CN111268960A - Cement-based paint for inducing sessile organisms on surface of ocean engineering and preparation method thereof - Google Patents
Cement-based paint for inducing sessile organisms on surface of ocean engineering and preparation method thereof Download PDFInfo
- Publication number
- CN111268960A CN111268960A CN201911210521.9A CN201911210521A CN111268960A CN 111268960 A CN111268960 A CN 111268960A CN 201911210521 A CN201911210521 A CN 201911210521A CN 111268960 A CN111268960 A CN 111268960A
- Authority
- CN
- China
- Prior art keywords
- powder
- cement
- calcium carbonate
- marine
- concrete
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004568 cement Substances 0.000 title claims abstract description 83
- 230000001939 inductive effect Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003973 paint Substances 0.000 title description 17
- 238000012407 engineering method Methods 0.000 title description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 168
- 239000000843 powder Substances 0.000 claims abstract description 153
- 238000000576 coating method Methods 0.000 claims abstract description 72
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 71
- 239000011248 coating agent Substances 0.000 claims abstract description 68
- 239000000463 material Substances 0.000 claims abstract description 68
- 239000011575 calcium Substances 0.000 claims abstract description 54
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 44
- 239000000049 pigment Substances 0.000 claims abstract description 33
- 239000004576 sand Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008030 superplasticizer Substances 0.000 claims abstract description 21
- 239000011573 trace mineral Substances 0.000 claims abstract description 15
- 235000013619 trace mineral Nutrition 0.000 claims abstract description 15
- 229920001971 elastomer Polymers 0.000 claims abstract description 9
- 239000004567 concrete Substances 0.000 claims description 96
- 241000283690 Bos taurus Species 0.000 claims description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 230000000694 effects Effects 0.000 claims description 30
- 239000003513 alkali Substances 0.000 claims description 21
- 210000000988 bone and bone Anatomy 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 17
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 16
- 229960001763 zinc sulfate Drugs 0.000 claims description 15
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 15
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 13
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- 230000002829 reductive effect Effects 0.000 claims description 11
- 239000002893 slag Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000010881 fly ash Substances 0.000 claims description 7
- 235000014653 Carica parviflora Nutrition 0.000 claims description 6
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- 108010000912 Egg Proteins Proteins 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 210000003278 egg shell Anatomy 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 235000019738 Limestone Nutrition 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000006028 limestone Substances 0.000 claims description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- -1 dimethyl siloxane Chemical class 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
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- 239000003469 silicate cement Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 235000011010 calcium phosphates Nutrition 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000012860 organic pigment Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 3
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021532 Calcite Inorganic materials 0.000 claims description 2
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- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 239000001054 red pigment Substances 0.000 claims description 2
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- 239000010703 silicon Substances 0.000 claims description 2
- 230000003075 superhydrophobic effect Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 3
- 230000001070 adhesive effect Effects 0.000 claims 3
- 238000000034 method Methods 0.000 abstract description 15
- 239000011150 reinforced concrete Substances 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 10
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- 241000237502 Ostreidae Species 0.000 description 94
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- 239000000203 mixture Substances 0.000 description 18
- 239000000758 substrate Substances 0.000 description 17
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 15
- 229910001424 calcium ion Inorganic materials 0.000 description 15
- 238000011160 research Methods 0.000 description 14
- 241000251468 Actinopterygii Species 0.000 description 11
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 11
- 239000011398 Portland cement Substances 0.000 description 9
- 230000035699 permeability Effects 0.000 description 9
- 238000010276 construction Methods 0.000 description 7
- 239000000411 inducer Substances 0.000 description 7
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- 239000013535 sea water Substances 0.000 description 7
- 241000238586 Cirripedia Species 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 230000006870 function Effects 0.000 description 5
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- 238000000227 grinding Methods 0.000 description 4
- 239000010440 gypsum Substances 0.000 description 4
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- 239000004033 plastic Substances 0.000 description 4
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- 230000001737 promoting effect Effects 0.000 description 4
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- 150000003839 salts Chemical class 0.000 description 4
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- 235000015170 shellfish Nutrition 0.000 description 2
- 241000590031 Alteromonas Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 241000548230 Crassostrea angulata Species 0.000 description 1
- 241001207609 Crassostrea hongkongensis Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000490567 Pinctada Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01K—ANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
- A01K61/00—Culture of aquatic animals
- A01K61/50—Culture of aquatic animals of shellfish
- A01K61/54—Culture of aquatic animals of shellfish of bivalves, e.g. oysters or mussels
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/24—Sea water resistance
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention relates to a cement coating technology for inducing attachment of marine periphyton, in particular to a cement-based coating for inducing periphyton on the surface of marine engineering and a preparation method thereof, belonging to the crossing field of marine periphyton and marine engineering coatings. The invention is prepared from a cementing material, sand, water, a dark pigment, biological calcium powder, calcium carbonate powder, trace elements, lignocellulose, dispersible rubber powder and a superplasticizer. The invention is applied to newly-built ocean engineering, in particular to a great number of active engineering in the ocean. The method can improve the durability of the reinforced concrete structure and simply and economically realize the restoration of the marine ecological environment. The method not only greatly widens the corrosion prevention application of the marine sessile organisms in the serving reinforced concrete structure, but also can be widely applied to marine ecological environment restoration engineering.
Description
Technical Field
The invention relates to a cement coating technology for inducing attachment of marine periphyton, in particular to a cement-based coating for inducing periphyton on the surface of marine engineering and a preparation method thereof, belonging to the cross field of marine periphyton and marine engineering coatings.
Background
In marine concrete structure anticorrosion technology, surface coating protection is the most common marine anticorrosion technology due to its economy and practicality. However, for marine concrete structures in a tidal range area and a full immersion area, the general coating cannot meet the requirements because the sea concrete structures are in a wet state or are always immersed in water due to tidal rise and tidal fall. There is therefore a need for a coating which can be applied and cured directly in seawater or in a humid environment. Currently, anticorrosive coatings for underwater and wet interfaces such as polyester resin systems, vinyl resin systems, and epoxy resin systems have been developed. However, the method has the problems of insufficient adhesion with the concrete interface, short service time, high manufacturing cost and the like, and particularly, some plant and microbial films and the like are often adhered to the concrete surface because the anticorrosive paint has higher requirements on the adhesion surface, but the surface is difficult to remove to the extent that the anticorrosive paint can be brushed.
