Method for constructing ecological breakwaters using rubble, attraction-type cement-based paint, and method for manufacturing the same.

Abstract

To provide a cement coating material and application technique for inducing settlement of marine sessile organisms, especially method for constructing an ecological riprap breakwater, induced cement-based coating and method for producing the induced cement-based coating.SOLUTION: A cement coating for inducing the settlement of marine sessile organisms is applied onto surfaces of stones, and a reasonable spatial layout is applied, such that each stone pile (stone block) can effectively break waves and ensure smooth exchange between water bodies on two sides. After oysters attached to each rock pile (block) breed a large amount, the water bodies can be cleaned, and the ecological environment in the surrounding sea area can be improved.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] This application claims the benefit of priority of Chinese Patent Application No. 201911210502.6, "Method for Constructing an Ecological Rubble-Mound Breakwater", filed on December 2, 2019, and claims the benefit of priority of Chinese Patent Application No. 201911210521.9, "Cement-Based Paint for Attracting Fouling Organisms on the Surface of Marine Projects and Its Manufacturing Method", filed on December 2, 2019. The entire contents of both are incorporated herein by reference.

[0002] The present invention relates to ecological breakwater technology, particularly to a method for constructing an ecological rubble-mound breakwater, an attracting-type cement-based paint and its manufacturing method, which belongs to the field of marine ecological engineering.

Background Art

[0003] In the past few decades, with the rapid economic development in the coastal areas of China but without due attention to environmental protection, large-scale destruction of the ecological systems in the coastal areas of China has been caused, which has had a profound impact on the ecological systems and economy in the coastal areas of China. Currently, with the implementation of a series of relevant national policies, the construction of marine projects in China is also announcing the arrival of the peak period. At the same time, breakwaters that ensure the large-scale construction of marine projects and the stabilization of the surrounding sea areas are already further destroying the already fragile marine ecological systems. Without proper protection of the ecological environment, it will more severely damage the ecological systems in the coastal areas of China. At the same time, most of the infrastructure in the coastal areas of China cannot be disassembled, and since the ecological systems in its sea areas need to be restored, people are gradually realizing that by applying ecological technologies to many infrastructures, the ecological systems in the sea areas can be effectively improved or restored. Therefore, constructing breakwaters with high ecological effects or ecologicalizing existing breakwaters is very important and urgent for the improvement of the ecological environment in the coastal areas of China.

Summary of the Invention

[0004] The objective of this invention is to provide a method for constructing a highly durable, ecologically sound breakwater, thereby solving the problems of current breakwater expansion and repair destroying coastal ecosystems and the short service life of existing breakwaters. As a result, the breakwater will also have excellent wave-dissipating properties, a long service life, and high environmental efficiency.

[0005] Based on the fact that oysters prefer to adhere to dark substrates and the surface of their own shells, and that higher alkalinity affects oyster adhesion and metamorphosis, and considering the effects of simultaneously mixed-in external additives on the cement-based paint and concrete performance, this invention determines the design, molding, and curing methods for paints and concrete that attract oysters to adhere. The specific technical solutions are as follows.

[0006] (1) In order to survey the sea area where the ecological project will be constructed, the dominant oyster species and the presence or absence of oyster attachment in the sea area shall be investigated, and the air temperature, seawater temperature, dissolved oxygen, planktonic organisms, total dissolved inorganic nitrogen, active phosphate, active silicate, and Ca in the sea area in different seasons shall be investigated. 2+ Zn 2+ , K + We will investigate these factors, and further investigate the number of typhoons that have occurred in the past and their intensity.

[0007] (2) When manufacturing a concrete adhesive base, one of the following shapes is manufactured: a plate-shaped adhesive base, a corrugated adhesive base, and a cylindrical adhesive base.

[0008] (3) In order to quantitatively harvest and cultivate oyster larvae, during the period when oyster larvae in the local sea area concentrate on attaching and undergoing metamorphosis, the attachment substrate should be placed in a nearby sea area spat collection area, and the amount of oyster larvae attached should be 15-25 per 100 cm. 2 In that case, spat collection is stopped, and then the substrate is moved to a sea area rich in food and floated aquaculture is performed.

[0009] (4) Regarding the treatment of the rock surface, the rock surface is washed, and once the saturated surface is dry, a cement-based coating is sprayed or applied to the marine project surface to attract sessile organisms.

[0010] (5) Regarding the placement of the rocks, in the second year, during the period when the oyster larvae concentrate in the local sea area to attach and metamorphose, the rocks are placed in a dispersed manner, and rocks with a volume exceeding 1 cubic meter are placed individually, each rock is covered with a cage made of rope, and the cage made of rope covers multiple rocks with a volume of less than 1 cubic meter, thereby forming a pile of rocks with a volume of 1 to 5 cubic meters, the internal void ratio of which is 40% to 60%, and the rocks or piles of rocks are connected with rope or the like.

[0011] (6) When placing the oyster attachment bases on site, transport the bases to which oysters in the mature stage of gonadal development as described in (2) will attach to the sea area where the breakwater will be constructed, place a lightweight concrete oyster attachment base with a rough surface on each block of stone or pile of stones, and secure the block of stone or pile of stones with rope, and feed or add nutrients for the feed as needed based on the condition of planktonic organisms in the local sea area.

[0012] (7) Regarding monitoring and managing larval attachment, the attachment status of oyster larvae on the concrete surface should be monitored, and 30-40 larvae / 100cm should be monitored. 2 In such cases, the oyster attachment substrate will be removed, and the ecological condition of the breakwater will be monitored over the long term, with improvement measures being taken according to the actual situation.

[0013] Regarding the lightweight concrete oak adhesion substrate with a rough surface described in the specific countermeasures in (2), the components of the material are cementitious material, lightweight coarse aggregate, lightweight fine aggregate, water, dark pigment, biocalcium powder, calcium carbonate powder, trace elements, short fibers, and superplasticizer, and their weight percentages are, in order, 21.8%~34.5%, 24.6%~37.5%, 15.8%~29.6%, 8.4%~16.4%, 0.6%~3.0%, 0.4%~2.0%, 0.4%~2.0%, 0.2%~1.8%, 0.15%~1.5%, and 0.03%~0.18%.

[0014] Preferably, the dark pigment is one or two of the following: iron black, aniline black, carbon black, antimony sulfide, red iron oxide, and organic red pigment.

[0015] Preferably, the dark pigments are modified according to their degree of influence on the concrete performance, and one of the following materials is used for the modification: a transparent resin, organosilicon, dimethylsiloxane, or a superhydrophobic material.

[0016] Preferably, the biocalcium powder is bovine bone powder. , or It contains one or more combinations of oyster shell powder, fish bone powder, eggshell powder, and coral powder, with a fineness of 100 mesh to 1000 mesh. Here, oyster shell powder, fish bone powder, eggshell powder, and coral powder refer to biocalcium carbonate powder. )

[0017] Preferably, the biocalcium powder is prepared by treating 100-500 mesh eggshell powder, coral powder, oyster shell powder, and fish bone powder with one or two of ethaneic acid, acetic acid, silicic acid, and sulfurous acid, and then treating 100-500 mesh bovine bone powder with one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid.

[0018] Preferably, the calcium carbonate powder is one or more of the following: calcite, chalk, limestone, marble, aragonite, travertine powder, and processed light calcium carbonate, activated calcium carbonate, calcium carbonate whiskers, and ultrafine light calcium carbonate, with a fineness exceeding 200 mesh.

[0019] Preferably, the trace elements zinc, iron, potassium, and phosphorus are modified by selecting natural minerals, industrial products, or chemical reagents containing one or more of the following: zinc sulfate, calcium phosphate, zinc phosphate, potassium sulfate, potassium nitrate, iron sulfate, ammonium nitrate, potassium phosphate, ammonium phosphate, and iron phosphate, in order to achieve sustained release of the corresponding ions and reduce or eliminate adverse effects on concrete performance. However, in eutrophic regions, substances containing nitrogen or phosphorus are not selected.

[0020] Preferably, the cementitious material is one of Portland cement mixed with mineral admixtures, sulfoaluminate cement, or alkali-activated cementitious material. Of these, Portland cement mixed with mineral admixtures includes one or more combinations of silica fume, slag powder, and fly ash; sulfoaluminate cement includes one or two of fast-setting sulfoaluminate cement, high-strength sulfoaluminate cement, and expansive sulfoaluminate cement; and alkali-activated cementitious material includes one of alkali-activated slag or alkali-activated slag + fly ash.

[0021] Preferably, the short fibers are inorganic fibers (12-20 mm in length) containing one or more of basalt fibers, alkali-resistant glass fibers, and carbon fibers.

[0022] Preferably, the lightweight coarse aggregate is one or two of crushed lightweight porous basalt and lightweight ceramsite with a maximum particle size of less than 20 mm.

[0023] Preferably, the lightweight fine aggregate consists of one or two of crushed zeolite and lightweight ceramic sand, with a particle size of 0.2 mm to 5 mm.

[0024] A method for manufacturing a cement concrete substrate with a rough surface for attaching oysters is: Step S1 involves designing different roughness levels according to the oyster larvae's preference for attaching to rough surfaces, and then manufacturing molds with different roughness levels. Step S2 involves weighing cementitious material, lightweight coarse aggregate, lightweight fine aggregate, water, dark pigment, biocalcium powder, calcium carbonate powder, trace elements, short fibers, and superplasticizer. First, lightweight coarse aggregate and lightweight fine aggregate are placed in a concrete mixer and stirred for 0.5 to 1 minute. Next, cementitious material, dark pigment, biocalcium powder, calcium carbonate powder, and trace elements are added and stirred for a further 1 to 2 minutes. Then, short fibers, water, and superplasticizer are added and stirred for 2 to 6 minutes. After uniform stirring, the mixture is injected and vibrated in step S3. The step S4 includes taking the concrete test specimens from which the mold has been removed, placing them in a curing box with high-concentration CO2 according to the situation for curing for 0.5 to 5 hours to reduce the alkalinity of the cement specimens, and then performing standard curing for 28 days or curing according to the actual situation.

