CN111253124A

CN111253124A - Construction method of ecological high-durability concrete structure in marine environment

Info

Publication number: CN111253124A
Application number: CN201911210464.4A
Authority: CN
Inventors: 吕建福; 胡新宇
Original assignee: Harbin Engineering University
Current assignee: Harbin Engineering University
Priority date: 2019-12-02
Filing date: 2019-12-02
Publication date: 2020-06-09

Abstract

The invention relates to marine concrete ecological engineering, in particular to a method for building an ecological high-durability concrete structure in a marine environment, and belongs to the field of marine ecological engineering. The construction method comprises the following steps: (1) surveying the sea area of the building position of the concrete structure; (2) culturing oyster eyespot larvae; (3) building a concrete structure; (4) attaching on site; (5) larva attachment and management was monitored. The invention adopts the novel anti-corrosion technology of marine periphyton, can greatly improve the durability of reinforced concrete, simultaneously improve the ecological environment of the sea area, change the current situation that the ecological environment is damaged by building concrete projects, and can restore the damaged ecological environment.

Description

Construction method of ecological high-durability concrete structure in marine environment

Technical Field

The invention relates to marine concrete ecological engineering, in particular to a construction method of an ecological high-durability concrete knot in a marine environment, and belongs to the field of marine ecological engineering.

Background

The sea is not only a treasure house of human resources, but also a natural corrosive environment. In marine concrete structures, corrosion of steel reinforcement by chloride ion attack greatly reduces the durability of the concrete. In order to improve the durability of concrete and thus the service life of marine concrete structures, researchers and technicians have proposed corrosion protection measures such as high-performance concrete, surface coatings, FRP ribs, reinforcing steel bar rust inhibitors, and electrochemical protection technologies. However, these corrosion prevention techniques have one or more of the disadvantages of difficult construction, poor aging durability, long-term unpredictability, high cost, and the like. In addition, the current anti-corrosion technology easily causes certain influence on the ecological environment of the ocean. Like an electrochemical corrosion method, the current field of the sea area around the structure is changed, the formation of biological community diversity is excluded, and adverse effects are generated on the propagation and development of marine organisms; the coating adopted by the surface coating method is also easy to cause pollution to the marine environment and destroy the original ecological environment.

The surfaces of concrete projects in tidal range are often covered with a large number of sessile organisms, such as oysters, barnacles, etc. Researches show that the biogel secreted by oysters and barnacles can block capillary pores on the surface layer of concrete, block the entrance and exit of ions and gas, improve the impermeability of the concrete and further improve the durability of the concrete, and the more compact the attachment of sessile organisms is, the more obvious the protection effect is. The marine periphyton corrosion prevention is utilized, so that the marine periphyton corrosion prevention not only has the characteristics of initiative, economy and environmental protection, but also makes up the limitation of the existing reinforced concrete corrosion prevention technology in tidal range areas and underwater areas. The method is a cross of the subjects of marine concrete and marine sessile biology, and opens up a new research field of reinforced concrete structure corrosion prevention.

Meanwhile, as coastal economy develops rapidly in recent decades without paying attention to environmental protection, coastal ecology is broken down on a large scale, and the coastal ecology and economy in China are greatly influenced. At present, a series of relevant policies of China emerge, the ocean engineering construction of China also faces a peak period, and simultaneously, the ocean engineering constructed in a large scale and the breakwater which ensures the stability of the surrounding sea area further destroy the originally fragile ecosystem of the ocean. Without proper ecological environment protection, the method brings about greater disasters to the ecology on the coastal areas of the ocean. Meanwhile, most coastal infrastructures cannot be dismantled, and the ecology in the sea area needs to be restored, so that people gradually realize the application of ecological technologies on a large number of infrastructures, and the ecology in the sea area can be effectively improved or restored. Therefore, it is very important and urgent to construct a concrete project having a good ecological effect, or to ecologically improve the offshore ecological environment for the existing concrete project, etc.