At present, researches show that sessile organisms attached to the surface of concrete, such as oysters and barnacles, can improve the impermeability of the concrete and further improve the durability of a marine concrete structure, and the more compact the sessile organisms are attached, the more obvious the protection effect is. The marine periphyton anticorrosion has the characteristics of initiative, economy and environmental protection, and makes up the limitation of the existing reinforced concrete anticorrosion technology in tidal range areas and underwater areas. However, in practical engineering, sessile organisms are affected by the external environment, and the phenomena of sparse attachment, loose attachment and even no attachment often occur. Recent studies have shown that oyster attachment and growth are associated with the substrate, and concrete is a preferred substrate. The attachment amount of oyster larvae is increased by adding calcium materials such as biological calcium carbonate powder, gypsum powder and the like into cement; oyster is also easier to adhere to dark substrates, and the like. For concrete structures in service, it is not practical to change the substrate by dismantling the reconstruction. The concrete surface is treated and painted to realize the function of inducing attachment of sessile organisms. However, the paint coated on the concrete surface induces the attachment of attachment organisms, and relevant data are not found in the corrosion prevention of the reinforced concrete structure in the marine environment. Therefore, there is a need to develop a coating capable of rapidly increasing the amount of adhesion of marine periphyton on the surface of concrete, particularly a coating capable of rapidly inducing the adhesion and metamorphosis of periphyton and promoting long-term growth, and having the characteristics of simple construction and easy painting. The application field of marine sessile organisms in the corrosion prevention of reinforced concrete is greatly widened.
CN104938384 is to mix 150-200 mesh biological calcium carbonate powder (fishbone, coral, egg shell and shell are 1:1:1:1) and shell fragment which are 10-20% of the cement mass into the artificial fish reef, which shows that the induced biomass is gradually increased along with the increase of the calcium carbonate mixing amount, and the biomass (marine plant and marine organism) induced by the biological calcium carbonate is the most when the mixing amount is the maximum (20% of the cement weight). In order to reduce the alkalinity of the surface of the concrete artificial fish reef, microorganisms and algae are easier to attach, the biomass and the population quantity are increased, and the fish collecting effect is better. The biological calcium carbonate cement mortar coating layer educt is harmless to the environment and the organism. Although the biological calcium carbonate powder, the oyster shell fragments and the like are doped into concrete for artificial fish reef manufacturing and biological attachment experiments, the biological calcium carbonate powder indeed enhances the biological enrichment effect, but mainly enriches marine plants and microorganisms.
Meanwhile, as coastal economy develops rapidly in recent decades without paying attention to environmental protection, coastal ecology is broken down on a large scale, and the coastal ecology and economy in China are greatly influenced. At present, a series of relevant policies of China emerge, the ocean engineering construction of China also faces a peak period, and simultaneously, the ocean engineering constructed in a large scale and the breakwater which ensures the stability of the surrounding sea area further destroy the originally fragile ecosystem of the ocean. If proper ecological environment protection measures are not taken, a greater disaster is certainly brought to the ecology along the shore of the ocean. Meanwhile, most coastal infrastructures cannot be dismantled, and the ecology in the sea area needs to be restored, so that people gradually realize the application of ecological technologies on a large number of infrastructures, and the ecology in the sea area can be effectively improved or restored. Therefore, it is very important and urgent to construct a concrete project with good ecological effects, or to ecologize the existing concrete project, etc. to improve the offshore ecological environment. However, until now, the ecological technology of projects such as breakwaters in tidal ranges is still in a blank state in China.
Oysters are ecological engineers and are mainly concentrated in a tidal range area and underwater within 30 meters, and the oysters like to be attached to shells of the same type to form a thick oyster reef, so that the oysters are attached to the breakwater compactly, and the ecology of the breakwater can be realized; in addition, the existing oyster reefs are seriously damaged, and most oysters need to be attached again in a large scale to realize ecological restoration. The ecological function of the oysters can be realized through mass propagation of the oysters when the marine ecological engineering construction and the oyster reef restoration are carried out. Therefore, the mixed concretion oyster attaching base has great demand. At present, relevant researches on oyster attachment at home and abroad are as follows:
first, the influence of ions on the attachment and metamorphosis of marine periphyton larva
The research on the marine periphyton larva attachment and metamorphosis induction at home and abroad mainly focuses on the influence of the ion concentration in the solution, and the deeply researched ions and substances have K+、NH3、Ca2+And Cu2+The first three ions or substances can promote the adhesion or metamorphosis of oyster at proper concentration, but Cu2+The promoting effect is not obvious, and even the death rate of larvae is increased at a large concentration. K+Inducing larval metamorphosis by affecting the behavior of cell membranes; NH (NH)3It is intracellular, leading to an increase in intracellular pH, which subsequently causes depolarization of neurons that are behavioral pathways, thereby inducing sessile metamorphosis. Although the study on the attachment and metamorphosis of more sessile organisms on the surfaces of different substances such as polyethylene plates, shells, tiles and the like is carried out in solution, the method is not easy to realize or has high cost when being applied to the actual marine concrete engineering.
At present, with the great application of concrete in ocean engineering, particularly recent oyster reef repair engineering and the like, the concrete becomes a substrate material which is most commonly attached by marine periphyton. However, the concrete material is different from the traditional shells, limestone, rubber tires, plastic plates and the like. The concrete has high alkalinity and high calcium ion, also contains rich other ions, such as potassium and sodium ions, and has great influence on the attachment and growth of the oysters. At present, although some oyster reef repair projects and the like adopt newly manufactured concrete members, waste concrete and the like as repair substrates, the effect is not ideal.
Second, the influence of concrete of different types of cement on marine plants and sessile organisms
At present, portland cement concrete is almost adopted in ocean concrete engineering and has high alkalinity (the pH value of a pore solution is generally 12.0-13.0), and the pH value of seawater is generally 7.9-8.4. Due to the existence of alkali concentration gradient, the concrete contacted with the seawater can continuously release alkali, thereby improving the pH value of the seawater in the sea area and damaging the local ecological system. Has a great inhibiting effect on the attachment growth of sessile organisms on the surface of the biological filter, and particularly has great influence on alkalinity sensitive organisms. The current domestic and foreign research shows that: the artificial fish reef made of different cement types has obvious difference on biological attachment effect, aluminate cement and fly ash portland cement have good biological attachment effect, and the alkalinity of the artificial fish reef is lower than that of common portland cement concrete. Similarly, the cement concrete has better ecological effect by adding 40-60% of fly ash and slag powder. In addition, the types and the quantity of the attachment organisms of the travertine cementing material concrete are more than those of the cement concrete, and the higher the content of the travertine cementing material is, the better the ecological effect is. The ecological concrete engineering for building the United states adopts low-alkalinity cement concrete, such as aluminate cement, particularly slag portland cement, wherein the replacement amount of slag powder reaches 50 percent, and the ecological effect of enriching marine plants, animals and the like is better. By adopting cement with lower alkalinity to prepare concrete, biomass (mainly marine plants) sensitive to alkali can be effectively improved, but the improvement of the attachment amount and the attachment density of oysters is limited.