[0025] Thereby, a cement concrete oyster adhering base with a rough surface and excellent attracting effect can be manufactured.

[0026] Regarding the lightweight concrete oyster adhering base with a rough surface described in the specific countermeasures in (2), the components of its materials are dark-colored pigments, cementitious materials, lightweight coarse aggregates, lightweight fine aggregates, water, and superplasticizers. Here, the weight percentages of the dark-colored pigments, cementitious materials, lightweight coarse aggregates, lightweight fine aggregates, water, and superplasticizers are 0.6 to 3.0%, 21.8% to 34.5%, 24.6% to 37.5%, 15.8% to 29.6%, 8.4% to 16.4%, and 0.03% to 0.18% in sequence.

[0027] Regarding the lightweight concrete oyster adhering base with a rough surface described in the specific countermeasures in (2), the components of its materials are calcium carbonate powder, cementitious materials, lightweight coarse aggregates, lightweight fine aggregates, water, and superplasticizers. Here, the weight percentages of the calcium carbonate powder, cementitious materials, lightweight coarse aggregates, lightweight fine aggregates, water, and superplasticizers are 0.4 to 2.35%, 21.8% to 34.5%, 24.6% to 37.5%, 15.8% to 29.6%, 8.4% to 16.4%, and 0.03% to 0.18% in sequence.

[0028] Regarding the lightweight concrete oyster adhering base with a rough surface described in the specific countermeasures in (2), the components of its materials are bovine bone powder, cementitious materials, lightweight coarse aggregates, lightweight fine aggregates, water, and superplasticizers. Here, the weight percentages of the bovine bone powder, cementitious materials, lightweight coarse aggregates, lightweight fine aggregates, water, and superplasticizers are 0.4 to 2.35%, 21.8% to 34.5%, 24.6% to 37.5%, 15.8% to 29.6%, 8.4% to 16.4%, and 0.03% to 0.18% in sequence.

[0029] Regarding the lightweight concrete oak substrate with a rough surface described in the specific countermeasures in (2), the components of the material are modified dark pigment, calcium carbonate powder, cementitious material, lightweight coarse aggregate, lightweight fine aggregate, water, and superplasticizer, where the weight percentages of the modified dark pigment, calcium carbonate powder, cementitious material, lightweight coarse aggregate, lightweight fine aggregate, water, and superplasticizer are, respectively, 0.6-3.0%, 0.4-2.35%, 21.8%-34.5%, 24.6%-37.5%, 15.8%-29.6%, 8.4%-16.4%, and 0.03%-0.18%.

[0030] In the cement-based bio-attachment substrate described in (2) for specific measures, circular holes with a diameter of 3 to 5 mm are created during molding.

[0031] Regarding the period of concentrated attachment and metamorphosis of oyster larvae described in the specific countermeasures in (3), it is generally from May to August in North China and from April to October in South China.

[0032] Regarding the cement-based coating for attracting sessile organisms to the surface of marine projects, as described in (4) as a specific measure, the specific technical solutions are as follows:

[0033] The components of the material are cementitious material, sand, water, dark pigment, biocalcium powder, calcium carbonate powder, trace elements, wood fiber, dispersible rubber powder, and superplasticizer, with their weight ratios being 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).

[0034] Preferably, the dark pigment is one or two of the following: iron black, aniline black, carbon black, antimony sulfide, red iron oxide, and organic red pigment.

[0035] Preferably, the dark pigments are modified according to their degree of influence on the concrete performance, and one of the following materials is used for the modification: a transparent resin, organosilicon, dimethylsiloxane, or a superhydrophobic material.

[0036] Preferably, the biocalcium powder is bovine bone powder. , or It contains one or more combinations of oyster shell powder, fish bone powder, eggshell powder, and coral powder, with a fineness of 100 mesh to 1000 mesh. Here, oyster shell powder, fish bone powder, eggshell powder, and coral powder refer to biocalcium carbonate powder. )

[0037] Preferably, the biocalcium powder is prepared by treating 100-500 mesh eggshell powder, coral powder, oyster shell powder, and fish bone powder with one or two of ethaneic acid, acetic acid, silicic acid, and sulfurous acid, and then treating 100-500 mesh bovine bone powder with one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid.

[0038] Preferably, the calcium carbonate powder is one or more of the following: calcite, chalk, limestone, marble, aragonite, travertine powder, and processed light calcium carbonate, activated calcium carbonate, calcium carbonate whiskers, and ultrafine light calcium carbonate, with a fineness exceeding 200 mesh.

[0039] Preferably, the trace elements zinc, iron, potassium, and phosphorus are modified by selecting natural minerals, industrial products, or chemical reagents containing one or more of the following: zinc sulfate, calcium phosphate, zinc phosphate, potassium sulfate, potassium nitrate, iron sulfate, ammonium nitrate, potassium phosphate, ammonium phosphate, and iron phosphate, in order to achieve sustained release of the corresponding ions and reduce or eliminate adverse effects on concrete performance. However, in eutrophic regions, substances containing nitrogen or phosphorus are not selected.

[0040] Preferably, the cementitious material is one of Portland cement mixed with mineral admixtures, sulfoaluminate cement, or alkali-activated cementitious material. Of these, Portland cement mixed with mineral admixtures includes one or more combinations of silica fume, slag powder, and fly ash; sulfoaluminate cement includes one or two of fast-setting sulfoaluminate cement, high-strength sulfoaluminate cement, and expansive sulfoaluminate cement; and alkali-activated cementitious material includes one of alkali-activated slag or alkali-activated slag + fly ash.

[0041] Preferably, the sand is one or more of the following with a particle size of 0.16 mm to 2.36 mm: river sand, machine-made sand (with limestone, basalt, or granite as the base material), and sea sand.

[0042] Preferably, the superplasticizer is, for example, one of a carboxylic acid or a naphthalene-based agent.

[0043] A cement-based coating for attracting sessile organisms to the surface of marine projects and a method for manufacturing the same are: Step S1 involves weighing cementitious material, sand, water, dark pigment, biocalcium powder, calcium carbonate powder, trace elements, wood fiber, dispersible rubber powder, and superplasticizer. Step S2 involves placing cementitious material, dark pigment, biocalcium powder, calcium carbonate powder, and trace elements into a material mixer and mixing them uniformly for 2 to 5 minutes at a rotation speed of 1000 to 1500 revolutions per minute. Next, in step S3, the sand, wood fiber, and dispersible rubber powder are placed in a mixer and mixed for 5 to 10 minutes at a rotation speed of 500 to 1000 revolutions per minute. Step S4 includes thoroughly dissolving the powdered superplasticizer in water, then putting it together with the mixed materials into a high-speed mixer and stirring for 5 to 10 minutes at a rotation speed of 1000 to 1500 revolutions per minute.

[0044] This makes it possible to manufacture cement coatings with excellent attracting properties for attracting sessile organisms to the surface of marine projects.

[0045] The rope described in the specific measures in (5) is one of the following: palm fiber rope, glass fiber rope, or basalt fiber rope.

[0046] The objective of this invention is to invent a coating that can be directly applied and cured in a humid environment, which allows sessile organisms to adhere rapidly and densely to concrete surfaces, utilizing the adhesive properties of oysters to achieve a biological corrosion protection effect. The large number of sessile organisms also play a role in the purification of water bodies and the restoration of ecosystems. This solves the problems of limited effectiveness, short service life, high costs, and the need for rapid restoration of marine ecosystems due to ecosystem degradation in tidal zones and underwater areas of marine concrete projects.

[0047] The method for realizing the present invention is as follows. In this invention, a cement-based paint is manufactured by using a low-alkali cementitious material, wood fiber, dispersible rubber powder, and superplasticizer, and adding modified dark pigments, modified biocalcium powder, calcium carbonate powder, and trace elements to the paint. This paint has the function of effectively inducing the attachment and metamorphosis of oyster larvae, resulting in the effect of oysters adhering at high density and uniformly, improving the durability of concrete structures by utilizing the adhesion characteristics of oysters, and without polluting the marine environment.

[0048] The present invention further has the following structural features.

[0049] The components of the material are cementitious material, sand, water, dark pigment, biocalcium powder, calcium carbonate powder, trace elements, wood fiber, dispersible rubber powder, and superplasticizer, with their weight ratios being 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).

[0050] Preferably, the dark pigment is one or two of the following: iron black, aniline black, carbon black, antimony sulfide, red iron oxide, and organic red pigment.

[0051] Preferably, the dark pigments are modified according to their degree of influence on the concrete performance, and one of the following materials is used for the modification: a transparent resin, organosilicon, dimethylsiloxane, or a superhydrophobic material.

[0052] Preferably, the biocalcium powder is bovine bone powder. , or It contains one or more combinations of oyster shell powder, fish bone powder, eggshell powder, and coral powder, with a fineness of 100 mesh to 1000 mesh. Here, oyster shell powder, fish bone powder, eggshell powder, and coral powder refer to biocalcium carbonate powder. )

[0053] Preferably, the biocalcium powder is prepared by treating 100-500 mesh eggshell powder, coral powder, oyster shell powder, and fish bone powder with one or two of ethaneic acid, acetic acid, silicic acid, and sulfurous acid, and then treating 100-500 mesh bovine bone powder with one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid.

[0054] Preferably, the calcium carbonate powder is one or more of the following: calcite, chalk, limestone, marble, aragonite, travertine powder, and processed light calcium carbonate, activated calcium carbonate, calcium carbonate whiskers, and ultrafine light calcium carbonate, with a fineness exceeding 200 mesh.

[0055] Preferably, the trace elements zinc, iron, potassium, and phosphorus are modified by selecting natural minerals, industrial products, or chemical reagents containing one or more of the following: zinc sulfate, calcium phosphate, zinc phosphate, potassium sulfate, potassium nitrate, iron sulfate, ammonium nitrate, potassium phosphate, ammonium phosphate, and iron phosphate, in order to achieve sustained release of the corresponding ions and reduce or eliminate adverse effects on concrete performance. However, in eutrophic regions, substances containing nitrogen or phosphorus are not selected.

