood or graphene oxide are modified.
Brief description of the drawings
Fig. 1 is 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 according to embodiments of the invention 1 (a), comparative example 1 (b), comparative example 2 (c) and comparative example
The XRD result figures of modified bamboo block prepared by 3 (d)；
Fig. 3 is according to embodiments of the invention 1 (a), comparative example 1 (b), comparative example 2 (c) and comparative example
The TG result figures of modified bamboo block prepared by 3 (d)；
Fig. 4 is to be changed according to prepared by embodiments of the invention 1, comparative example 1, comparative example 2 and comparative example 3
The Bactericidal test result figure of property bamboo block.
Embodiment
Preparation in accordance with the present invention, bamboo material is pre-processed in step 1), such as scraper can be utilized
Or sand paper etc. carries out the surface treatment such as polish to the surface of bamboo material, on the one hand ensures bamboo material surfacing, the opposing party
Face ensures bamboo material surface not by outside contamination.
In step 2) to by step 1) processing after bamboo material carry out impregnation, that is, be totally submerged in point
Dissipating has in the zinc salt mixed liquor of graphene oxide nanometer sheet, and by being evacuated to below 0.01MPa, is ultrasonically treated 10 minutes
Zinc salt and stannic oxide/graphene nano piece is set to fill as far as possible inside bamboo material.Wherein in order that zinc salt immerses bamboo material as far as possible
Inside, the concentration of zinc salt is as higher as possible in solution, such as can use the zinc solution of saturated concentration, while at ultrasound
Reason improves the permeability of bamboo wood pit membrane by using ultrasonication effect, greatly accelerates circulation speed of the moisture on pit
Degree, so that zinc solution is more easy to infiltrate into inside bamboo wood；And vacuumizing helps to discharge the air inside bamboo material, enter
And be advantageous to the immersion of zinc solution.Therefore the zinc salt can be with the big zinc salt of Selective dissolution degree, such as can be zinc chloride, sulphur
One or more in sour zinc, zinc nitrate, zinc acetate, zinc dihydrogen phosphate, the zinc salt concentration are 0.5~3mol/L, preferably 2
~3mol/L.Based on it is same the reasons why, the concentration of the stannic oxide/graphene nano piece is preferably 0.5~10g/L, further preferably
For 2~5g/L.
In step 5) to after processing bamboo material carry out hydro-thermal process, but in the hydrothermal process zinc salt concentration
(the step 4) in the range of 0.005~2mol/L should be controlled).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 the zinc oxide generated as zinc salt concentration too high (such as larger than 2mol/L), during hydro-thermal
Bulky grain is more likely formed, bamboo wood duct is blocked, declines zinc oxide content, 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, it 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 being limited to general sense and dictionary meanings, and inventor should allowed
On the basis of appropriate 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 not intended to limitation originally merely for the sake of the preferred embodiment for illustrating purpose
The scope of invention, it will thus be appreciated that without departing from the spirit and scope of the present invention, it can be obtained by it
His equivalents or improved procedure.
Following examples are enumerated only as the example of embodiment of the present invention, do not form any limit to the present invention
System, it will be appreciated by those skilled in the art that the modification in the range of without departing from the essence of the present invention and design each falls within the present invention
Protection domain.
Hereinafter, the preferred embodiment of the disclosure is described in detail with reference to the accompanying drawings.Before described, should
The term that solution uses in specification and appended, and general and dictionary meaning is should not be interpreted as limited to, but should
When suitably defining the principle of term based on the best explanation of inventor is allowed, based on the meaning corresponding to the technology of the present invention aspect
Justice and concept explain.Therefore, the preferred embodiment of description in this only for illustration purpose, and not refer to the limitation present invention
Scope, it is therefore to be understood that, other can be made without departing from the spirit and scope of the invention and equally implement and repair
Change.