Therefore, the oysters are attached to the surface of the concrete densely in a large amount, and the method has great significance for ocean engineering construction and ocean ecological environment. The method is characterized in that: not only can improve the durability of concrete, but also can purify water and restore marine environment by oyster which is an ecological engineer, thereby realizing ecological restoration, promoting harmonious development of human and nature, and achieving the win-win situation!

However, in some sea areas, sessile organisms are affected by the external environment, and the phenomena of sparse attachment, loose attachment and even no attachment often occur. The construction of the ecological high-durability concrete structure in the marine environment is greatly disturbed, and how to make oysters quickly and compactly adhere to concrete, deform and quickly grow is the most critical part for the construction of the ecological high-durability concrete structure. At present, the relevant research on marine periphyton at home and abroad is as follows:

first, the influence of ions on the attachment and metamorphosis of marine periphyton larva

The research on the marine periphyton larva attachment and metamorphosis induction at home and abroad mainly focuses on the influence of the ion concentration in the solution, and the deeply researched ions and substances have K⁺、NH₃、Ca²⁺And Cu²⁺The first three ions or substances can promote the adhesion or metamorphosis of oyster at proper concentration, but Cu²⁺The promoting effect is not obvious, and even the death rate of larvae is increased at a large concentration. K⁺Inducing larval metamorphosis by affecting the behavior of cell membranes; NH (NH)₃It is intracellular, leading to an increase in intracellular pH, which subsequently causes depolarization of neurons that are behavioral pathways, thereby inducing sessile metamorphosis. Although carried out in solutionThe study on the adhesion and metamorphosis of more sessile organisms on the surfaces of different substances such as polyethylene plates, shells, tiles and the like is carried out, but when the method is applied to the actual marine concrete engineering, the method is not easy to realize or has high cost.

At present, with the great application of concrete in ocean engineering, particularly recent oyster reef repair engineering and the like, the concrete becomes a substrate material which is most commonly attached by marine periphyton. However, the concrete material is different from the traditional shells, limestone, rubber tires, plastic plates and the like. The concrete has high alkalinity and high calcium ion, also contains rich other ions, such as potassium and sodium ions, and has great influence on the attachment and growth of the oysters. At present, although some oyster reef repair projects and the like adopt newly manufactured concrete members, waste concrete and the like as repair substrates, the effect is not ideal.

Second, the influence of concrete of different types of cement on marine plants and sessile organisms

At present, portland cement concrete is almost adopted in ocean concrete engineering and has high alkalinity (the pH value of a pore solution is generally 12.0-13.0), and the pH value of seawater is generally 7.9-8.4. Due to the existence of alkali concentration gradient, the concrete contacted with the seawater can continuously release alkali, thereby improving the pH value of the seawater in the sea area and damaging the local ecological system. Has a great inhibiting effect on the attachment growth of sessile organisms on the surface of the biological filter, and particularly has great influence on alkalinity sensitive organisms. The current domestic and foreign research shows that: the artificial fish reef made of different cement types has obvious difference on biological attachment effect, aluminate cement and fly ash portland cement have good biological attachment effect, and the alkalinity of the artificial fish reef is lower than that of common portland cement concrete. Similarly, the cement concrete has better ecological effect by adding 40-60% of fly ash and slag powder. In addition, the types and the quantity of the attachment organisms of the travertine cementing material concrete are more than those of the cement concrete, and the higher the content of the travertine cementing material is, the better the ecological effect is. The ecological concrete engineering for building in the United states adopts cement concrete with low alkalinity, such as aluminate cement, particularly slag portland cement, wherein the replacement amount of slag reaches 50 percent, and the ecological effect of enriching marine plants, animals and the like is better. By adopting cement with lower alkalinity to prepare concrete, biomass (mainly marine plants) sensitive to alkali can be effectively improved, but the improvement of the attachment amount and the attachment density of oysters is limited.