[0056] Preferably, the cementitious material is one of Portland cement mixed with mineral admixtures, sulfoaluminate cement, or alkali-activated cementitious material. Of these, Portland cement mixed with mineral admixtures includes one or more combinations of silica fume, slag powder, and fly ash; sulfoaluminate cement includes one or two of fast-setting sulfoaluminate cement, high-strength sulfoaluminate cement, and expansive sulfoaluminate cement; and alkali-activated cementitious material includes one of alkali-activated slag or alkali-activated slag + fly ash.

[0057] Preferably, the sand is one or more of the following with a particle size of 0.16 mm to 2.36 mm: river sand, machine-made sand (with limestone, basalt, or granite as the base material), and sea sand.

[0058] Preferably, the superplasticizer is one of a carboxylic acid or a naphthalene-based agent.

[0059] A cement-based coating for attracting sessile organisms to the surface of marine projects and a method for manufacturing the same are: Step S1 involves accurately weighing cementitious material, sand, water, dark pigment, biocalcium powder, calcium carbonate powder, trace elements, wood fiber, dispersible rubber powder, and superplasticizer. Step S2 involves placing cementitious material, dark pigment, biocalcium powder, calcium carbonate powder, and trace elements into a material mixer and mixing them uniformly for 2 to 5 minutes at a rotation speed of 1000 to 1500 revolutions per minute. Next, in step S3, the sand, wood fiber, and dispersible rubber powder are placed in a mixer and mixed for 5 to 10 minutes at a rotation speed of 500 to 1000 revolutions per minute. The present invention is characterized by comprising step S4, which involves thoroughly dissolving a powdered superplasticizer in water, then placing it together with the mixed materials into a high-speed mixer and stirring at a rotation speed of 200 to 500 revolutions per minute for 5 to 10 minutes.

[0060] This makes it possible to manufacture cement-based coatings with excellent attracting properties for attracting sessile organisms to the surface of marine projects.

[0061] Compared to the conventional technology, the beneficial effects of the present invention are as follows:

[0062] In this invention, a cement-based coating for attracting sessile organisms is applied to the surface of natural stone blocks on the surface of a marine project, and a rough-surfaced concrete oyster attachment substrate is placed on the stone piles. This allows oyster larvae to attach to the stone blocks quickly and densely, and enables the oysters to obtain sufficient nutrients during the process of attachment, metamorphosis, and development. Furthermore, by using a rational spatial layout, each stone pile (stone block) effectively dissipates waves when the load of ocean currents is high, and the water on both sides of the breakwater can be smoothly exchanged on normal days. After a large number of oysters have proliferated attached to each stone pile (stone block), the ecological breakwater can also purify the water and improve the ecological environment of the surrounding sea area. In this way, the problems that conventional breakwaters have, such as hindering the exchange of water on both sides, changing the pH value of the local sea area, and further destroying the ecological environment, are completely solved, and the ecological environment of the sea area can be restored.

[0063] Currently, there are no environmentally friendly and economical methods for improving the durability of marine concrete or for ecologically restoring marine concrete projects. Oysters, as marine "ecological engineers," have the function of densifying the surface of concrete structures and improving the ecological environment. The cement-based coating for attracting sessile organisms provided by this invention not only has the characteristic of rapidly attracting sessile organisms to attach, metamorphose, and promote long-term growth, but also has the characteristics of being easy to apply and install. It can be applied to new marine projects, especially large-scale marine projects in use. It can not only improve the durability of reinforced concrete structures but also easily and economically realize the restoration of the marine ecological environment. It can not only greatly expand the application of marine sessile organism corrosion prevention on reinforced concrete structures in use, but can also be widely used in marine ecological environment restoration projects. [Brief explanation of the drawing]

[0064] [Figure 1] This situation involves mold growing on the surface of concrete with a different mixing ratio, specifically one containing 10% cow bone powder. [Figure 2] These are different mixing ratios when mixing in 10% modified bovine bone powder with a fineness of 200 mesh. [Figure 3] This is a schematic diagram of a 210-day experiment involving attachment to the actual ocean. [Figure 4] This is a schematic diagram of a 300-day experiment involving adhesion in the actual ocean. [Figure 5] This is a schematic diagram of the concrete substrate to which the oysters are attached. [Figure 6] This is a schematic diagram of the concrete substrate to which the oysters are attached. [Figure 7] This is a schematic diagram of the concrete substrate to which the oysters are attached. [Modes for carrying out the invention]

[0065] The present invention will be described in detail below with reference to examples, which are used solely for the purpose of illustrating the present invention and are not intended to limit the scope of the invention.

[0066] The specific technical solutions to the project plan are as follows:

[0067] (Example 1) (1) In order to investigate the sea area where the breakwater will be constructed, the dominant oyster species and the presence or absence of oyster attachment in the sea area will be investigated, and tests will be conducted 15 times every quarter, recording the air temperature, seawater temperature, dissolved oxygen, planktonic organisms, total dissolved inorganic nitrogen, active phosphate, active silicate, Ca2+, Zn2+, and K+ ions in the sea area. Furthermore, the number and intensity of past typhoons will be investigated, meteorological and hydrological data of the sea area over many years will be examined, and feasible methods and solutions for the construction of an ecological breakwater will be analyzed.

[0068] (2) In the manufacture of the concrete adhesive base, eco-concrete is used to manufacture a lightweight concrete adhesive base with a rough surface. The size of the adhesive base is 10cm x 10cm x 2cm. After molding, it is immediately subjected to CO2 curing at 10 atmospheres for 1 hour, followed by standard curing for 28 days.

[0069] (3) In order to harvest and cultivate oyster larvae quantitatively at a set time, in July, a coarse, lightweight concrete oyster attachment substrate is placed in a nearby sea area for spat collection. When the amount of oyster larvae attached is 20 per 100 cm2, spat collection is stopped, and the attachment substrate is then moved to a sea area rich in food for floating cultivation.

[0070] (4) Regarding the treatment of the rock surface, the rock surface is inspected, any rock surface containing impurities and chemical contaminants is cleaned, and once the saturated surface is dry, a cement-based coating is applied to the marine project surface to attract sessile organisms.

[0071] (5) Regarding the placement of the stone blocks, in June of the second year, they shall be placed in a dispersed manner, with stone blocks exceeding 1 cubic meter in volume placed individually, each stone block covered with a basket made of rope, and the baskets made of rope shall cover multiple stone blocks with a volume of less than 1 cubic meter, thereby forming a pile of stones with a volume of 1 to 5 cubic meters, the internal void ratio of which shall be 50%, the rocks or piles of stones shall be connected with rope or the like, and the distance between each stone block (pile of stones) shall be maintained at 4 meters.

[0072] (6) When placing the oyster attachment bases on site, transport bases that allow oysters (in the mature stage of gland development) to adhere well to the concrete surface to the construction area of ​​the breakwater, place the oyster attachment bases on each block of stone (piles of stones), and secure the blocks of stone or piles of stones with ropes.

[0073] (7) In managing and monitoring larval attachment, if the attachment density of oyster larvae on the concrete surface reaches 35 larvae / 100 cm2, the oyster attachment substrate shall be removed, and at the same time, a decision shall be made on whether or not to feed the oysters based on the types and numbers of planktonic organisms in the area.

[0074] (Example 2) (1) In order to investigate the sea area where the breakwater will be constructed, the dominant oyster species and the presence or absence of oyster attachment in the sea area will be investigated, and tests will be conducted 15 times every quarter, recording the air temperature, seawater temperature, dissolved oxygen, planktonic organisms, total dissolved inorganic nitrogen, active phosphate, active silicate, Ca2+, Zn2+, and K+ ions in the sea area. Furthermore, the number and intensity of past typhoons will be investigated, and meteorological and hydrological data of the sea area over many years will be examined to analyze feasible methods and solutions for the construction of an ecological breakwater.

[0075] (2) In the manufacture of the concrete adhesive base, eco-concrete is used to manufacture a lightweight concrete adhesive base with a rough surface. The size of the adhesive base is 10cm x 10cm x 3cm. After molding, it is immediately subjected to CO2 curing at 10 atmospheres for 1.5 hours, followed by standard curing for 28 days.

[0076] (3) In order to harvest and cultivate oyster larvae quantitatively at a set time, in August, a coarse lightweight concrete oyster attachment substrate is placed in a spat collection area in a nearby sea area. When the number of oyster larvae attached reaches 25 per 100 cm2, spat collection is stopped, and the attachment substrate is then moved to a sea area rich in food for floating cultivation.

[0077] (4) Regarding the treatment of the rock surface, the rock surface is inspected, any rock surface containing impurities and chemical contaminants is cleaned, and once the saturated surface is dry, a cement-based coating is applied to the marine project surface to attract sessile organisms.

[0078] (5) Regarding the placement of the stone blocks, in July of the second year, they shall be placed in a dispersed manner, with stone blocks exceeding 1 cubic meter in volume placed individually, each stone block covered with a basket made of rope, and the baskets made of rope shall cover multiple stone blocks with a volume of less than 1 cubic meter, thereby forming a pile of stones with a volume of 1 to 5 cubic meters, the internal void ratio of which shall be 60%, the rocks or piles of stones shall be connected with rope or the like, and the distance between each stone block (pile of stones) shall be maintained at 5 meters.

[0079] (6) When placing the oyster attachment bases on site, bases that allow oysters (in the mature stage of gland development) to adhere well to the concrete surface are transported to the construction area of ​​the breakwater, and the oyster attachment bases are placed for each block of stone (pile of stones), and the blocks of stone or piles of stones are secured with ropes.

[0080] (7) In managing and monitoring larval attachment, if the attachment density of oyster larvae on the concrete surface reaches 40 larvae / 100 cm2, the oyster attachment substrate shall be removed, and at the same time, a decision shall be made on whether or not to feed the oysters based on the types and numbers of planktonic organisms in the area.

[0081] The mixing ratios of the oyster adhesion substrate and cement-based paint described in Example 1 and Example 2 are as follows, and the specific shape design of the concrete oyster adhesion substrate can be found in Figures 5 to 7.