Embodiment
Material characterization instrument：
SEM：Model S-4800Hitachi, manufacturer are Hitachi Hitachi, Ltds
X-ray diffractometer：Model D8Advance, manufacturer are German Bruker companies
Thermogravimetric analyzer：Model Q600, manufacturer are TA companies 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) is scraped off into very thin one layer in surface with scraper, about 1~2mm or so, then spend from
30 minutes sub- water, ethanol vacuum ultrasonic purged of impurities, after 40 DEG C of dryings, it is totally submerged in 20mL saturated acetic acids zinc and oxidation stone
Black alkene nanometer sheet (2g/L) mixed liquor, it is ultrasonically treated 10 minutes in vacuum condition, 1mol/L monoethanols is added dropwise after standing 24h
Amine aqueous solution adjusts solution ph to 10, is ultrasonically treated 10 minutes in vacuum condition, takes out bamboo block after impregnating 24h, use deionized water
The impurity on surface is rinsed well, 60 DEG C of dryings；
It is 0.05mol/L by the concentration that the stannic oxide/graphene nano piece aqueous solution that 1.5mL concentration is 10g/L adds 20mL
Zinc nitrate solution in, ultrasound 30 minutes is well mixed, and monoethanolamine solution (1mol/L) is added dropwise to pH value of solution=10, stirs
Mix 1h and be allowed to well mixed, then move on in water heating kettle, the bamboo block (1cm × 1cm × 1cm) after addition processing, in 120 DEG C of hydro-thermals
3h is handled, cooling, bamboo block is taken out, is washed with water 5 times, dries, that is, it is compound to obtain stannic oxide/graphene nano piece/zinc oxide/bamboo wood
Material (ZGB).
Modified circle bamboo manufactured in the present embodiment is intercepted one piece with blade, top layer is cut into 2~3mm or so, after in centre
One piece of thin slice is cut at position, and SEM signs are carried out to it.Fig. 1 d are the SEM photograph according to modified bamboo block manufactured in the present embodiment, by shining
Piece can see according to material modified, the nano oxygen in composite manufactured in the present embodiment, prepared by the method for this method
Change zinc and stannic oxide/graphene nano piece is most of in bamboo block growth inside.XRD results show (see Fig. 2 a) that 2 θ are 15 ° and 22 °
Diffraction maximum is respectively belonging to cellulose (110) and (002) crystal face；2 θ are that 11.3 ° of diffraction maximum is the characteristic peak of graphene oxide,
Belong to its (001) crystal face；2 θ are 32.1 °, 34.8 °, 36.6 °, 47.8 ° and 56.8 ° and are respectively belonging to wurtzite-type zinc oxide
(100), (002), (101), (102) and (110) crystal face, this result illustrates nano zine oxide and stannic oxide/graphene nano piece
It is deposited in bamboo wood.Thermal gravimetric analysis results show (see Fig. 3), are modified by nano zine oxide and stannic oxide/graphene nano piece
Bamboo wood heat endurance is better than unmodified sample.
Comparative example 1：
Bamboo block (1cm × 1cm × 1cm) after surface preparation as in Example 1 and cleaning is totally submerged in 20mL
In stannic oxide/graphene nano piece (2g/L) solution, it is ultrasonically treated 10 minutes in vacuum condition, takes out bamboo block after impregnating 24h, spend
Ionized water rinses the impurity on surface well, 60 DEG C of dryings；
The 1.5mL stannic oxide/graphene nano piece aqueous solution (10g/L) is added in 20mL water, 1mol/L monoethanolamine solutions are adjusted
Solution ph is saved to 10, is ultrasonically treated 10 minutes in vacuum condition, then moves on in water heating kettle, the bamboo block after addition processing,
120 DEG C of hydro-thermal process 3h, cooling, bamboo block is taken out, be washed with water repeatedly, dry, that is, obtain graphene oxide/bamboo composite
(GB)。
Comparative example 2：
Bamboo block (1cm × 1cm × 1cm) after surface preparation as in Example 1 and cleaning is totally submerged in 20mL
Saturated acetic acid zinc solution, it is ultrasonically treated 10 minutes in vacuum condition, stands 24h, 1mol/L monoethanolamine solutions tune is added dropwise
Solution ph is saved to 10, is ultrasonically treated 10 minutes in vacuum condition, bamboo block is taken out after impregnating 24h, with deionized water by surface
Impurity is rinsed well, 60 DEG C of dryings；
Monoethanolamine solution (1mol/L) is added dropwise to pH value of solution=10, stirring toward 20mL zinc nitrates (0.05mol/L)
1h is allowed to well mixed, then moves on in water heating kettle, the bamboo block after addition processing, in 120 DEG C of hydro-thermal process 3h, cools down, takes out
Bamboo block, it is washed with water repeatedly, dries, that is, obtain zinc oxide/bamboo composite (ZB).