Third, the influence of calcium substances on the adhesion of marine sessile organisms
Domestic and foreign researches show that the chemical element composition of the attaching substrate obviously influences the attachment, metamorphosis and later growth of oyster larvae. The most commonly used calcium-containing substrates (limestone and concrete) are effective in inducing adhesion of oyster larvae with an inducing effect comparable to that of shellfish shells. This indicates that calcium is a vital role in the attachment, metamorphosis and growth of oyster larvae.
Recently, in addition to conventional substrates, studies have been made on the adhesion of oyster larvae by adding calcium to cement-based materials and increasing the content of calcium in concrete. In the literature, 80-mesh cattle bone powder, calcium carbonate powder and gypsum powder (the mixing amount is 62.5 percent and 375 percent of the weight of cement) are singly mixed into mortar to carry out an oyster attachment experiment, and the sequence of the inducing capacity of the calcium excipient for the adhesion of oyster larvae under the same condition is obtained: the bovine bone meal is calcium carbonate which is calcium sulfate; the calcium carbonate powder is doped in an amount of 5-60% of the mortar (41.7-500.0% of the cement), and the effect is best when the calcium carbonate powder is doped in an amount of 20% (166.7% of the cement). Although the attachment amount of the oysters can be increased by adding the bovine bone meal, the calcium carbonate powder and the gypsum powder, the added proportion is too large (the weight of the calcium powder is more than 41.7 percent of that of the cement and even reaches 500.0 percent), the mechanical property and the durability of the concrete are seriously influenced, and the oyster powder is not suitable for being used in concrete engineering under marine environment. In addition, although the bovine bone meal has a good effect of inducing adhesion of oysters, when the amount of the bovine bone meal exceeds 10% of the cement, the concrete is mildewed. Therefore, at present, although calcium substances such as bovine bone meal, calcium carbonate and the like are doped into concrete, the influence of marine environment on the durability of a concrete structure is not considered, so that the concrete cannot be applied to severe marine environment at all. In CN104529286 patent: from the aspect of waste utilization, oyster shell fragments of 5 mm-8 mm with the mass of 10% -20% of cement are mixed into the artificial fish reef, and the concrete which does not influence biological attachment and does not pollute the environment is obtained. Although the addition of oyster shell pieces does enhance the biological enrichment, the sea plants and microorganisms are mainly enriched.
In summary, calciumThe content of the calcium carbonate is important for the attachment of oyster larvae, and the addition of a proper amount of calcium carbonate substances into the cement-based material can promote the attachment and growth of the oyster larvae as proved by some current experimental results. However, cement concrete contains a large amount of calcium ions, the pH value of a pore solution is generally greater than 12.5, and the pH value of a saturated calcium hydroxide solution is about 12 at normal temperature, so that the concentration of the calcium ions in the mixed concrete pore solution is about 5 mmol/L; the solubility of calcium carbonate is very low, and is only 9.5X 10 at 25 DEG C-5mol/L (9.5×10-2mmol/L). At present, the optimal range of calcium ion concentration for inducing shellfish adhesion is considered to be 10-25 mmol/L, and even if oyster larvae are placed in saturated calcium carbonate solution, enough Ca is not available2+The concentration of Ca is suitable for providing proper Ca for the adhesion of oysters2+And (4) concentration. Further, Ca (OH) in the inside of the cement concrete2Can be released more quickly, and the dissolution of calcium carbonate needs longer time. Therefore, it was confirmed that incorporation of calcium carbonate material into concrete promotes adhesion of oyster larvae, Ca2+Not the dominant role.
In addition, the doping amount of the shell powder is too large, the weight ratio of the shell powder to the cement is more than 10%, and some shell powder even reaches 500%, so that the durability of the concrete is greatly influenced. Although the proper amount of calcium carbonate material can prevent the concrete from being reduced in impermeability or better, the excessive amount of calcium carbonate material is very unfavorable for the concrete to resist the corrosion of sulfuric acid and sulfate in seawater.
Therefore, the problem of marine sessile organism larva induced adhesion by doping calcium substances such as biological calcium carbonate, bovine bone meal, calcium carbonate powder and the like into concrete still exists, and particularly the problems of concrete performance caused by excessive doping of the calcium substances, mildew caused by doping of the bovine bone meal and the like exist.
Fourth, the influence of color on the adhesion of marine periphyton
The color of the substrate has certain influence on the attachment, metamorphosis and growth of the larvae of the marine periphyton. Overseas has reported that in a sea area with a low temperature, a dark substrate can promote the growth of oysters. Domestic research shows that oyster larvae have certain selectivity on color. The color selectivity of the crassostrea hongkongensis larvae on the plastic anchoring base is as follows: black > white > red. Crassostrea gigas larvae prefer to attach to black and gray plastic plates and it is believed that black and gray may be a protective color for oyster larvae to avoid natural enemy attacks. Barnacles prefer to adhere to red substrates. Pearl oyster also prefers dark (black, red), non-reflective substrates, showing non-photosensitive behavior. And the bacterium alteromonas melellii attracts oyster larvae by producing a compound involved in melanin synthesis.
The research on the influence of the color of the substrate on the adhesion of marine periphyton larvae is limited to organic polymer plates such as plastic plates and polyethylene plates, asbestos plates and the like. The concrete is used as a most potential substitute substrate, is particularly used for the current oyster reef repair, the construction of artificial ecological engineering and the corrosion prevention of marine reinforced concrete, and the influence of the color on the attachment amount of sessile organism larvae is not referred to related data
Although the above studies are currently carried out, such as the effect of different substrates and colors on marine periphyton attachment, the effect of incorporating calcareous materials into concrete on marine periphyton attachment has recently been studied. But no relevant research for inducing marine anchorage biological coatings exists at present. The in-service concrete engineering, waste concrete and the like can realize the ecological environment restoration of ocean engineering by surface treatment and coating and inducing the adhesion of sessile organisms, is a research direction of engineering ecology with great potential, and is particularly used for oyster reef restoration, artificial ecological engineering construction and corrosion prevention of ocean reinforced concrete currently carried out. Due to the knowledge of related subjects such as marine organisms, marine microorganisms, marine chemistry, marine concrete engineering materials and structures, the subject direction difference is large, so that more problems are encountered in cross research, such as the above-mentioned problems that the cement-based materials are not clear in water-cement ratio, the adhesion mechanism of the calcium carbonate materials induced oysters is not clear, the concrete durability is seriously insufficient due to excessive calcium powder added in the cement, the added bovine bone meal is easy to mildew, and the like.