[0082] The concrete mix ratios for the lightweight concrete oyster attachment substrate (1-25) with a rough surface, and the cement-based coating (26-35) for attracting sessile organisms to the surface of marine projects are as follows:

[0083] 1. Regarding the concrete mix ratio for ordinary Portland cement, the weight percentages of ordinary Portland cement, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, respectively, 29.37%, 33.53%, 24.48%, 12.59%, and 0.03%.

[0084] Of these, the lightweight coarse aggregate is one or two of crushed lightweight porous basalt and lightweight ceramsite with a maximum particle size of less than 20 mm. The lightweight fine aggregate is one or two of crushed zeolite and lightweight ceramic sand, with a particle size of 0.2 mm to 5 mm and of high grade. The water must meet the quality standards for concrete water (JGJ63-2006), have a Cl- content <1000 mg / L, a pH value >4.5, and have little effect on the initial hardening time difference and final hardening time, strength, and permeability of the cement. Furthermore, the materials selected for 1 to 25 are the same.

[0085] 2. Regarding the mix ratio of standard concrete, the weight percentages of ordinary Portland cement, silica fume, blast furnace slag powder, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, respectively, 17.62%, 1.47%, 10.28%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0086] 3. The weight percentages of unmodified dark pigments, ordinary Portland cement, silica fume, blast furnace slag powder, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, respectively, 0.87%, 17.62%, 1.36%, 9.52%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0087] 4. The weight percentages of unmodified dark pigments, ordinary Portland cement, silica fume, blast furnace slag powder, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, respectively, 1.47%, 17.62%, 1.28%, 8.99%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0088] 5. The weight percentages of unmodified dark pigments, ordinary Portland cement, silica fume, blast furnace slag powder, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, respectively, 2.35%, 17.62%, 1.18%, 8.23%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0089] 6. The weight percentages of the modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), ordinary Portland cement, silica fume, blast furnace slag powder, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, respectively, 0.87%, 17.62%, 1.36%, 9.52%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0090] 7. The weight percentages of the modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), ordinary Portland cement, silica fume, blast furnace slag powder, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, respectively, 1.47%, 17.62%, 1.28%, 8.99%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0091] 8. The weight percentages of the modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), ordinary Portland cement, silica fume, blast furnace slag powder, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder were, respectively, 2.35%, 17.62%, 1.18%, 8.23%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0092] The modified dark pigment is 196 transparent resin, which is mixed with 3% hardener and 1.5% accelerator, with a volume ratio of pigment to resin of 1:0.2. It hardens at room temperature for 4 hours, then at 60°C for 4 hours, and then it is simply crushed by hammering and pulverized in a vibratory mill until the powderiness exceeds 400 mesh.

[0093] 9. The weight percentages of calcium carbonate powder, ordinary Portland cement, silica fume, blast furnace slag powder, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, respectively, 0.87%, 17.62%, 1.36%, 9.52%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0094] 10. The weight percentages of calcium carbonate powder, ordinary Portland cement, silica fume, blast furnace slag powder, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, respectively, 1.47%, 17.62%, 1.28%, 8.99%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0095] 11. The weight percentages of calcium carbonate powder, ordinary Portland cement, silica fume, blast furnace slag powder, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, respectively, 2.35%, 17.62%, 1.18%, 8.23%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0096] 12. The weight percentages of the modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), calcium carbonate powder, ordinary Portland cement, silica fume, blast furnace slag powder, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, in order, 1.47%, 0.87%, 17.62%, 1.18%, 8.23%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0097] 13. The weight percentages of the modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), calcium carbonate powder, ordinary Portland cement, silica fume, blast furnace slag powder, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, in order, 1.47%, 1.47%, 17.62%, 1.10%, 7.71%, 33.57%, 24.48%, 12.59%, and 0.03%, respectively.

[0098] 14. The weight percentages of the modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), calcium carbonate powder, ordinary Portland cement, silica fume, blast furnace slag powder, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, in order, 1.47%, 2.35%, 17.62%, 0.99%, 6.94%, 33.57%, 24.48%, 12.59%, and 0.03%, respectively.

[0099] 15. The weight percentages of unmodified bovine bone powder, ordinary Portland cement, silica fume, blast furnace slag powder, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, respectively, 0.87%, 17.62%, 1.36%, 9.52%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0100] 16. The weight percentages of unmodified bovine bone powder, ordinary Portland cement, silica fume, blast furnace slag powder, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, respectively, 1.47%, 17.62%, 1.28%, 8.99%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0101] 17. The weight percentages of unmodified bovine bone powder, ordinary Portland cement, silica fume, blast furnace slag powder, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, respectively, 2.35%, 17.62%, 1.18%, 8.23%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0102] 18. The weight percentages of modified bovine bone powder, ordinary Portland cement, silica fume, blast furnace slag powder, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, respectively, 0.87%, 17.62%, 1.36%, 9.52%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0103] 19. The weight percentages of modified bovine bone powder, ordinary Portland cement, silica fume, blast furnace slag powder, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, respectively, 1.47%, 17.62%, 1.28%, 8.99%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0104] 20. The weight percentages of modified bovine bone powder, ordinary Portland cement, silica fume, blast furnace slag powder, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, respectively, 2.35%, 17.62%, 1.18%, 8.23%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0105] The method for modifying bovine bone powder is as follows: Add 100-mesh bovine bone powder to a 2% phosphoric acid solution, with a weight ratio of 1:3, at a temperature of 20-30°C, and stir for 30 minutes in a mixer with a rotation speed of 200-500 revolutions / minute. Centrifuge for 3 minutes in a centrifuge with a rotation speed of 3000-5000 revolutions / minute, discard the supernatant, and wash the centrifuged solids 2-3 times with water. The washing water should not be acidic. Vacuum dry the centrifuged solids at 40°C, mix the dried bovine bone powder and slag powder in a 1:4 ratio, and grind in a vibratory mill until the fineness exceeds 200 mesh, preparing for use.

[0106] 21. The weight percentages of calcium carbonate powder, zinc sulfate, modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), ordinary Portland cement, blast furnace slag powder, silica fume, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, in order, 2.35%, 0.5%, 1.47%, 17.62%, 0.93%, 6.50%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0107] 22. The weight percentages of calcium carbonate powder, zinc sulfate, modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), ordinary Portland cement, blast furnace slag powder, silica fume, lightweight coarse aggregate, lightweight fine aggregate, water, and polycarboxylate water-reducing agent powder are, in order, 2.35%, 1.2%, 1.47%, 17.62%, 0.84%, 5.89%, 33.57%, 24.48%, 12.59%, and 0.03%, respectively.

[0108] 23. The weight percentages of zinc sulfate, modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), modified biocalcium powder (modified bovine bone powder:oyster shell powder = 2:1), calcium carbonate powder, ordinary Portland cement, silica fume, blast furnace slag powder, crushed stone, sand, water, and polycarboxylate water-reducing agent powder are, in order, 0.5%, 1.47%, 1.47%, 0.87%, 17.62%, 0.93%, 6.50%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0109] 24. The weight percentages of zinc sulfate, modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), modified biocalcium powder (modified bovine bone powder:oyster shell powder = 2:1), calcium carbonate powder, ordinary Portland cement, silica fume, blast furnace slag powder, crushed stone, sand, water, and polycarboxylate water-reducing agent powder are, respectively, 0.6%, 1.47%, 1.47%, 0.87%, 17.62%, 0.84%, 5.89%, 33.57%, 24.48%, 12.59%, and 0.03%.

[0110] The method for modifying zinc sulfate is as follows: Select diatomaceous earth with an SiO2 content >90% and a fineness of 600 mesh. Add 150g of water to it in a 60°C mixer, then add 100g of zinc sulfate and stir until completely dissolved, preparing it for use. Subsequently, heat 150g of the above diatomaceous earth to 60°C, add it to the solution, stir for 10 minutes in a mixer at a rotation speed of 200-500 revolutions per minute, and then dry it in a drying oven at a drying temperature of 100°C to obtain modified zinc sulfate.

[0111] 25. The weight percentages of zinc sulfate, modified dark pigment, modified biocalcium powder (modified bovine bone powder:oyster shell powder = 2:1), calcium carbonate powder, ordinary Portland cement, silica fume, blast furnace slag powder, crushed stone, sand, water, short fibers, and polycarboxylate water-reducing agent powder are, in order, 0.5%, 1.47%, 1.47%, 0.87%, 17.62%, 0.93%, 6.50%, 33.07%, 24.18%, 12.59%, 0.8%, and 0.03%.

[0112] 26. The weight ratio of cementitious material, sand, water, modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), modified biocalcium powder (modified bovine bone powder:oyster shell powder = 2:1), calcium carbonate powder, zinc sulfate, wood fiber, dispersible rubber powder, and superplasticizer is 1:0.5:0.4:0.03:0.03:0.03:0.02:0.06:0.06:0.05.

[0113] 27. The weight ratios of cementitious material, sand, water, modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), modified biocalcium powder (modified bovine bone powder:oyster shell powder = 2:1), calcium carbonate powder, zinc sulfate, wood fiber, dispersible rubber powder, and superplasticizer are, in order, 1:0.5:0.4:0.05:0.05:0.05:0.02:0.06:0.06:0.05.

[0114] 28. The weight ratios of cementitious material, sand, water, modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), modified biocalcium powder (modified bovine bone powder:oyster shell powder = 2:1), calcium carbonate powder, zinc sulfate, wood fiber, dispersible rubber powder, and superplasticizer are, in order, 1:0.5:0.4:0.05:0.05:0.05:0.04:0.08:0.09:0.005.

[0115] 29. The weight ratios of cementitious material, sand, water, modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), modified biocalcium powder (modified bovine bone powder:oyster shell powder = 2:1), calcium carbonate powder, zinc sulfate, wood fiber, dispersible rubber powder, and superplasticizer are, in order, 1:0.5:0.4:0.08:0.08:0.08:0.04:0.08:0.09:0.005.

[0116] 30. The weight ratios of cementitious material, sand, water, modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), modified biocalcium powder (modified bovine bone powder:oyster shell powder = 2:1), calcium carbonate powder, zinc sulfate, wood fiber, dispersible rubber powder, and superplasticizer are, in order, 1:0.5:0.4:0.08:0.08:0.08:0.06:0.10:0.12:0.005.