Comparative example 3：
To 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：
Bacteriostatic test is carried out to sample using inhibition zone method, sample may determine that according to the size of inhibition zone around antibacterial substance
The quality of product antimildew and antibacterial.Escherichia coli antibacterial is carried out to the modified bamboo block prepared in embodiment 1 and comparative example 1 to 3
Performance test, specific operation process are：Prepare the culture medium needed for antibacterial experiment：Yeast extract powder 2.5g, albumen are weighed respectively
Peptone 5g, NaCl 5g, agar powder 7.5g are poured into conical flask, add 500ml deionized waters, using 1mol/L NaOH adjust pH to
7.4, the 20min that sterilizes is placed in 120 DEG C of autoclave sterilizers after stirring 20min, then moves to nutrient solution in super-clean bench, point
It is attached in sterile petri dish, treats that its natural coagulation into solid medium, takes the Escherichia coli after diluting twice to be applied to culture medium, so
Sample is fixed in the medium afterwards, is placed in 37 DEG C of culture 24h in constant incubator.Fig. 4 be according to embodiments of the invention 1,
The Bactericidal test result figure of modified bamboo block prepared by comparative example 1, comparative example 2 and comparative example 3.Upper left in figure
OB is the design sketch of the unmodified bamboo block of comparative example 3, it can be seen that without inhibition zone, illustrates no fungistatic effect；It is right
Upper ZB is zinc oxide/bamboo block of comparative example 2, stannic oxide/graphene nano piece/bamboo block of lower-left GB comparative examples 1 and bottom right
ZGB be embodiment 1 stannic oxide/graphene nano piece/zinc oxide/bamboo block be respectively to the inhibition zone of Escherichia coli 1.25cm, 1cm,
2.15cm.This result illustrates that 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 is far above individually with oxidation
The bamboo wood that zinc or stannic oxide/graphene nano piece are modified.This illustrates that there is collaboration suppression between nano zine oxide and graphene oxide
The effect of bacterium, immobilized nano zine oxide can promote the formation of peroxide on bamboo culm wall, effectively decompose and destroy bacterium
Structure, so as to bacteria growing inhibiting, reach sterilizing and antibacterial effect；And stannic oxide/graphene nano piece can by machine cuts come
Bacillus coli cells film is destroyed, reaches the purpose of sterilizing, the hydroxyl on carbonyl and bamboo cell membrane on stannic oxide/graphene nano piece
Between formed hydrogen bond also effectively strengthen its antibacterial stability；In addition, nano zine oxide and the zinc ion concentration that is released are in oxidation
On graphene nanometer sheet surface, the chance of bacterium and zinc contact is substantially increased, this is probably zinc oxide and graphene oxide
It is composite modified that there is the main reason for collaboration inhibitory effect.
EXPERIMENTAL EXAMPLE 2：
Bamboo wood (1cm × 1cm × 1cm) is surface-treated according to the method described in embodiment 1, then by its containing
2g/L nano zine oxide (being purchased from Chemical Reagent Co., Ltd., Sinopharm Group) and the aqueous solution of 2g/L stannic oxide/graphene nano pieces
Middle dipping 12h, take out bamboo wood and cleaned, dried with water, and it is subjected to Escherichia coli antibacterial with the identical technique of EXPERIMENTAL EXAMPLE 1
Performance test, its inhibition zone to Escherichia coli are 1.5cm.