Disclosure of Invention
The invention aims to invent a coating capable of being directly brushed and cured in a humid environment, which can induce sessile organisms to be quickly and compactly attached to the surface of concrete, achieve the biological anti-corrosion effect by utilizing the fixation characteristic of oysters, and achieve the aims of purifying water bodies and restoring ecology by virtue of large-scale attachment of the sessile organisms. The problems of limited effect, short service time, high manufacturing cost and the like of corrosion prevention measures in tidal range areas and underwater areas of ocean concrete projects and the problem that ocean ecological restoration is urgently needed due to ecological deterioration are solved.
The invention aims to realize that the prepared cement-based coating has high capability of inducing adhesion and metamorphosis of oyster larvae, realizes the effects of compact and uniform adhesion of oysters, improves the durability of a concrete structure by utilizing the fixation characteristic of the oysters and does not pollute the marine environment by using a low-alkalinity cementing material, lignocellulose, dispersible rubber powder and a superplasticizer and adding a modified dark color pigment, modified biological calcium powder, calcium carbonate powder and trace elements into the coating.
The invention also includes such structural features:
the material components are as follows: the weight ratio of the cementing material, the sand, the water, the dark pigment, the biological calcium powder, the calcium carbonate powder, the trace elements, the lignocellulose, the dispersible rubber powder and the superplasticizer is as follows in sequence: 1: (0.35-0.7): (0.20-0.60): (0.02-0.10): (0.02-0.10): (0.02-0.10): (0.01-0.08): (0.04-0.12): (0.05-0.15): (0.001-0.010).
Preferably, the dark color pigment is: one or two of iron oxide black, aniline black, carbon black, antimony sulfide, iron oxide red and organic pigment red.
Preferably, the dark color pigment is: according to the influence degree on the performance of concrete, the pigments are modified by adopting one of transparent resin, organic silicon, dimethyl siloxane and super-hydrophobic materials.
Preferably, the biological calcium powder is: the biological calcium carbonate powder is one or a plurality of compounds of oyster shell powder, fishbone powder, egg shell powder and coral powder, and the fineness of the biological calcium carbonate powder is 100-1000 meshes.
Preferably, the biological calcium powder is: treating 100-500 mesh egg shell powder, coral powder, oyster shell powder and fishbone powder with acid selected from one or two of acetic acid, silicic acid and sulfurous acid; and treating the 100-500-mesh bovine bone powder by using one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid.
Preferably, the calcium carbonate powder is: calcite, chalk, limestone, marble, aragonite, travertine powder, and one or more of light calcium carbonate, activated calcium carbonate, calcium carbonate whisker and superfine light calcium carbonate which are processed, and the fineness is more than 200 meshes.
Preferably, the trace elements of zinc, iron, potassium and phosphorus can be selected from natural minerals, industrial products or chemical reagents, including one or more of zinc sulfate, calcium phosphate, zinc phosphate, potassium sulfate, potassium nitrate, ferric sulfate, ammonium nitrate, potassium phosphate, ammonium phosphate and iron phosphate, and are modified to realize slow release of corresponding ions and reduce or eliminate adverse effects on the performance of concrete. However, nitrogen and phosphorus are not selected for the eutrophic area.
Preferably, the cementing material is one of silicate cement, sulphoaluminate cement and alkali-activated cementing material doped with mineral admixture. Wherein the mineral admixture in the silicate cement blended with the mineral admixture comprises one or more of silica fume, slag powder and fly ash; the sulphoaluminate cement comprises one or two of quick-hardening sulphoaluminate cement, high-strength sulphoaluminate cement and expansion sulphoaluminate cement; the alkali-activated cementing material comprises one of alkali-activated slag, alkali-activated slag and fly ash.
Preferably, the sand is one or more of river sand with the particle size of 0.16-2.36 mm, machine-made sand (mother rock can be limestone, basalt or granite) and sea sand.
Preferably, the superplasticizer is one of polycarboxylic acid and naphthalene series.
A cement-based paint for inducing sessile organisms on the surface of ocean engineering and a preparation method thereof are characterized by comprising the following steps:
s1: accurately weighing a cementing material, sand, water, a dark pigment, biological calcium powder, calcium carbonate powder, trace elements, lignocellulose, dispersible rubber powder and a superplasticizer;
s2: placing the cementing material, the deep color pigment, the biological calcium powder, the calcium carbonate powder and the trace elements into a mixer, wherein the rotating speed is 1000-1500 rpm, the mixing time is 2-5 minutes, and the materials are uniformly mixed;
s3: then placing the sand, the lignocellulose and the dispersible rubber powder into a stirrer, wherein the rotating speed is 500 plus 1000 revolutions per minute, and the mixing time is 5-10 minutes;
s4: fully dissolving the powdery superplasticizer in water, then putting the mixed materials into a high-speed stirrer together, wherein the rotating speed of the stirrer is 200 plus 500 rpm, and stirring for 5-10 minutes.
Thus obtaining the cement-based coating with good induction effect for inducing sessile organisms on the surface of ocean engineering.
Compared with the prior art, the invention has the beneficial effects that:
at present, no matter the durability of the marine concrete or the ecological engineering of the marine concrete, a green and economic method is lacked. The oyster is used as an ecological engineer of the sea, and has the functions of densifying the surface of a concrete structure, improving the ecological environment and the like. The cement-based paint for inducing sessile organisms provided by the invention has the characteristics of rapidly inducing attachment and metamorphosis of the sessile organisms and promoting long-term growth, and also has the characteristics of simple construction and easy painting. Can be applied to newly-built ocean engineering, in particular to a great number of active engineering in the ocean. The method can improve the durability of the reinforced concrete structure, and simply and economically realize the restoration of the marine ecological environment. The method not only greatly widens the corrosion prevention application of the marine periphyton in the serving reinforced concrete structure, but also can be widely applied to marine ecological environment restoration engineering.
Detailed Description
The present invention will be described in detail with reference to the following examples, which are provided only for illustrating the present invention and do not limit the scope of the present invention. The coating mix proportions of the examples are as follows:
example 1: the weight ratio of the cementing material to the sand to the water to the modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), the weight ratio of the modified biological calcium powder (modified bovine bone powder: oyster shell powder is 2:1), the calcium carbonate powder, the zinc sulfate, the lignocellulose to the dispersible gelatine powder to the superplasticizer is as follows: 1:0.5:0.4:0.03:0.03:0.03:0.02:0.06:0.06: 0.005.
example 2: the weight ratio of the cementing material to the sand to the water to the modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), the weight ratio of the modified biological calcium powder (modified bovine bone powder: oyster shell powder is 2:1), the calcium carbonate powder, the zinc sulfate, the lignocellulose to the dispersible gelatine powder to the superplasticizer is as follows: 1:0.5:0.4:0.05:0.05: 0.05:0.02:0.06:0.06:0.005.