[0117] 31. The weight ratio of cementitious material, sand, water, modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), modified biocalcium powder (modified bovine bone powder:oyster shell powder = 2:1), calcium carbonate powder, zinc sulfate, wood fiber, dispersible rubber powder, and superplasticizer is 1:0.5:0.4:0.03:0.03:0.03:0.04:0.06:0.06:0.05.

[0118] 32. The weight ratios of cementitious material, sand, water, modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), modified biocalcium powder (modified bovine bone powder:oyster shell powder = 2:1), calcium carbonate powder, zinc sulfate, wood fiber, dispersible rubber powder, and superplasticizer are, in order, 1:0.5:0.4:0.05:0.05:0.05:0.04:0.06:0.06:0.005.

[0119] 33. The weight ratios of cementitious material, sand, water, modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), modified biocalcium powder (modified bovine bone powder:oyster shell powder = 2:1), calcium carbonate powder, zinc sulfate, wood fiber, dispersible rubber powder, and superplasticizer are, in order, 1:0.5:0.4:0.05:0.05:0.05:0.02:0.08:0.09:0.005.

[0120] 34. The weight ratios of cementitious material, sand, water, modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), modified biocalcium powder (modified bovine bone powder:oyster shell powder = 2:1), calcium carbonate powder, zinc sulfate, wood fiber, dispersible rubber powder, and superplasticizer are, in order, 1:0.5:0.4:0.08:0.08:0.08:0.06:0.08:0.09:0.005.

[0121] 35. The weight ratios of cementitious material, sand, water, modified dark pigment (mass ratio of iron black:aniline black mixture = 1:1), modified biocalcium powder (modified bovine bone powder:oyster shell powder = 2:1), calcium carbonate powder, zinc sulfate, wood fiber, dispersible rubber powder, and superplasticizer are, in order, 1:0.5:0.4:0.03:0.03:0.03:0.06:0.10:0.12:0.005.

[0122] The method for modifying the dark pigment is as follows: Using 196 transparent resin, mix in 3% hardener and 1.5% accelerator, then mix with the pigment, with a volume ratio of pigment to resin of 1:0.2. Curing is performed at room temperature for 4 hours, then at 60°C for 4 hours, and then it is simply crushed by striking and pulverized with a vibratory mill until the powderiness exceeds 400 mesh.

[0123] The method for modifying bovine bone powder is as follows: Add 100-mesh bovine bone powder to a 2% phosphoric acid solution, with a weight ratio of 1:3, at a temperature of 20-30°C, and stir for 30 minutes in a mixer with a rotation speed of 200-500 revolutions / minute. Centrifuge for 3 minutes in a centrifuge with a rotation speed of 3000-5000 revolutions / minute, discard the supernatant, and wash the centrifuged solids 2-3 times with water. The washing water should not be acidic. Vacuum dry the centrifuged solids at 40°C, mix the dried bovine bone powder and slag powder in a 1:4 ratio, and grind in a vibratory mill until the fineness exceeds 200 mesh, preparing for use.

[0124] The method for modifying zinc sulfate is as follows: Select diatomaceous earth with an SiO2 content >90% and a fineness of 600 mesh. Add 150g of water to it in a 60°C mixer, then add 100g of zinc sulfate and stir until completely dissolved, preparing it for use. Subsequently, heat 150g of the above diatomaceous earth to 60°C, add it to the solution, stir for 10 minutes in a mixer at a rotation speed of 200-500 revolutions per minute, and then dry it in a drying oven at a drying temperature of 100°C to obtain modified zinc sulfate.

[0125] Reference 1, Living Breakwaters: Green Infrastructure on the New York Coast - Sun Il-hek

[0126] In Reference 1, the construction of a "living" breakwater was carried out, and the number of marine organisms was increased by macro-design, surface texture, and concrete members manufactured with low-alkali cement. The increased marine organisms were marine plants and marine sessile organisms, mainly marine plants. In the present invention, in addition to lowering the alkalinity of the cement, dark-colored pigments, biocalcium powder, calcium carbonate powder, and trace elements are mixed into the concrete to attract oyster larvae. This attraction is characterized by its rapid and dense nature, is highly effective, and can significantly improve the ecological environment of the marine area.

[0127] Compared to Reference 2, Biomimetic Concrete Artificial Reef and Method for Manufacturing the Same (2015 CN104938384 A), the differences are as follows:

[0128] (1) The purpose of the present invention differs from that of reference document 2, in which a cement mortar mixed with crushed oyster shells is applied to the concrete surface, but its purpose is to improve the aquatic environment by attracting fish, microorganisms, and algae through biomimetic surface action and increasing the number of microorganisms, and oysters are not mentioned. The purpose of the cement-based coating of the present invention is to attract oysters to adhere to it.

[0129] (2) According to Reference 2, in cement mortar, bio-calcium carbonate powder (150-200 mesh) in amounts less than 10% of the cement is ineffective against adhesion by attraction. However, in the course of research for the present invention, using a cement-based coating (powder density 100-1000 mesh) mixed with modified bovine bone powder and bio-calcium carbonate powder, it was found that the optimal dosage of bovine bone powder and bio-calcium carbonate powder is 10% or less of the cementitious material.

[0130] (3) Modifying bovine bone powder and biocalcium carbonate powder specifically involves treating 100-500 mesh eggshell powder, coral powder, oyster shell powder and fish bone powder with one or two of ethane acid, acetic acid, silicic acid, sulfurous acid, etc., and treating 100-500 mesh bovine bone powder with one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid.

[0131] (4) In the references, embedding oyster shells into the concrete surface is difficult, and not all project surfaces use this method, making it impractical. The present invention can achieve the excellent effect of attracting sessile organisms by applying a cement-based coating layer to the concrete surface, eliminating the need to embed oyster shells, making it easy to apply, and significantly improving the amount of oysters that adhere to it.

[0132] (5) In recent years, severe corrosion of artificial reefs has frequently occurred in marine environments. This severe corrosion is mainly caused by the combined action of biological sulfuric acid secreted by anaerobic microorganisms such as Thiobacillus bacteria and acidic substances secreted by other bacteria. However, calcium carbonate has very poor acid corrosion resistance, so if the content of finely powdered calcium carbonate is too high, it can cause severe acid corrosion.

[0133] Compared to the findings in Reference 3, Fan Ruiliang, "The influence of substrate type on oyster attachment, growth, population establishment and reef development [D]), the differences are as follows:

[0134] (1) In Reference 3, 80-mesh bovine bone powder, calcium powder, and gypsum powder are taken and mixed independently into the concrete. The fineness of all calcium-based materials in this invention exceeds 100 mesh, which is greater than the fineness of the materials in Reference 3. Similarly, the bovine bone powder is modified for mixing, and the grading of the paint and concrete particles and their attracting ability are taken into consideration.

[0135] (2) When bovine bone powder is crushed in a vibrating mill under room temperature conditions, after the fineness exceeds 80 mesh, it clumps together because the bovine bone powder contains a large amount of collagen, making it impossible to continue crushing. In the present invention, when dilute acid modification technology is used and crushed together with other substances, a modified biocalcium powder with a small particle size and a fineness >200 mesh is obtained. The obtained biocalcium powder retains the original biocalcium substance, improves the release rate of substances that attract oyster larvae to attach, and reduces the amount of biocalcium powder administered, thereby reducing the impact on paint and concrete performance.

[0136] (3) Bovine bone powder contains a large amount of organic substances such as collagen. When large amounts of these substances are mixed in, it reduces the strength and penetration resistance of the paint and concrete. In particular, when the dosage is increased after exceeding 5%, the strength of the paint and concrete rapidly decreases, the penetration resistance becomes significantly lower, and mold grows on the surface of the paint and concrete under standard curing conditions. Figure 1 shows the situation when mold grows on the concrete surface. Figure 2 shows the surface condition of the modified concrete.

[0137] As can be seen in Figure 1, the mold on the concrete surface is white and cottony, covering almost the entire surface of the concrete. In contrast, when the bovine bone powder, age, and curing conditions are the same, there is no mold on the concrete surface in Figure 2.

[0138] This invention utilizes dilute acid modification and composite grinding technology to fully utilize the attracting ability of bovine bone powder, significantly reducing the amount of bovine bone powder used, and performing corrosion prevention treatment and modification to produce a composite attractant mainly composed of bovine bone powder. This attractant has a low dosage, hardly affects the strength and permeability of paints and concrete, and simultaneously has a high adhesion ability for oyster larvae, solving the problem of mold growth on paints and concrete. Furthermore, compared to concrete without the attractant, the number of oyster larvae attached to concrete with the attractant mixed in is significantly increased. See Figure 3 for details.

[0139] As can be seen from the references and researched materials, calcium content is essential for oyster larva attachment, and similarly, some current test results also prove that mixing an appropriate amount of calcium carbonate into cement-based materials can promote oyster larva attachment and growth. However, cement paint and cement concrete contain large amounts of calcium ions, and the pH value of the pore solution generally exceeds 12.5. At room temperature, the pH value of a saturated calcium hydroxide solution is approximately 12, and therefore the calcium ion concentration in the concrete pore solution is approximately 5 mmol / L. The solubility of calcium carbonate is very low, only 9.5 × 10⁻⁵ mol / L (9.5 × 10⁻² mmol / L) at 25°C. Currently, the optimal range of calcium ion concentration to attract oysters to attach is considered to be 10-25 mmol / L, and even when oyster larvae are placed in a saturated calcium carbonate solution, there is not enough Ca²⁺ concentration to provide a suitable ion concentration for oyster attachment. Furthermore, while Ca(OH)₂ can be rapidly released in cement paint and concrete, the dissolution of calcium carbonate takes time. Therefore, when calcium carbonate materials are mixed into paints and concrete to promote oyster larval attachment, it can be concluded that Ca2+ does not play a dominant role. Early attachment and metamorphosis of oysters are related to HCO3-, and during metamorphosis, a secondary shell of calcium carbonate is formed together with Ca2+. After calcium carbonate is mixed in, it reacts with CO2 and water to produce Ca(HCO3)2, which then participates in attachment, and this is the basic mechanism that promotes oyster larval attachment.