EXPERIMENTAL EXAMPLE 3：
Entered with the surface of the bamboo wood to being prepared in the bamboo wood and EXPERIMENTAL EXAMPLE 2 that are prepared in embodiment 1 such as scraper or sand paper
Row processing, wipes 2~3mm of top layer or so off, Escherichia coli anti-microbial property survey is carried out with the identical technique of EXPERIMENTAL EXAMPLE 1 respectively
Examination, its inhibition zone to Escherichia coli is respectively 2cm and 0.8cm.This explanation bamboo wood in use as surface is worn or
When secondary operation causes the 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 deeper into bamboo wood inside and be securely joined with.
EXPERIMENTAL EXAMPLE 4：
Relative humidity will be placed on as in 90% high humidity closed environment according to the sample of embodiment 1, comparative example 1 to 3,
It can be found that the unmodified bamboo wood of comparative example 3 starts mildew occur in 1 day or so, and after placing 30 days, comparative example 1
The bamboo wood that is modified of graphene oxide there is a small amount of mildew, after placing 90 days, the bamboo wood of the modified zinc oxide of comparative example 2
Also there is a small amount of mildew, but the bamboo wood that is modified of the zinc oxide of embodiment 1 and stannic oxide/graphene nano piece is still without fungus growth, this
Illustrate nano zine oxide and the composite modified fungicidal properties that bamboo wood is greatly improved of graphene oxide.
Claims (11)
1. a kind of preparation method of stannic oxide/graphene nano piece-zinc oxide-bamboo composite, methods described includes following step
Suddenly：
1) bamboo material is pre-processed, the surface of bamboo material handled first, using scraper or sand paper to bamboo wood
The surface of raw material carries out polishing surface treatment, then successively with deionized water, 30 minutes purged of impurities of ethanol vacuum ultrasonic, 40
DEG C drying；
2) bamboo material by step 1) processing is totally submerged in being dispersed with the zinc salt mixed liquor of stannic oxide/graphene nano piece, is taken out
For vacuum to below 0.01MPa, being ultrasonically treated makes zinc salt and graphene oxide fill as far as possible inside bamboo material for 10 minutes, stands
24h；
3) solution ph is adjusted to 10 toward 1mol/L monoethanolamine solutions are added dropwise in step 2) mixed liquor, be evacuated to again
Below 0.01MPa, after being ultrasonically treated 10 minutes, bamboo material is taken out after impregnating 24h, it is with deionized water that the impurity on its surface is clear
Wash clean, 60 DEG C of dryings；
4) suspension for being dispersed with stannic oxide/graphene nano piece is added in zinc solution, wherein stannic oxide/graphene nano piece is dense
It is 0.005~2mol/L to spend for 0.02~3g/L, zinc solution concentration, and ultrasound is well mixed for 30 minutes, and concentration, which is added dropwise, is
1mol/L monoethanolamine solution regulation pH value of solution=10, stirring 1h are allowed to well mixed；
5) mixed liquor obtained by step 4) is moved on in water heating kettle, the bamboo material added after the dipping obtained by step 3), bamboo wood with
Mixeding liquid volume ratio is 1:3 to 1:20,60~200 DEG C are heated under hydrothermal reaction condition, is incubated 1~96 hour, is cooled down, is taken out
Bamboo wood, it is washed with water 3 to 5 times, dries, that is, obtain stannic oxide/graphene nano piece-zinc oxide-bamboo composite.
2. the preparation method of stannic oxide/graphene nano piece-zinc oxide-bamboo composite according to claim 1, it is special
Sign is that the concentration of stannic oxide/graphene nano piece described in step 4) is 0.2~1g/L.
3. the preparation method of stannic oxide/graphene nano piece-zinc oxide-bamboo composite according to claim 1, it is special
Sign is, is heated to 70~130 DEG C described in step 5) under hydrothermal reaction condition, is incubated 2~12 hours.