Third, the influence of calcium substances on the adhesion of marine sessile organisms

Domestic and foreign researches show that the chemical element composition of the attaching substrate obviously influences the attachment, metamorphosis and later growth of oyster larvae. The most commonly used calcium-containing substrates (limestone and concrete) are effective in inducing adhesion of oyster larvae with an inducing effect comparable to that of shellfish shells. This indicates that calcium is a vital role in the attachment, metamorphosis and growth of oyster larvae.

Recently, in addition to conventional substrates, studies have been made on the adhesion of oyster larvae by adding calcium to cement-based materials and increasing the content of calcium in concrete. In the literature, 80-mesh cattle bone powder, calcium carbonate powder and gypsum powder (the mixing amount is 62.5 percent and 375 percent of the weight of cement) are singly mixed into mortar to carry out an oyster attachment experiment, and the sequence of the inducing capacity of the calcium excipient for the adhesion of oyster larvae under the same condition is obtained: the bovine bone meal is calcium carbonate which is calcium sulfate; the calcium carbonate powder is doped in an amount of 5-60% of the mortar (41.7-500.0% of the cement), and the effect is best when the calcium carbonate powder is doped in an amount of 20% (166.7% of the cement). Although the attachment amount of the oysters can be increased by adding the bovine bone meal, the calcium carbonate powder and the gypsum powder, the added proportion is too large (the weight of the calcium powder is more than 41.7 percent of that of the cement and even reaches 500.0 percent), the mechanical property and the durability of the concrete are seriously influenced, and the oyster powder is not suitable for being used in concrete engineering under marine environment. In addition, although the bovine bone meal has a good effect of inducing adhesion of oysters, when the amount of the bovine bone meal exceeds 10% of the cement, the concrete is mildewed. Therefore, at present, although calcium substances such as bovine bone meal, calcium carbonate and the like are doped into concrete, the influence of marine environment on the durability of a concrete structure is not considered, so that the concrete cannot be applied to severe marine environment at all.

In CN104529286 patent: from the aspect of waste utilization, oyster shell fragments of 5 mm-8 mm with the mass of 10% -20% of cement are mixed into the artificial fish reef, and the concrete which does not influence biological attachment and does not pollute the environment is obtained. CN104938384 is that 150-200 mesh biological calcium carbonate powder (fishbone, coral, egg shell and shell are 1:1:1:1) and shell fragment, which account for 10-20% of the mass of cement, are simultaneously mixed into the artificial fish reef, which shows that the induced biomass is gradually increased along with the increase of the mixing amount of calcium carbonate, and the biomass (marine plants and marine organisms) induced by the biological calcium carbonate is the most when the mixing amount is the maximum (20% of the weight of the cement). In addition, the alkalinity of the surface of the concrete artificial fish reef is reduced, so that microorganisms and algae are easier to attach, the biomass and the population quantity are increased, and the fish collecting effect is better. The biological calcium carbonate cement mortar coating layer educt is harmless to the environment and the organism. Although the biological calcium carbonate powder, the oyster shell fragments and the like are doped into concrete for artificial fish reef manufacturing and biological attachment experiments, the biological calcium carbonate powder indeed enhances the biological enrichment effect, but mainly enriches marine plants and microorganisms.

In a word, the calcium content is important for the attachment of oyster larvae, and the current experimental results also prove that the addition of a proper amount of calcium carbonate substances in the cement-based material can promote the attachment and growth of the oyster larvae. However, cement concrete contains a large amount of calcium ions, the pH value of a pore solution is generally greater than 12.5, and the pH value of a saturated calcium hydroxide solution is about 12 at normal temperature, so that the concentration of the calcium ions in the mixed concrete pore solution is about 5 mmol/L; the solubility of calcium carbonate is very low, and is only 9.5X 10 at 25 DEG C^-5mol/L (9.5×10^-2mmol/L). At present, the optimal range of calcium ion concentration for inducing shellfish adhesion is considered to be 10-25 mmol/L, and even if oyster larvae are placed in saturated calcium carbonate solution, enough Ca is not available²⁺The concentration of Ca is suitable for providing proper Ca for the adhesion of oysters²⁺And (4) concentration. Further, Ca (OH) in the inside of the cement concrete₂Can be released more quickly, and the dissolution of calcium carbonate needs longer time. Therefore, it was confirmed that incorporation of calcium carbonate material into concrete promotes adhesion of oyster larvae, Ca²⁺Is not startedLeading the effect.