[0140] There is an optimal amount of calcium carbonate for cement-based materials, and this can be explained from the following three aspects.

[0141] 1) With the same amount of alternative cement, increasing the amount of calcium carbonate administered dilutes the alkali in the paint and concrete, reducing the total alkalinity. However, increasing the amount of calcium carbonate administered improves the solubility of calcium carbonate in the paint and concrete, increasing the HCO3- content in the solution, thus promoting adhesion and transformation. However, if the dosage is too high, the permeability of the paint and concrete increases rapidly, causing alkali and carbonates in the paint and concrete to leach out rapidly. The adverse effects of alkali become pronounced, and the critical effect or adverse effects of carbonates begin to appear, resulting in a decrease in adhesion.

[0142] 2) With the same amount of alternative aggregate, as the dosage increases, the permeability of the paint and concrete decreases, and the leaching of calcium ions and OH- decreases. However, the permeability of carbonate ions gradually improves, and once it reaches a certain value, oyster attachment reaches its maximum. As the dosage continues to increase, calcium ions decrease significantly, and carbonates may also decrease. The calcium ion concentration limits oyster larva attachment, which manifests as a decrease in the amount of attachment.

[0143] 3) With the same amount of alternative mineral admixture, as the dosage increases, the permeability also improves, and the increase in calcium carbonate brings the HCO3- concentration necessary for oyster attachment to an appropriate range, which manifests as an improvement in the amount of oyster larvae attached. As the dosage of mineral admixture continues to increase, the dosage of mineral admixture decreases, and the amount of leached alkali and carbonate increases. However, if there is too much alkali and HCO3- ions, it inhibits the attachment of oyster larvae.

[0144] Compared to Reference 4 (Li Zhenzhen, Gong Pihai, Guan Changtao, et al. Biofouling effects of concrete artificial reefs of various cement types [J]. Advances in Fisheries Science, 2017, 38(5):57-63.), the differences are as follows:

[0145] Reference 4 describes the use of composite Portland cement, slag Portland cement, pozzolanic Portland cement, fly ash Portland cement, and alumina cement. In the present invention, a low-alkali segment is achieved by compounding and mixing ordinary Portland cement with mineral admixtures. Here, silica fume is one of the mineral admixtures, and its high activity and appropriate dosage have a clear effect on improving the durability of reinforced concrete in marine environments. Through optimized design and testing, a low-alkali cement with excellent strength and durability can be obtained. At the same time, due to the high penetration-resistant properties of silica fume concrete, a large number of oyster larvae can attach, metamorphose, and grow even if the alkalinity inside the concrete is high. Furthermore, by compounding with low-alkali sulfoaluminate cement, the alkalinity of the cement concrete is adjusted, providing an appropriate pH value for oyster larva attachment. Furthermore, marine plants and sessile organisms such as oysters and barnacles have different alkali tolerances, and the environmental requirements differ between the attachment stage and the later stages. For example, attachment, metamorphosis, and later growth of barnacles and oysters require large amounts of calcium ions.

[0146] In Reference 4, concrete is used to attract marine organisms, primarily due to the size and diversity of the fouling organisms, which are various types of algae. In the present invention, the research objective is to attract oysters, however, oysters and barnacles have higher alkali resistance than algae, and oyster attachment and metamorphosis require large amounts of calcium ions. Therefore, although the two types of concrete look similar, they are actually quite different. Figures 4 and 5 compare the biofouling situation after an actual ocean fouling experiment of approximately 210 days in Reference 3 with the biofouling situation after a 300-day actual ocean fouling experiment in the present invention, respectively.

[0147] In Reference 4, concrete is used to attract marine organisms, primarily due to the size and diversity of the sessile organisms, which are various types of algae. In this invention, the research objective is to attract oysters, however, oysters and barnacles have higher alkali resistance than algae, and oyster attachment and metamorphosis require large amounts of calcium ions. Therefore, although the two types of concrete look similar, they are actually quite different.

[0148] Therefore, similarly, knowledge in this area, with respect to the interdisciplinary integration of marine sessile organisms, marine plants, and marine concrete engineering, cannot be obtained by those skilled in the art in the field of concrete engineering or marine biology, as can be seen from Reference 3, in the present invention, where the reduction in alkalinity of concrete and the balance of calcium ion concentration are closely related to the attachment of marine sessile organisms.

[0149] Furthermore, the unique features of this invention and their beneficial effects are as follows.

[0150] Dark pigments

[0151] By utilizing the phototaxis of oyster eyespot larvae, one or two dark pigments (iron black, aniline black, carbon black, antimony sulfide, red iron oxide, or organic red pigment) are mixed into the concrete to change its color. The darker color of the concrete makes the oyster larvae perceive it as a dark environment, attracting them to the dark concrete surface on their own. This increases the probability of contact between the oyster larvae and the concrete surface, thereby increasing the probability of them attaching to the concrete. Specifically, the method is as follows:

[0152] (Researchers in marine biology have considered studying the attachment of marine sessile organisms using substrates of different colors to cultivate and increase or eliminate undesirable populations, and this belongs to the field of marine biology. It is completely different from marine concrete engineering and concrete materials science, and is entirely two major fields. The interdisciplinary fusion of marine sessile organisms and concrete materials science involves using dark-colored paints and concrete to attract oyster larvae to attach. This invention involves adding dark pigments to darken the color of the paint and concrete and promote the attachment of oyster larvae. Other materials are mixed into the paint and concrete, affecting their performance. This invention takes into account that concrete of different cements has different surface colors. Therefore, The dosage of the dark pigment is determined based on the type and amount of the pigment used. Dark pigments also affect the performance of the paint and concrete. Most importantly, if the penetration rate of alkali and Ca2+ in the paint and concrete is not controlled at the same time as mixing in the dark pigment, the released alkali will affect the adhesion, metamorphosis, and growth of sessile organism larvae, and if the dosage exceeds a predetermined value, the amount of larvae attached will decrease. In this invention, the penetration prevention properties of concrete are designed and controlled, and the main measures are the selection of the type of dark pigment, the control of the dosage, and modification. As the dosage of the dark pigment increases, the amount of larvae attached increases, and when the dosage is 0.5% to 6% of the cementitious material, the amount of larvae attached is at its highest, but thereafter it increases only slightly or does not change.

[0153] trace elements

[0154] Oysters contain a large amount of zinc, far more than in the seawater in which they live, and at the same time, they also contain many iron, phosphorus, and potassium elements. Simultaneously, appropriate concentrations of Zn2+ and K+ in the solution can promote early attachment and metamorphosis of oyster larvae. Therefore, zinc phosphate, potassium phosphate, ammonium phosphate, zinc sulfate, potassium sulfate, potassium nitrate, iron sulfate, ammonium nitrate, iron phosphate, and calcium phosphate are mixed into concrete as trace elements.

[0155] By modifying these substances, the strength and permeability of the concrete remain essentially unchanged, while significantly improving the rate at which oyster larvae attach. Specifically, the effects are as follows:

[0156] Marine biologists study the effects of different ions on the attachment and metamorphosis of marine sessile organisms in order to clarify the attachment mechanism of oysters and the purpose of aquaculture and propagation. This belongs to the field of marine biology. It is completely different from marine concrete engineering and concrete materials science, and is entirely two major fields. Through the interdisciplinary integration of marine sessile organisms and concrete materials science, it is found that by adding corresponding substances to paints and concrete, it is possible to attract oyster larvae to attach to the concrete surface. Since soluble salts have a significant impact on concrete performance such as initial workability, hardening time, and later strength and penetration resistance, this invention uses diatomaceous earth as a carrier to fix these inorganic salts inside the diatomaceous earth, thereby reducing the impact of soluble salts on paint and concrete performance. At the same time, it utilizes the effect of diatomaceous earth in improving paint and concrete performance, enabling the excellent performance of paints and concrete to be maintained even when these attractants are added. Furthermore, because diatomaceous earth has a sustained release effect as a carrier, the release of soluble salts is relatively slow, and especially after immersion in seawater for a predetermined time or longer, the release rate is kept at a very low level. Therefore, similarly, knowledge in this area, with respect to the interdisciplinary integration of marine sessile organisms, chemistry, and marine concrete engineering, will not be found by those skilled in the art in the field of concrete engineering or marine biology, given the conventional background, to be able to obtain technical features closely related to paints and concrete that are excellent in their ability to attract oyster larvae to attach, by mixing trace elements into paints and concrete, changing the ion content of trace elements on the surface of paints and concrete, and controlling the permeability of concrete in the present invention.

[0157] Penetration of paints and concrete

[0158] The strength and permeability of paints and concrete are the two most important performance characteristics of paints and concrete. Mixing different attractants into paints and concrete affects their performance. Therefore, when mixing different substances to promote the attachment, metamorphosis, and subsequent growth of oyster larvae, it is necessary to first control the overall process so as not to significantly affect the strength and permeability of the paint and concrete. Secondly, raw materials should be selected according to their suitability, and if the performance of the raw materials does not meet the actual requirements, the desired function can be achieved by modifying them before adding the raw materials. However, in fact, the aforementioned related research considers the effect of calcium content on oyster larva attachment, but does not consider the performance of the concrete itself, such as the water-cement ratio, calcium content, and curing. As a result, changes in the permeability of paints and concrete alter the permeability of alkalis and ions within the paint and concrete. The lower the penetration resistance of the paint and concrete, the higher the permeability of alkalis and ions within it, and this can increase exponentially. Therefore, these released alkalis and ions have a significant impact on the larvae, ranging from promoting adhesion to inhibiting it, and this situation can become more severe, especially when the cement dosage is high. Accordingly, when mixing attractants into paints and concrete, it is necessary to ensure that the changes in the penetration resistance of the paints and concrete remain within a controllable range, for example, the change should not exceed 10%. In this way, these attractant effects can be compared; otherwise, it is impossible to evaluate the impact of mixing attractants independently or in combination on the attraction effect on oyster larvae.