Example 3: the weight ratio of the cementing material to the sand to the water to the modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), the weight ratio of the modified biological calcium powder (modified bovine bone powder: oyster shell powder is 2:1), the calcium carbonate powder, the zinc sulfate, the lignocellulose to the dispersible glue powder to the superplasticizer are as follows: 1:0.5:0.4:0.05:0.05:0.05:0.04:0.08:0.09:0.005.
Example 4: the weight ratio of the cementing material to the sand to the water to the modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), the weight ratio of the modified biological calcium powder (modified bovine bone powder: oyster shell powder is 2:1), the calcium carbonate powder, the zinc sulfate, the lignocellulose to the dispersible glue powder to the superplasticizer are as follows: 1:0.5:0.4:0.08:0.08:0.08:0.04:0.08:0.09:0.005.
Example 5: the weight ratio of the cementing material to the sand to the water to the modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), the weight ratio of the modified biological calcium powder (modified bovine bone powder: oyster shell powder is 2:1), the calcium carbonate powder, the zinc sulfate, the lignocellulose to the dispersible glue powder to the superplasticizer are as follows: 1:0.5:0.4:0.08:0.08:0.08:0.06:0.10:0.12:0.005.
Example 6: the weight ratio of the cementing material to the sand to the water to the modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), the weight ratio of the modified biological calcium powder (modified bovine bone powder: oyster shell powder is 2:1), the calcium carbonate powder, the zinc sulfate, the lignocellulose to the dispersible gelatine powder to the superplasticizer is as follows: 1:0.5:0.4:0.03:0.03:0.03:0.04:0.06:0.06:0.005.
Example 7: the weight ratio of the cementing material to the sand to the water to the modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), the weight ratio of the modified biological calcium powder (modified bovine bone powder: oyster shell powder is 2:1), the calcium carbonate powder, the zinc sulfate, the lignocellulose to the dispersible glue powder to the superplasticizer are as follows: 1:0.5:0.4:0.05:0.05:0.05:0.04:0.06:0.06:0.005.
Example 8: the weight ratio of the cementing material to the sand to the water to the modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), the weight ratio of the modified biological calcium powder (modified bovine bone powder: oyster shell powder is 2:1), the calcium carbonate powder, the zinc sulfate, the lignocellulose to the dispersible glue powder to the superplasticizer are as follows: 1:0.5:0.4:0.05:0.05:0.05:0.02:0.08:0.09:0.005.
Example 9: the weight ratio of the cementing material to the sand to the water to the modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), the weight ratio of the modified biological calcium powder (modified bovine bone powder: oyster shell powder is 2:1), the calcium carbonate powder, the zinc sulfate, the lignocellulose to the dispersible glue powder to the superplasticizer are as follows: 1:0.5:0.4:0.08:0.08:0.08:0.06:0.08:0.09:0.005. .
Example 10: the weight ratio of the cementing material to the sand to the water to the modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), the weight ratio of the modified biological calcium powder (modified bovine bone powder: oyster shell powder is 2:1), the calcium carbonate powder, the zinc sulfate, the lignocellulose to the dispersible rubber powder to the superplasticizer are as follows in sequence: 1:0.5:0.4:0.03:0.03:0.03:0.06:0.10:0.12:0.005.
The method for modifying the dark pigment comprises the following steps: 196 transparent resin is adopted, 3 percent of curing agent and 1.5 percent of accelerating agent are added and mixed with pigment, and the volume ratio of the pigment to the resin is as follows: 1: 0.2; curing at normal temperature for 4h, curing at 60 deg.C for 4h, then breaking, and grinding with vibration mill to obtain the final product with fineness greater than 400 meshes.
The method for modifying the bovine bone meal comprises the following steps: adding 100-mesh bovine bone meal into 2% phosphoric acid solution, wherein the weight ratio of the bovine bone meal to the phosphoric acid solution is 1:3, the temperature is 20-30 ℃, the mixture is stirred for 30 minutes in a stirrer with the rotating speed of 200-500 r/min, a centrifugal machine with the rotating speed of 3000-5000 r/min is adopted for centrifugation for 3 minutes, supernatant is poured off, solid matters of the centrifuged solid matters are washed for 2-3 times by water, and washing water does not show acidity any more; vacuum drying the centrifuged solid substance at 40 deg.C, mixing the dried Os bovis Seu Bubali powder and slag powder at a ratio of 1:4, and grinding with vibration mill to fineness of more than 200 meshes.
The modification method of zinc sulfate comprises the following steps: selecting diatomite SiO2Adding 150g of water and 100g of zinc sulfate into diatomite with the content of more than 90 percent and the fineness of 600 meshes in a stirrer at the temperature of 60 ℃, and stirring until the mixture is completely dissolved for later use; and then 150g of the diatomite is heated to 60 ℃ and added into the solution, the mixture is stirred for 10 minutes in a stirrer with the rotating speed of 200-500 rpm, and then the mixture is dried in a drying box with the drying temperature of 100 ℃ to obtain the modified zinc sulfate.
Compared with the comparative document 1 (a bionic concrete artificial fish reef and a preparation method 2015CN104938384A), the differences are that:
(1) the object in the present invention is different from comparative document 1: in comparison document 1, although a layer of cement mortar mixed with ground oyster shells is coated on the surface of concrete, the purpose is mainly achieved by surface bionic property, fish, microorganisms and algae are collected, the number of microorganisms is increased, and the water environment is improved, and oyster is not mentioned. The cement-based coating aims to induce attachment of sessile organisms, mainly oysters, and takes barnacles into consideration when the reinforced concrete in the tidal range zone is used for corrosion prevention.
(2) The comparison document 1 indicates that in cement mortar, the biological calcium carbonate powder (150-200 meshes) with the cement mass of less than 10% is not obvious in induced adhesion. However, in the research process, the modified bovine bone powder and the biological calcium carbonate powder are mixed with the cement-based coating (the fineness is 100-1000 meshes), and the optimal mixing amount of the bovine bone powder and the biological calcium carbonate powder is within 10 percent of the cementing material.
(3) By modifying bovine bone powder and biological calcium carbonate powder, specifically, egg shell powder, coral powder, oyster shell powder and fishbone powder of 100-500 meshes are treated by the following acids, including one or two of acetic acid, silicic acid and sulfurous acid; the 100-500 mesh bovine bone powder is treated by one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid.
(4) The contrast document is difficult to construct by embedding oyster shells on the concrete surface, and the feasibility is low because the method can not be adopted on each engineering surface. The invention can achieve the effect of inducing sessile organisms by coating a layer of cement-based paint on the surface of concrete, does not need to be embedded with oyster shells, has simple construction and can greatly increase the attachment of the oysters.