In addition, the doping amount of the shell powder is too large, the weight ratio of the shell powder to the cement is more than 10%, and some shell powder even reaches 500%, so that the durability of the concrete is greatly influenced. Although the proper amount of calcium carbonate material can prevent the concrete from being reduced in impermeability or better, the excessive amount of calcium carbonate material is very unfavorable for the concrete to resist the corrosion of sulfuric acid and sulfate in seawater.

Therefore, the problem of marine sessile organism larva induced adhesion by doping calcium substances such as biological calcium carbonate, bovine bone meal, calcium carbonate powder and the like into concrete still exists, and particularly the problems of concrete performance caused by excessive doping of the calcium substances, mildew caused by doping of the bovine bone meal and the like exist.

Fourth, the influence of color on the adhesion of marine periphyton

The color of the substrate has certain influence on the attachment, metamorphosis and growth of the larvae of the marine periphyton. Overseas has reported that in a sea area with a low temperature, a dark substrate can promote the growth of oysters. Domestic research shows that oyster larvae have certain selectivity on color. The color selectivity of the crassostrea hongkongensis larvae on the plastic anchoring base is as follows: black > white > red. Crassostrea gigas larvae prefer to attach to black and gray plastic plates and it is believed that black and gray may be a protective color for oyster larvae to avoid natural enemy attacks. Barnacles prefer to adhere to red substrates. Pearl oyster also prefers dark (black, red), non-reflective substrates, showing non-photosensitive behavior. And the bacterium alteromonas melellii attracts oyster larvae by producing a compound involved in melanin synthesis.

At present, the research on the influence of the color of the substrate on the adhesion of marine periphyton larvae is limited to organic polymer plates such as plastic plates and polyethylene plates, asbestos plates and the like. The concrete is used as a most potential substitute substrate, is particularly used for oyster reef repair, artificial ecological engineering construction and marine reinforced concrete corrosion prevention at present, and the influence of the color of the concrete on the attachment amount of sessile organism larvae is not referred to related data.

Fifth, the influence of roughness on the adhesion of marine periphyton larvae

Generally, the roughness of the surface of the substrate has a certain influence on the adhesion of oysters and barnacle larvae. Domestic and foreign researches show that under the same other conditions, oysters and barnacle larvae attached to the rough surface are more than those attached to the smooth surface. The rough surface provides better tactile stimulation for the crawling and attachment of oyster and barnacle larvae so as to help the larvae to stay on the substrate; the presence of cracks and pits can protect the larvae from predators; and a microbial environment that is larger in area, and potentially more abundant and diverse, than a smooth surface. Recent studies have shown that textured concrete surfaces adhere more marine organisms than smooth surfaces, promoting the attachment and metamorphosis of larvae. However, some studies have shown that coarseness has no significant effect on attachment metamorphosis of larvae.

In summary, while the above studies have been conducted, such as different substrates, and the effects of color and roughness on marine periphyton attachment, the effect of incorporating calcareous materials into concrete on marine periphyton attachment has recently been studied. However, due to the knowledge of related subjects such as marine organisms, marine microorganisms, marine chemistry, marine concrete engineering materials and structures, and the like, the subject directions are different greatly, so that many problems are encountered in the cross research, such as the above-mentioned problems that the cement-based material has an unclear water-cement ratio, the mechanism of oyster adhesion induced by calcium carbonate materials is unclear, calcium powder doped in cement is excessive, the durability of concrete is seriously insufficient, and the doped bovine bone meal is easy to mildew, and in addition, professional technicians of the marine concrete engineering materials and structures lack the professional knowledge required for marine sessile organisms to adhere, so that the cooperation of multiple professional technicians is required to solve the problems of quick and compact adhesion of marine sessile organisms on the surface of concrete and the durability of concrete after the inducer is doped, so that a novel biological anticorrosion method for a reinforced concrete structure can be formed, and constructing a high-durability ecological reinforced concrete project.