[0159] It is necessary to understand the optimal environment required for marine sessile organisms to attach, metamorphose, and grow in their later stages, and to design paints and concrete starting from the impermeability of the paints and concrete, and not to ignore the fact that simply considering the dosage of various raw materials will result in changes in the impermeability of the paints and concrete. Accordingly, knowledge in this area is also relevant to the interdisciplinary integration of marine sessile organisms, chemistry, and marine concrete engineering. Whether one is skilled in the field of concrete engineering or marine biology, given the conventional background, in this invention, the overall control of the impermeability of the paints and concrete cannot be obtained, and the attractant cannot acquire technical features closely related to the ability of the attractant to effectively attract oysters to attach.

[0160] Therefore, similarly, knowledge in this area, with respect to the interdisciplinary integration of marine sessile organisms, marine plants, and marine concrete engineering, cannot be obtained by those skilled in the art in the field of concrete engineering or marine biology, as can be seen from References 2-3, in the present invention, the color change by mixing dark pigments into concrete, the modification of bovine bone powder, the crushing technology, and the control of the permeability of paint and concrete are closely related to the ability to effectively attract oysters and paint and concrete to have high durability. Furthermore, as can be seen from Reference 4, in the present invention, the reduction in the alkalinity of concrete and the balance of calcium ion concentration are closely related to the attachment of marine sessile organisms.

[0161] The present invention will be described in detail below with reference to Examples A1 to A10, and the specific implementation methods of these Examples A1 to A10 are the same as the implementation methods of the cement-based coatings (26 to 35) for attracting sessile organisms to the surface of marine projects described above.

[0162] Compared to Reference 2 (Biomimetic Concrete Artificial Reef and Method for Manufacturing the Same 2015 CN104938384 A), the differences are as follows:

[0163] (1) The purpose of the present invention differs from that of reference document 2, in which a cement mortar mixed with crushed oyster shells is applied to the concrete surface, but its purpose is to attract fish, microorganisms, and algae through biomimetic surface action and to improve the aquatic environment by increasing the number of microorganisms, and oysters are not mentioned. The purpose of the cement-based coating of the present invention is to attract oysters to adhere, which are mainly oysters, but barnacle adhesion is also considered if the reinforced concrete in the tidal zone has a corrosion-resistant effect.

[0164] (2) According to Reference 2, in cement mortar, bio-calcium carbonate powder (150-200 mesh) in amounts less than 10% of the cement is ineffective against adhesion by attraction. However, in the course of research for the present invention, using a cement-based coating (powder density 100-1000 mesh) mixed with modified bovine bone powder and bio-calcium carbonate powder, it was found that the optimal dosage of bovine bone powder and bio-calcium carbonate powder is 10% or less of the cementitious material.

[0165] (3) Modifying bovine bone powder and biocalcium carbonate powder specifically involves treating 100-500 mesh eggshell powder, coral powder, oyster shell powder and fish bone powder with one or two of ethane acid, acetic acid, silicic acid, sulfurous acid, etc., and treating 100-500 mesh bovine bone powder with one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid.

[0166] (4) In the references, embedding oyster shells into the concrete surface is difficult, and not all project surfaces use this method, making it impractical. The present invention can achieve the excellent effect of attracting sessile organisms by applying a cement-based coating layer to the concrete surface, eliminating the need to embed oyster shells, making it easy to apply, and significantly improving the amount of oysters that adhere to it.

[0167] (5) In recent years, severe corrosion of artificial reefs has frequently occurred in marine environments. This severe corrosion is mainly caused by the combined action of biological sulfuric acid secreted by anaerobic microorganisms such as Thiobacillus bacteria and acidic substances secreted by other bacteria. However, calcium carbonate has very poor acid corrosion resistance, so if the content of finely powdered calcium carbonate is too high, it can cause severe acid corrosion.

[0168] Compared to the findings in Reference 3, Fan Ruiliang, "The influence of substrate type on oyster attachment, growth, population establishment and reef development [D]), the differences are as follows:

[0169] (1) In Reference 3, 80-mesh bovine bone powder, calcium powder, and gypsum powder are taken and mixed independently into the concrete. The fineness of all calcium-based materials in this invention exceeds 100 mesh, which is greater than the fineness of the materials in Reference 3. In addition, modified bovine bone powder is mixed in, and the particle grading of the paint and its attracting ability are taken into consideration.

[0170] (2) When bovine bone powder is crushed in a vibrating mill under room temperature conditions, after the fineness exceeds 80 mesh, it clumps together because the bovine bone powder contains a large amount of collagen, making it impossible to continue crushing. In the present invention, when dilute acid modification technology is used and crushed together with other substances, a modified biocalcium powder with a small particle size and a fineness >200 mesh is obtained. The obtained biocalcium powder retains the original biocalcium substance, improves the release rate of substances that attract oyster larvae to attach, and reduces the amount of biocalcium powder administered, thereby reducing the impact on paint performance.

[0171] (3) Bovine bone powder contains a large amount of organic substances such as collagen, and when large amounts of these substances are mixed in, it leads to a decrease in the strength and penetration resistance of the paint. In particular, when the dosage is increased after it exceeds 5%, the strength of the paint rapidly decreases, the penetration resistance becomes significantly lower, and mold grows on the paint under standard curing conditions.

[0172] This invention utilizes dilute acid modification and composite pulverization technology to fully utilize the attracting ability of bovine bone powder, significantly reducing the amount of bovine bone powder used, and performing corrosion prevention treatment and modification to produce a composite attractant primarily composed of bovine bone powder. This method results in a low dosage that has little impact on paint performance, while simultaneously providing high adhesion ability for oyster larvae and solving the problem of mold growth after paint application. The amount of oyster larvae adhering to concrete coated with paint containing the attractant is significantly increased compared to paint without the attractant.

[0173] As can be seen from the references and researched materials, calcium content is essential for oyster larva attachment, and similarly, some current test results also prove that mixing an appropriate amount of calcium carbonate into cement-based materials can promote oyster larva attachment and growth. However, cement-based paints contain a large amount of calcium ions, and the pH value of the pore solution generally exceeds 12.5. At room temperature, the pH value of a saturated calcium hydroxide solution is approximately 12, and therefore the calcium ion concentration in that pore solution is approximately 5 mmol / L. The solubility of calcium carbonate is very low, only 9.5 × 10⁻⁵ mol / L (9.5 × 10⁻² mmol / L) at 25°C. Currently, the optimal range of calcium ion concentration to attract oysters to attach is considered to be 10-25 mmol / L, and even when oyster larvae are placed in a saturated calcium carbonate solution, there is not enough Ca²⁺ concentration to provide a suitable ion concentration for oyster attachment. Furthermore, while Ca(OH)₂ can be rapidly released from the paint, the dissolution of calcium carbonate takes time. Therefore, when calcium carbonate materials are mixed into paint to promote oyster larval attachment, it can be concluded that Ca2+ does not play a dominant role. Early attachment and metamorphosis of oysters are related to HCO3-, and in the case of metamorphosis, a secondary shell of calcium carbonate is formed together with Ca2+. After calcium carbonate is mixed in, it reacts with CO2 and water to produce Ca(HCO3)2, which then participates in attachment, and this is the basic mechanism that promotes oyster larval attachment.

[0174] There is an optimal amount of calcium carbonate for cement-based materials, and this can be explained from the following three aspects.

[0175] 1) With the same amount of alternative cement, increasing the amount of calcium carbonate administered dilutes the alkali in the cement base material, reducing the total alkalinity. However, increasing the amount of calcium carbonate administered improves the solubility of calcium carbonate in the cement base material, increasing the HCO3- content in the solution, thus promoting oyster adhesion and transformation. However, if the dosage is too high, the permeability of the cement base material increases rapidly, causing the alkali and carbonate to leach out rapidly. The adverse effects of alkali become pronounced, and the critical effect or adverse effects of carbonate begin to appear, reducing the amount of adhesion.

[0176] 2) With the same amount of alternative aggregate, as the dosage increases, the permeability of the cement base material decreases, and the leaching of calcium ions and OH- decreases. However, the permeability of carbonate ions gradually improves, and once it reaches a certain value, oyster attachment reaches its maximum. As the dosage continues to increase, calcium ions decrease significantly, and carbonates may also decrease. The calcium ion concentration limits oyster larval attachment, which manifests as a decrease in the amount of attachment.

[0177] 3) With the same amount of alternative mineral admixture, as the dosage increases, the permeability also improves, and the increase in calcium carbonate brings the HCO3- concentration necessary for oyster attachment to an appropriate range, which manifests as an improvement in the amount of oyster larvae attached. As the dosage of mineral admixture continues to increase, the dosage of mineral admixture decreases, and the amount of leached alkali and carbonate increases. However, if there is too much alkali and HCO3- ions, it inhibits the attachment of oyster larvae.

[0178] Compared to Reference 4 (Li Zhenzhen, Gong Pihai, Guan Changtao, et al. Biofouling effects of concrete artificial reefs of various cement types [J]. Advances in Fisheries Science, 2017, 38(5):57-63.), the differences are as follows:

[0179] Reference 4 describes the use of composite Portland cement, slag Portland cement, pozzolanic Portland cement, fly ash Portland cement, and alumina cement. In the present invention, a low-alkali segment is achieved by compounding and mixing ordinary Portland cement with mineral admixtures. Here, silica fume is one of the mineral admixtures, and its high activity and appropriate dosage have a clear effect on improving the durability of reinforced concrete in marine environments. Through optimized design and testing, a low-alkali cement with excellent strength and durability can be obtained. At the same time, due to the high penetration-resistant properties of silica fume concrete, a large number of oyster larvae can attach, metamorphose, and grow even if the alkalinity inside the concrete is high. Furthermore, by compounding with low-alkali sulfoaluminate cement, the alkalinity of the cement-based coating is adjusted, providing an appropriate pH value for oyster larva attachment. Furthermore, marine plants and sessile organisms such as oysters and barnacles have different alkali tolerances, and the environmental requirements differ between the attachment stage and the later stages. For example, attachment, metamorphosis, and later growth of barnacles and oysters require large amounts of calcium ions.