(5) In the marine environment, the phenomenon that the artificial fish reef is seriously corroded for many times in recent years appears, and the serious corrosion is mainly caused by the combined action of biological sulfuric acid secreted by anaerobic microorganism thiobacillus, acid substances secreted by other bacteria and the like. Calcium carbonate is weak against acid corrosion, and thus, too high a calcium carbonate content having a large fineness causes severe acid corrosion.
Compared to reference 2 (Vanreilin. influence of matrix type on oyster attachment, growth, population establishment and reef development [ D ]), the difference is:
(1) in comparison document 2, 80-mesh bovine bone powder, calcium powder and gypsum powder were used, each separately blended in concrete. The fineness of all the calcium materials in the invention is more than 100 meshes and more than that of the materials in the comparison document 3. And the modified bovine bone meal is added, and the grain composition and the induction capability thereof in the coating are considered.
(2) Grinding the bovine bone powder by using a vibration mill at normal temperature, wherein when the fineness is more than 80 meshes, the bovine bone powder contains a large amount of collagen and is seriously agglomerated, so that the bovine bone powder cannot be continuously ground. The invention adopts dilute acid modification technology and is compounded with other substances and ground to obtain the modified biological calcium powder with small particle size and fineness of more than 200 meshes. The prepared biological calcium powder retains the original substances of the biological calcium, increases the release rate of substances which induce oyster larvae to adhere to the biological calcium powder, and reduces the doping amount of the biological calcium powder, thereby reducing the influence on the performance of the coating.
(3) Because the bovine bone meal contains rich organic substances such as collagen, the strength and impermeability of the coating are reduced when the bovine bone meal is mixed in a large amount, particularly after the content of the organic substances exceeds 5 percent, the mixing amount is increased, the strength of the coating is rapidly reduced, the impermeability is obviously reduced, and the coating can grow mildewed under standard curing conditions.
The invention fully exerts the inducting ability of the bovine bone meal by controlling and adopting the dilute acid modification and composite grinding technology, greatly reduces the mixing amount of the bovine bone meal, carries out anti-corrosion treatment and modification, realizes the composite inducer mainly comprising the bovine bone meal, has small mixing amount, hardly influences the performance of the coating, simultaneously has strong oyster larva attaching ability, and solves the problem of mildewing of the coating after being coated. Compared with the coating without the inducer, the number of the oyster larvae attached to the concrete coated with the inducer-doped coating is obviously increased.
The comparison documents and the reference documents show that: the calcium content is important for the attachment of oyster larvae, and the addition of a proper amount of calcium carbonate substances into the cement-based material is also proved by some current experimental results to promote the attachment and growth of the oyster larvae. However, the cement-based coating contains a large amount of calcium ions, the pH value of the pore solution is generally greater than 12.5, the pH value of the saturated calcium hydroxide solution is about 12 at normal temperature, and the concentration of the calcium ions in the pore solution is about 5 mmol/L; the solubility of calcium carbonate is very low, and is only 9.5X 10 at 25 DEG C-5mol/L(9.5×10-2mmol/L). At present, the optimal range of calcium ion concentration for inducing oyster attachment is considered to be 10-25 mmol/L, and even if oyster larvae are placed in saturated calcium carbonate solution, enough Ca is not available2+The concentration provides a suitable ionic concentration for adhesion of the oysters. Further, Ca (OH) in the interior of the dope2Can be released more quickly, while the dissolution of calcium carbonate takes longer. Therefore, it was confirmed that calcium carbonate material, Ca, was incorporated in the paint to promote adhesion of oyster larvae2+Not the dominant role. Early attachment, metamorphosis and HCO of oyster3 -Related to Ca in allergy2+Together generating a secondary shell of calcium carbonate. After calcium carbonate is added, the calcium carbonate is mixed with CO2Reacting with water to form Ca (HCO)3)2The later participation in the attachment is the fundamental mechanism for promoting the attachment of oyster larvae.
The calcium carbonate doping amount in the cement-based material has an optimal doping amount, which can be explained from the following three aspects:
1) for equivalent substituted cement, as the calcium carbonate content is increased, the alkali in the cement-based material is diluted and the total alkalinity is reduced, but as the calcium carbonate content is increased, the dissolution probability of the calcium carbonate in the cement-based material is increased, and HCO in the solution is increased3 -The content is increased, so that the attachment and metamorphosis of oysters are promoted; when the mixing amount is too large, the permeability of the cement-based material is increased sharply, alkali and carbonate in the cement-based material rapidly seep out, so that the negative effect of the alkali is obvious, and the critical or negative effect of the carbonate is initially obvious, so that the adhesion amount is reduced;
2) for the same amount of substituted aggregate, the permeability of the cement-based material is reduced along with the increase of the mixing amount, which can cause calcium ions and OH-The bleeding of (2) is reduced, but the permeation rate of carbonate ions is gradually increased, and when reaching a certain value, the adhesion of the oyster reaches the maximum value; as the doping amount continues to increase, the calcium ions decrease greatly, carbonate ions may decrease, and the concentration of the calcium ions can limit the attachment of oyster larvae, which is expressed as the decrease of the attachment amount;
3) for the same amount of mineral-substituted admixtures, the permeability is increased along with the increase of the admixture, and the HCO required for the oyster adhesion requirement is increased due to the increase of calcium carbonate3 -The concentration reaches a proper range, which is shown as the attachment of oyster larvae is increased; as the addition of the mineral admixture continues to increase, the addition of the mineral admixture is reduced, so that the amount of alkali exuded increases, carbonate increases, but excess alkali and HCO3 -The ions inhibit adhesion of oyster larvae.
Compared with the comparison document 3 (plum true, public and green, closed and long billows, et al. the biological adhesion effect of concrete artificial fish reefs of different cement types [ J ] fishery science progress, 2017,38(5):57-63.), the differences are that:
in comparison document 3, composite portland cement, slag portland cement, pozzolanic portland cement, fly ash portland cement, and aluminate cement are used: the invention adopts the composite doping of ordinary portland cement and mineral admixture to realize low-alkalinity cement; the silica fume is one of mineral admixtures, has high activity, has obvious effect of improving the durability of reinforced concrete in the marine environment by proper mixing amount, and can obtain low-alkalinity cement with excellent strength and durability through optimized design and experiments. Meanwhile, by utilizing the characteristic of high impermeability of the silica fume concrete, a large amount of oyster larvae are attached, distorted and grown even if the alkalinity of the interior of the concrete is higher. And the alkalinity of the cement-based coating is regulated and controlled by adopting the composition of the low-alkalinity sulphoaluminate cement, so that a proper pH value is provided for the adhesion of oyster larvae. In addition, marine plants and sessile organisms such as oysters and barnacles have different alkali resistance and different environments required in the attachment period and later period, such as the attachment, metamorphosis and later growth of barnacles and oysters, need a large amount of calcium ions.