Disclosure of Invention

The invention aims to provide a method for building an ecological high-durability concrete structure in a marine environment, which aims to solve the problems that the service life of the reinforced concrete structure in the marine environment is short and the reinforced concrete structure is unfavorable for ecology.

The purpose of the invention is realized as follows: the construction method comprises the following steps:

(1) survey of sea area of concrete structure construction position

(2) Culture of oyster eyespot larvae

(3) Construction of concrete structures

(4) In situ attachment

(5) Monitoring larva attachment and management:

the invention also includes such structural features:

the concrete material comprises the following components: the weight ratio of the cementing material, the broken stone, the sand, the water, the dark pigment, the biological calcium powder, the calcium carbonate powder, the trace elements, the chopped fiber and the superplasticizer is as follows in sequence: 12.5% -22.0%, 39.4% -49.8%, 24.9% -37.3%, 6.2% -8.7%, 0.2% -1.7%, 0.15% -1.0%, 0.1% -1.0% and 0.02% -0.1%.

The specific technical scheme comprises the following steps:

(1) surveying the sea area of the building position of the concrete structure: investigating the species of the oyster in the sea area and whether the oyster is attached, and performing temperature, seawater temperature, dissolved oxygen, plankton, total dissolved inorganic nitrogen, active phosphate, active silicate, and Ca in different seasons on the sea area²⁺、Zn²⁺、K⁺The like, and the times, the intensity and the like of typhoon in the past year;

(2) culturing oyster eyespot larvae: collecting mature oyster parent in local sea area, obtaining sperm and ovum by dissection, artificial insemination, and indoor culturing to eye point larva stage. The seawater is filtered by sand in the cultivation process, the density is 2-10/mL, the water is changed once every two days, the chrysophyceae or diatom concentrated bait is fed, and the feeding amount is gradually increased from 2 ten thousand cells/mL to 9 ten thousand cells/mL according to the larval development condition.

(3) Construction of concrete structure: pouring the fiber-reinforced ecological concrete with high induction of marine periphyton attachment, metamorphosis and growth promotion into a prepared template by adopting a cast-in-place method, and maintaining for more than 14 d;

(4) field attachment: in the oyster planktonic larvae concentrated attachment metamorphosis period, a fixing frame is additionally arranged on the structure, the lower part of a low tide line is sealed and enclosed, the upper part of the low tide line is tightly connected with the lower sealed and enclosed baffle by using a 80-200-mesh screen, then the oyster eyepoint larvae in the step (2) are filtered, collected and then are transported to a construction site in a low-temperature dry exposure mode, and are placed in the enclosed baffle, and the seedling placing amount is 1-5/10 mL.

(5) Monitoring larva attachment and management: monitoring the adhesion condition of the oyster larvae on the surface of the concrete, and taking corresponding measures according to the actual condition.

The raw materials in the fiber reinforced ecological concrete in the third step are as follows:

preferably, the dark color pigment is: one or two of iron oxide black, aniline black, carbon black, antimony sulfide, iron oxide red and organic pigment red. According to the influence degree on the performance of concrete, the pigments are modified by adopting one of transparent resin, organic silicon, dimethyl siloxane and super-hydrophobic materials.

Preferably, the biological calcium powder is: the bovine bone powder and the biological calcium carbonate powder comprise one or more of oyster shell powder, fishbone powder, egg shell powder and coral powder, and the fineness of the biological calcium carbonate powder is 100-1000 meshes.

Preferably, the biological calcium powder modification method comprises the following steps: treating 100-500 mesh egg shell powder, coral powder, Concha Ostreae powder, and fishbone powder with one or two of acetic acid, silicic acid, and sulfurous acid; and treating 100-500 mesh bovine bone powder with one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid.

Preferably, the calcium carbonate powder is: calcite, chalk, limestone, marble, aragonite, travertine powder, and one or more of light calcium carbonate, activated calcium carbonate, calcium carbonate whisker and superfine light calcium carbonate after processing treatment, and the fineness is more than 200 meshes.