[0180] In Reference 4, concrete is used to attract marine organisms, primarily due to the size and diversity of the sessile organisms, which are various types of algae. In this invention, the research objective is to attract oysters, however, oysters and barnacles have higher alkali resistance than algae, and oyster attachment and metamorphosis require large amounts of calcium ions. Therefore, although the two types of cement-based materials look similar, they are actually quite different.

[0181] Furthermore, the unique features of this invention and their beneficial effects are as follows.

[0182] Dark pigments

[0183] By utilizing the phototaxis of oyster eyespot larvae, one or two dark pigments (iron black, aniline black, carbon black, antimony sulfide, red iron oxide, or organic red pigment) are mixed into the paint to change its color. The darker color of the paint makes the oyster larvae perceive it as a dark environment, attracting them to the dark concrete surface on their own. This increases the probability of contact between the oyster larvae and the concrete surface, thereby increasing the probability of them attaching to the surface. Specifically, the method is as follows:

[0184] Researchers in marine biology have considered studying the attachment of marine sessile organisms using substrates of different colors to cultivate, propagate, or eliminate undesirable populations; this belongs to the field of marine biology. It is entirely distinct from marine concrete engineering and concrete materials science, and is one of two major fields. An interdisciplinary fusion of marine sessile organisms and concrete materials science involves using dark-colored paints to attract oyster larvae to attach. This invention involves adding dark pigments to darken the color of the paint and promote oyster larva attachment. Mixing other materials into the paint affects its performance. This invention takes into account that paints of different cements have different surface colors. Therefore, the amount of dark substance to be added is determined based on the type and amount of cement. The dark pigment also affects the performance of the paint. Most importantly, if the permeability of alkali and Ca2+ in the paint is not controlled at the same time as mixing in the dark pigment, the released alkali will affect the attachment, metamorphosis, and growth of sessile organism larvae, and if the amount exceeds a predetermined value, the amount of larvae attached will decrease. In this invention, the penetration-preventing properties of cement-based coatings are designed and controlled, with the main measures being the selection of the type of dark pigment, control of the dosage, and modification. As the dosage of the dark substance increases, the amount of larvae adhering to the surface increases. When the dosage is 0.5% to 6% of the cementitious material, the amount of larvae adhering is at its highest, but then increases only slightly or remains unchanged.

[0185] trace elements

[0186] Oysters contain a large amount of zinc, far more than in the seawater in which they live, and at the same time, they contain many iron, phosphorus, and potassium elements. Simultaneously, appropriate concentrations of Zn2+ and K+ in the solution can promote early attachment and metamorphosis of oyster larvae. Therefore, by mixing zinc sulfate, potassium sulfate, potassium nitrate, iron sulfate, zinc phosphate, ammonium nitrate, potassium phosphate, ammonium phosphate, iron phosphate, and calcium phosphate as trace elements into the paint, the strength and penetration resistance of the paint remain essentially unchanged, while the rate of attracting oyster larvae to attach is significantly improved. Specifically, this is as follows:

[0187] Marine biologists study the effects of different ions on the attachment and metamorphosis of marine sessile organisms in order to clarify the attachment mechanism of oysters and the objectives of aquaculture and propagation. This belongs to the field of marine biology. It is completely different from marine concrete engineering and concrete materials science, and they are two entirely separate fields. Through the interdisciplinary integration of marine sessile organisms and concrete materials science, it has been found that by adding corresponding substances to the paint, it is possible to attract oyster larvae to attach to the concrete surface. Since soluble salts have a significant impact on the performance of the paint, such as initial workability, curing time, and later strength and penetration resistance, this invention uses diatomaceous earth as a carrier to fix these inorganic salts inside the diatomaceous earth, thereby reducing the impact of soluble salts on the performance of the paint. At the same time, it utilizes the effect of diatomaceous earth in improving the performance of cement-based paints, so that the excellent performance of the cement-based paint can be maintained even when these attractants are added. In addition, because diatomaceous earth has a sustained release effect as a carrier, the release of soluble salts is relatively slow, and especially after immersion in seawater for a predetermined time or longer, the release rate is kept at a very low level. Therefore, similarly, knowledge in this area, with respect to the interdisciplinary integration of marine sessile organisms, chemistry, and marine concrete engineering, can be obtained by those skilled in the art in the field of concrete engineering or marine biology, given the conventional background, by mixing trace elements into concrete, changing the ion content of trace elements on the paint surface, and controlling the permeability of the paint, in the present invention, and obtaining technical features closely related to a paint with excellent ability to attract oyster larvae to attach.

[0188] Concrete permeability

[0189] The strength and penetration of the paint are of paramount importance. Mixing different attractants into cement-based paint affects the paint's performance. Therefore, when mixing different substances to promote oyster larval attachment, metamorphosis, and subsequent growth, it is necessary to first control the overall mixture to avoid significantly impacting the paint's performance. Secondly, raw materials should be selected according to their suitability, and if the performance of the raw materials does not meet the actual requirements, the desired function can be achieved by modifying them before adding the raw materials. However, in fact, the aforementioned related research considers the effect of calcium content on oyster larval attachment, but does not consider the performance of the paint itself, the water-cement ratio, calcium content, and curing. Changes in the paint's penetration change the penetration rate of alkalis and ions within it. The lower the paint's penetration resistance, the higher the penetration rate of alkalis and ions within it, potentially increasing exponentially. Consequently, these released alkalis and ions have a significant impact on the larvae, ranging from promoting attachment to inhibiting it, and this situation can become more serious, especially when the cement dosage is high. Therefore, when mixing attractants into the paint, it is necessary to ensure that the change in the paint's performance remains within a controllable range, for example, not exceeding 10%. In this way, these attractant effects can be compared; otherwise, it would be impossible to evaluate the effect of mixing in attractants independently or in combination on attracting oyster larvae.

[0190] It is necessary to understand the optimal environment required for attachment, metamorphosis, and late-stage growth of marine sessile organisms, and to design paints starting from the paint's penetration resistance, and not to ignore the fact that simply considering the dosage of various raw materials will result in changes in the paint's penetration resistance. Therefore, similarly, knowledge in this area is relevant to the interdisciplinary integration of marine sessile organisms, chemistry, and marine concrete engineering. Whether one is skilled in the field of concrete engineering or marine biology, given the conventional background, in this invention, the overall control of the paint's penetration resistance cannot be obtained, and the attractant cannot acquire technical features closely related to the ability of the attractant to effectively attract oysters to attach.

[0191] Therefore, similarly, knowledge in this area, with respect to the interdisciplinary integration of marine sessile organisms, marine plants, and marine concrete engineering, cannot be obtained by those skilled in the art in the field of concrete engineering or marine biology, as can be seen from References 2-3, in the present invention, the color change by mixing dark pigments into the paint, the modification of bovine bone powder, the grinding technology, and the control of paint permeability cannot be obtained to obtain technical features closely related to the paint having the ability to effectively attract oysters and having high durability. Furthermore, as can be seen from Reference 4, in the present invention, the reduction in the alkalinity of the paint and the balance of calcium ion concentration cannot be obtained to obtain technical features closely related to the attachment of marine sessile organisms.

[0192] The present invention will be described with reference to examples, but those skilled in the art will understand that various changes, modifications, substitutions and variations can be made to these examples without departing from the principles and spirit of the invention, and that the scope of the invention is limited by the claims and their equivalents.

Claims

1. A cement-based coating for attracting sessile organisms to the surface of a stone breakwater, It is composed of cementitious material, sand, water, dark pigments, bio-derived biocalcium powder, non-biological calcium carbonate powder, trace elements, wood fiber, dispersible rubber powder, and superplasticizer. The weight ratios of the cementitious material, sand, water, dark pigment, bio-derived biocalcium powder, non-biological calcium carbonate powder, trace elements, wood fiber, dispersible rubber powder, and superplasticizer are, in order, 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). The aforementioned bio-derived biocalcium powder is one or more combinations of bovine bone powder, oyster shell powder, fish bone powder, eggshell powder, and coral powder. The non-biological calcium carbonate powder is one or more of the following: calcite, chalk, limestone, marble, aragonite, and travertine powder. A cement-based paint characterized by the following features.

2. The cement-based paint according to claim 1, characterized in that the dark pigment is one or two of the following: iron black, aniline black, carbon black, antimony sulfide, red iron oxide, and organic pigment red.

3. The cement-based paint according to claim 2, characterized in that the dark pigment is modified, and one of a transparent resin, organosilicon, dimethylsiloxane, and a superhydrophobic material is used for the modification treatment.

4. The cement-based coating according to claim 1, characterized in that the fineness of the non-biologically derived calcium carbonate powder exceeds 200 mesh.

5. The cement-based paint according to claim 1, characterized in that the sand is one or more of river sand, machine-made sand, and sea sand having a particle size of 0.16 mm to 2.36 mm.

6. The cement-based paint according to claim 1, characterized in that the superplasticizer is one of a carboxylic acid and a naphthalene-based agent.

7. A method for manufacturing a cement-based paint according to claim 1, Step S1 involves weighing cementitious material, sand, water, dark pigment, bio-derived biocalcium powder, non-biological calcium carbonate powder, trace elements, wood fiber, dispersible rubber powder, and superplasticizer. Step S2 involves placing cementitious material, dark pigment, bio-derived biocalcium powder, non-biological calcium carbonate powder, and trace elements into a material mixer and mixing them uniformly for 2 to 5 minutes at a rotation speed of 1000 to 1500 revolutions per minute. Next, in step S3, sand, wood fiber, and dispersible rubber powder are placed in a mixer and mixed for 5 to 10 minutes at a rotation speed of 500 to 1000 revolutions per minute. A manufacturing method comprising step S4, which involves thoroughly dissolving a powdered superplasticizer in water, then placing it together with the mixed material in a high-speed mixer and stirring for 5 to 10 minutes at a rotation speed of 200 to 500 revolutions per minute, thereby enabling the production of a cement coating with excellent attractive effect for attracting organisms to the surface of marine projects.

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