The concrete in the comparison document 3 is used for enriching marine organisms, mainly in view of the size and diversity of attached biomass, and the main attached organisms are various algae and the like. The aim of research in the invention is to induce oyster attachment, but the tolerance of oysters and barnacles to alkalinity is higher than that of algae, and a large amount of calcium ions are needed for oyster attachment and metamorphosis, so that two cement-based materials look the same and are greatly different.
In addition, the unique characteristics and the beneficial effects of the invention are as follows:
deep colour pigment
By utilizing the light-resistant characteristic of oyster eyespot larvae, deep color pigment (one or two of black iron oxide, nigrosine, carbon black, antimony sulfide, red iron oxide and organic pigment red) is doped into the coating, the color of the coating is changed, the color of the coating is darkened, the oyster larvae are considered as a dark environment, the oyster larvae are induced to arrive at the dark color concrete surface, the contact probability of the larvae and the concrete surface is increased, and the oyster larva induced attachment rate is increased. The method specifically comprises the following steps:
the researchers of marine organisms, in order to breed and proliferate or in order to eliminate undesirable populations, consider the study of the adhesion of marine periphyton with different colored substrates, belonging to the subject of marine biology. The discipline of marine concrete engineering or concrete materials is quite different and is two big disciplines. By crossing the marine sessile organisms with the concrete discipline, the oyster larva induced attachment by adopting the dark-color coating is obtained. In the invention, the addition of dark pigment is adopted to deepen the color of the coating to promote the attachment of oyster larvae. The incorporation of other materials into the coating can affect its performance. The invention considers the paint of different cement, which has different colors. Therefore, the amount of the dark color substance is determined according to the type and amount of the cement. Dark pigments also affect the properties of the coating. Most importantly, the deep color pigment is added, and alkali and Ca in the coating are not controlled2+When the permeation rate is equal, the released alkali can influence the attachment, metamorphosis and growth of sessile organism larvae, and when the mixing amount is more than a certain value, the attachment amount of the larvae is reduced. The impermeability of the cement-based paint is designed and controlled, and the main measures are as follows: selecting the type of the dark pigment, controlling the adding amount and modifying. The attachment rate of the larvae is increased along with the increase of the doped amount of the dark substance, and when the doped amount is 0.5-6% of the cementing material, the attachment amount of the larvae is maximum, but then the attachment amount is slightly increased or kept unchanged.
Trace elements
According to the enrichment of a large amount of zinc in the oyster body, the zinc is far higher than the seawater where the oyster lives, and meanwhile, the oyster body also contains more Fe, P and K elements. At the same time, the appropriate Zn in the solution2+，K+The concentration can promote early stage attachment and metamorphosis of oyster larva. Therefore, zinc sulfate, potassium nitrate, ferric sulfate, zinc phosphate, ammonium nitrate, potassium phosphate, ammonium phosphate, iron phosphate and calcium phosphate are adopted as trace elements to be mixed into the coating, and the strength of the coating is improved by modifying the substancesAnd the impermeability is basically kept unchanged, and the induced attachment rate of the oyster larvae is greatly increased. The method specifically comprises the following steps:
the marine organism researchers, in order to clarify the oyster attachment mechanism and the purpose of breeding and proliferation, research the attachment and metamorphosis of different ions to marine periphyton, belong to the marine biology subject. The method is different from the science of marine concrete engineering or concrete materials, and is completely two large disciplines. Through the crossing of marine sessile organisms and concrete disciplines, the method is obtained by adding corresponding substances into the coating to induce the adhesion of oyster larvae on the surface of concrete. Because the soluble salts greatly affect the performance of the coating, such as the early workability, the setting time and the later strength and impermeability, the invention adopts the diatomite as the carrier, fixes the inorganic salts in the diatomite, reduces the influence of the soluble salts on the performance of the coating, and simultaneously utilizes the function of the diatomite on improving the performance of the cement-based coating to realize that the good performance of the cement-based coating can still be maintained when the inducing substances are added. In addition, because the diatomite has a slow release effect as a carrier, the soluble salt is released slowly, and particularly, after the diatomite is soaked in seawater for a certain time, the release rate is maintained at a small rate. Therefore, this part of knowledge also relates to the intersection of marine organisms, chemistry and marine concrete engineering disciplines, and no one skilled in the concrete and engineering fields or marine organisms can obtain the technical characteristics of the present invention of incorporating trace elements into concrete, changing the ion content of trace elements on the surface of paint and controlling the paint permeability in close relation to paint with high ability to induce oyster larva attachment by means of the existing background.
Permeability of concrete
The strength and permeability of the coating are critical. When considering that different substances are added to promote adhesion, metamorphosis and later growth of oyster larvae, the performance of the coating is greatly influenced by the substances, the raw materials are selected according to the compatibility of various raw materials, and when the performance of the raw materials cannot meet the actual requirement, the raw materials are added after being modified, so that the expected functions are achieved. However, in the related researches, although the influence of the calcium content on the adhesion of the oyster larvae is considered, the performance of the coating material is not considered, the water cement ratio, the calcium content, maintenance and the like are not considered, the rate of alkali and ion leakage in the coating material is changed due to the change of the permeability of the coating material, and the poorer the impermeability of the coating material is, the larger the leakage rate of alkali and ion in the coating material is, and the increase of the permeability rate can be exponential. Thus, these released alkalis and ions have a great influence on the larvae, and there may be cases where the adhesion is promoted to be inhibited, which is more serious particularly when the cement is contained in a large amount. Therefore, the inducer is added into the coating, and the property change of the coating is ensured to be within a controllable range, such as the change is not more than 10%. The induction effects can only be compared, otherwise, the influence of the single-doped inducer or the compound-doped inducer on the induction effect of the oyster larvae cannot be evaluated.
Only the optimum environment required by the adhesion, metamorphosis and later growth of the marine periphyton is mastered, and the coating can be designed based on the high anti-permeability of the coating instead of only considering the mixing amount of various raw materials and neglecting the anti-permeability change of the coating. Therefore, this part of knowledge also relates to the intersection of marine periphyton, chemistry and marine concrete engineering disciplines, and no one skilled in the concrete and engineering fields or marine life fields can obtain the technical characteristics of the present invention that the overall control of the impermeability of the coating and the close association of the inducer to the ability of the inducer to promote the efficient induced adhesion of oysters by the existing background.