Preferably, the trace elements are: zinc, iron, potassium and phosphorus, which can be selected from natural minerals, industrial products or chemical reagents, including one or more of zinc sulfate, calcium phosphate, zinc phosphate, potassium sulfate, potassium nitrate, ferric sulfate, ammonium nitrate, potassium phosphate, ammonium phosphate and iron phosphate, and are modified to realize the slow release of corresponding ions and reduce or eliminate the adverse effect on the performance of the concrete. However, nitrogen and phosphorus are not selected for the eutrophic area.

Preferably, the chopped fibers are: inorganic fiber (length 12-40 mm), such as one or more of basalt fiber, glass fiber and carbon fiber.

Preferably, the cementing material is: one of silicate cement, sulphoaluminate cement and alkali-activated cementing material which are mixed with mineral admixture. Wherein the mineral admixture in the silicate cement doped with the mineral admixture comprises one or more of silica fume, slag powder and fly ash; the sulphoaluminate cement comprises one or two of quick-hardening sulphoaluminate cement, high-strength sulphoaluminate cement and expansion sulphoaluminate cement; the alkali-activated cementing material is one of alkali-activated slag, alkali-activated slag and fly ash.

Preferably, the sand is: one or more of river sand, machine-made sand (basalt or granite is used as parent rock) or desalted sea sand.

A preparation method of fiber reinforced ecological concrete comprises the following steps:

s1: accurately weighing a cementing material, broken stones, sand, water, a dark pigment, biological calcium powder, calcium carbonate powder, trace elements, chopped fibers and a superplasticizer;

s2: firstly, placing broken stone and sand into a concrete mixer to be mixed for 0.5-1 minute; then adding the cementing material, the dark pigment, the biological calcium powder, the calcium carbonate powder and the trace elements, and continuing stirring for 0.5-1 minute; then adding chopped fibers, water and a superplasticizer and stirring for 3-8 minutes; and after uniformly stirring, pouring and vibrating, and then performing standard maintenance for 28d or performing maintenance according to actual conditions to obtain the fiber reinforced ecological concrete.

Preferably, the oyster field attachment time mount of installing additional adopt fossil fragments-skeleton form, it is two kinds of structures from top to bottom, the lower part adopts high-strength, light sealed enclosure, and the upper portion adopts double-deck screen cloth, wherein outside screen cloth mesh aperture is 80 ~ 300 meshes, specific style is shown in figure 1.

The invention has the beneficial effects that:

the invention adopts the novel anti-corrosion technology of marine periphyton, can greatly improve the durability of reinforced concrete, simultaneously improve the ecological environment of the sea area, change the current situation that the construction of concrete projects destroys the ecological environment, and can restore the destroyed ecological environment.

Drawings

FIG. 1 is a form of an oyster larva field attachment enclosure;

FIG. 2 shows the surface mildew (under standard curing) of concrete mixed with 10% bovine bone meal at different mixing ratios;

FIG. 3 shows different mixing ratios of modified 10% bovine bone meal with a blending fineness of more than 200 meshes;

FIG. 4 shows the adhesion of larvae of oyster in laboratory on the basis of the mix proportion of concrete;

FIG. 5 shows the adhesion of oyster larvae in laboratory with composite inducer mainly containing Os bovis Seu Bubali powder;

FIG. 6 is a schematic diagram of a sea adhesion experiment 210 d;

fig. 7 is a schematic diagram of a sea adhesion experiment 300 d.

Detailed Description

The present invention will be described in detail with reference to the following examples, which are provided only for illustrating the present invention and do not limit the scope of the present invention.