4. the preparation method of stannic oxide/graphene nano piece-zinc oxide-bamboo composite according to claim 1, it is special
Sign is, the step 1) bamboo material is circle bamboo, bamboo chip, Bamboo veneer, bamboo silk, bamboo fibre, bamboo particle, comprising mao bamboon, black bamboo,
Firm bamboo, phyllostachys bambusoides or square bamboo bamboo kind, the bamboo material are shaped as irregular shape or regular shape.
5. the preparation method of stannic oxide/graphene nano piece-zinc oxide-bamboo composite according to claim 4, it is special
Sign is, the square shape for being shaped as 1cm × 1cm × 1cm or diameter 4cm × long 10cm of the bamboo material circle bamboo section.
6. the preparation method of stannic oxide/graphene nano piece-zinc oxide-bamboo composite according to claim 1, it is special
Sign is that zinc salt described in step 2) is a kind of or more in zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, zinc dihydrogen phosphate
Kind, zinc salt concentration is 0.5~3mol/L, and stannic oxide/graphene nano piece concentration of aqueous solution is 0.5~10g/L.
7. the preparation method of stannic oxide/graphene nano piece-zinc oxide-bamboo composite according to claim 6, it is special
Sign is that zinc salt concentration described in step 2) is 2~3mol/L, and stannic oxide/graphene nano piece concentration of aqueous solution is 2~5g/L.
8. the preparation method of stannic oxide/graphene nano piece-zinc oxide-bamboo composite according to claim 1, it is special
Sign is that zinc salt described in step 4) is a kind of or more in zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, zinc dihydrogen phosphate
Kind, concentration is 0.005~2mol/L.
9. the preparation method of stannic oxide/graphene nano piece-zinc oxide-bamboo composite according to claim 8, it is special
Sign is that the zinc salt concentration is 0.01~0.5mol/L.
10. a kind of preparation method of stannic oxide/graphene nano piece-zinc oxide-bamboo composite, it comprises the following steps：
The bamboo block of 1cm × 1cm × 1cm shapes is scraped off into very thin one layer of 1~2mm of surface with scraper, then with deionized water, second
30 minutes purged of impurities of alcohol vacuum ultrasonic, after 40 DEG C of dryings, it is totally submerged in 20mL saturated acetic acids zinc and 1.5g/L concentration
Stannic oxide/graphene nano piece mixed liquor, it is ultrasonically treated 10 minutes in vacuum condition, 1mol/L monoethanols is added dropwise after standing 24h
Amine aqueous solution adjusts solution ph to 10, is ultrasonically treated 10 minutes in vacuum condition, takes out bamboo block after impregnating 24h, use deionized water
The impurity on surface is rinsed well, 60 DEG C of dryings；
The nitre that concentration by the stannic oxide/graphene nano piece aqueous solution addition 20mL that 1.5mL concentration is 10g/L is 0.05mol/L
In sour zinc solution, ultrasound is well mixed for 30 minutes, and concentration 1mol/L monoethanolamine solution is added dropwise to pH value of solution=10, stirs
Mix 1h and be allowed to well mixed, then move on in water heating kettle, the bamboo block of 1cm × 1cm × 1cm shapes after addition processing, at 120 DEG C
Hydro-thermal process 3h, cooling, bamboo block is taken out, is washed with water 5 times, dried, that is, obtain stannic oxide/graphene nano piece-zinc oxide-bamboo wood
Composite.
11. a kind of stannic oxide/graphene nano piece-zinc oxide-bamboo composite, the stannic oxide/graphene nano piece-zinc oxide-
Bamboo composite is multiple by stannic oxide/graphene nano piece-zinc oxide-bamboo wood as claimed in any of claims 1 to 10
The preparation method of condensation material is prepared.
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| 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 |
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| CN110116444B (en) * | 2019-06-13 | 2021-05-14 | 福建省顺昌县升升木业有限公司 | Anti-corrosion modification treatment agent for cedar, preparation method and construction process thereof |
| CN110076869A (en) * | 2019-06-13 | 2019-08-02 | 毛克升 | A kind of bamboo wood anti-mould and anti-moth inorganic agent and preparation method thereof and construction technology |
| 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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