Therefore, since this part of knowledge relates to the intersection of marine periphytons, marine plants and marine concrete engineering disciplines, no matter the concrete and engineering field or the technical personnel in the marine organism field, the technical characteristics of color change, bovine bone meal modification, milling technology and control of paint permeability in the deep color pigment-doped paint of the present invention, which are closely related to the paint with high efficiency of inducing oyster attachment and high durability, can be obtained by comparing documents 1-2. And the technical feature of the present invention that the balance between the reduction in the alkalinity of the coating and the concentration of calcium ions is closely linked to the adhesion of marine periphyton cannot be obtained by comparison with document 3.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A cement-based coating for inducing sessile organisms on the surface of ocean engineering is characterized in that: the adhesive is prepared from a cementing material, sand, water, a dark color pigment, biological calcium powder, calcium carbonate powder, trace elements, lignocellulose, dispersible adhesive powder and a superplasticizer, wherein the cementing material, the sand, the water, the dark color pigment, the biological calcium powder, the calcium carbonate powder, the trace elements, the lignocellulose, the dispersible adhesive powder and the superplasticizer are sequentially prepared from the following raw materials in parts by weight: 1: (0.35-0.7): (0.20-0.60): (0.02-0.10): (0.02-0.10): (0.02-0.10): (0.01-0.08): (0.04-0.12): (0.05-0.15): (0.001-0.010).
2. The cement-based coating for inducing sessile organisms on the surface of ocean engineering as claimed in claim 1, characterized in that: the dark color pigment is as follows: one or two of iron oxide black, aniline black, carbon black, antimony sulfide, iron oxide red and organic pigment red.
3. The cement-based coating for inducing sessile organisms on the surface of ocean engineering as claimed in claim 2, characterized in that: the deep color pigment is modified according to the influence degree on the performance of concrete, and is modified by adopting one of transparent resin, organic silicon, dimethyl siloxane and super-hydrophobic materials.
4. The cement-based coating for inducing sessile organisms on the surface of ocean engineering as claimed in claim 1, characterized in that: the biological calcium carbonate powder is one or a plurality of compounds of oyster shell powder, fishbone powder, egg shell powder and coral powder, and the fineness of the biological calcium carbonate powder is 100-1000 meshes.
5. The cement-based coating for inducing sessile organisms on the surface of ocean engineering as claimed in claim 4, characterized in that: the biological calcium powder is prepared by treating 100-500 mesh egg shell powder, coral powder, oyster shell powder and fishbone powder with acid including one or two of acetic acid, silicic acid and sulfurous acid; and treating the 100-500-mesh bovine bone powder with one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid.
6. The cement-based coating for inducing sessile organisms on the surface of ocean engineering as claimed in claim 1, characterized in that: the calcium carbonate powder is as follows: calcite, chalk, limestone, marble, aragonite, travertine powder, and one or more of light calcium carbonate, activated calcium carbonate, calcium carbonate whisker and superfine light calcium carbonate which are processed, and the fineness is more than 200 meshes.
7. The cement-based coating for inducing sessile organisms on the surface of ocean engineering as claimed in claim 1, characterized in that: the trace elements of zinc, iron, potassium and phosphorus are selected from natural minerals, industrial products or chemical reagents, including one or more of zinc sulfate, calcium phosphate, zinc phosphate, potassium sulfate, potassium nitrate, ferric sulfate, ammonium nitrate, potassium phosphate, ammonium phosphate and iron phosphate, and are modified, so that the slow release of corresponding ions is realized, and the adverse effect on the performance of concrete is reduced or eliminated; however, nitrogen and phosphorus elements are not selected for eutrophic areas; the cementing material is one of silicate cement, sulphoaluminate cement and alkali-activated cementing material which are mixed with mineral admixture; wherein the mineral admixture in the silicate cement doped with the mineral admixture comprises one or more of silica fume, slag powder and fly ash; the sulphoaluminate cement comprises one or two of quick-hardening sulphoaluminate cement, high-strength sulphoaluminate cement and expansion sulphoaluminate cement; the alkali-activated cementing material comprises one of alkali-activated slag, alkali-activated slag and fly ash.
8. The cement-based coating for inducing sessile organisms on the surface of ocean engineering as claimed in claim 1, characterized in that: the sand is one or more of river sand, machine-made sand and sea sand with the particle size of 0.16-2.36 mm.
9. The cement-based coating for inducing sessile organisms on the surface of ocean engineering as claimed in claim 1, characterized in that: the superplasticizer is one of polycarboxylic acid and naphthalene series.
10. A preparation method of a cement-based coating for inducing sessile organisms on the surface of ocean engineering is characterized by comprising the following steps:
s1: weighing a cementing material, sand, water, a dark pigment, biological calcium powder, calcium carbonate powder, trace elements, lignocellulose, dispersible rubber powder and a superplasticizer;
s2: placing the cementing material, the deep color pigment, the biological calcium powder, the calcium carbonate powder and the trace elements into a mixer, wherein the rotating speed is 1000-1500 rpm, the mixing time is 2-5 minutes, and the materials are uniformly mixed;
s3: then placing the sand, the lignocellulose and the dispersible rubber powder into a stirrer, wherein the rotating speed is 500 plus 1000 revolutions per minute, and the mixing time is 5-10 minutes;
s4: fully dissolving the powdery superplasticizer into water, then placing the mixed materials into a high-speed stirrer together at the rotating speed of 200 plus materials of 500 rpm, and stirring for 5-10 minutes; thus obtaining the cement coating with good induction effect for inducing sessile organisms on the surface of ocean engineering.
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| CN201911210521.9A CN111268960B (en) | 2019-12-02 | 2019-12-02 | Cement-based paint for inducing sessile organisms on surface of ocean engineering and preparation method thereof |
| EP20895864.5A EP4071305A1 (en) | 2019-12-02 | 2020-12-01 | Construction method for ecological riprap breakwater, induced cement-based coating and preparation method therefor |
| PCT/CN2020/133082 WO2021109983A1 (en) | 2019-12-02 | 2020-12-01 | Construction method for ecological riprap breakwater, induced cement-based coating and preparation method therefor |
| KR1020227022564A KR20220144358A (en) | 2019-12-02 | 2020-12-01 | Ecological sandstone breakwater construction method, induction type cement-based paint and manufacturing method |
| JP2022533424A JP2023517785A (en) | 2019-12-02 | 2020-12-01 | Method for constructing an ecological riprap breakwater, attracting cement-based paint and method for producing the same |
| US17/831,294 US20220307213A1 (en) | 2019-12-02 | 2022-06-02 | Construction method for ecological riprap breakwater, induced cement-based coating and preparation method thereof |
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