The specific technical scheme of the engineering scheme comprises the following steps:

example 1:

(1) surveying the sea area of the building position of the concrete structure: investigating the species of the oyster in the sea area and whether the oyster is attachedAnd testing for 15 times per season and recording the air temperature, seawater temperature, dissolved oxygen, plankton, total dissolved inorganic nitrogen, active phosphate, active silicate and Ca in the sea area²⁺、Zn²⁺、K⁺Ions, and meanwhile, the typhoon frequency and strength of the whole year are investigated; looking up the sea area meteorological and hydrological data for many years; analyzing feasible methods and solving measures for the construction of the marine concrete engineering structure;

(2) culturing oyster eyespot larvae: collecting mature oyster parent shells in local sea areas, obtaining sperms and ova through a dissection method, performing artificial insemination, and culturing in a room until more than 60% of larvae reach the eyespot larva stage. The seawater is filtered by sand during the cultivation process, the density is 5/mL, the water is changed once every two days, the golden algae concentrated bait is fed, and the feeding amount is increased from 2 ten thousand cells/mL, 3 ten thousand cells/mL and 5 ten thousand cells/mL to 9 ten thousand cells/mL according to the development condition of the larvae.

(3) Construction of concrete structure: binding reinforcing steel bars at the built position 3 days before concrete pouring, supporting a concrete template, and checking before pouring; and preparing fiber reinforced ecological concrete for highly inducing attachment and metamorphosis of marine periphyton and promoting growth, casting the concrete on site in the weather with less stormy waves, and maintaining for 14d with a template.

(4) Field attachment: the mould removing time is ensured to be within the settlement and metamorphosis period of floating larvae of oysters, wherein the selection is 7 months in the north and 6 months in the south. After the form is removed, a fixed frame and a surrounding baffle are immediately installed on the surface of the concrete structure, the lower part of the concrete structure is connected by adopting a sealed surrounding baffle, a 150-mesh screen fence is adopted above a medium tide line and is tightly connected with the sealed surrounding baffle below the medium tide line. And (4) putting the oyster eyespot larvae which are filtered and collected in the step (II) and then are transported to a construction site into a fence at 5-7 pm, wherein the seedling putting amount is 2 per 10 mL.

(5) Monitoring larva attachment and management: monitoring the attachment density of oyster larvae on the surface of concrete to reach 40/100 cm²Stopping adhesion of oyster larvae, cleaning and collecting the rest larvae; and meanwhile, the type and the number of plankton in the sea area are monitored, and whether bait is continuously thrown or not and the enclosure is dismantled or not is determined.

Example 2:

(1) surveying the sea area of the building position of the concrete structure: researching the oyster dominant species of the sea area and whether oysters are attached, researching the typhoon frequency and strength of the past year, and looking up the meteorological and hydrological data of the sea area of the construction area for many years; simultaneously, the temperature of the sea water, dissolved oxygen, plankton, total dissolved inorganic nitrogen, active phosphate, active silicate and Ca in each season²⁺、Zn²⁺、K⁺Testing and recording ions, and analyzing feasible methods and solutions for the construction of the marine concrete engineering structure;

(2) culturing oyster eyespot larvae: collecting mature oyster parent shellfish in local sea area, obtaining sperm and ovum by dissection method, performing artificial insemination, and indoor culturing until more than 70% of larvae reach eyespot larva stage. The seawater is filtered by sand during the cultivation process, the density is 7/mL, the water is changed once every three days, the chrysophyte concentrated bait is fed, and the feeding amount is increased from 2.5 ten thousand cells/mL, 4 ten thousand cells/mL and 6 ten thousand cells/mL to 8 ten thousand cells/mL according to the development condition of the larvae.

(3) Construction of concrete structure: binding reinforcing steel bars at the built position 5 days before concrete pouring, supporting a concrete template, and checking before building; and preparing fiber reinforced ecological concrete for highly inducing attachment and metamorphosis of marine periphyton and promoting growth, casting the concrete on site in the weather with less stormy waves, and maintaining for 14d with a template.

(4) Field attachment: the mould removing time is ensured to be within the settlement and metamorphosis period of floating larvae of oysters, wherein 6 months are selected in the north and 5 months are selected in the south. After the form is removed, a fixed frame and a surrounding barrier are immediately installed on the surface of the concrete structure, a 180-mesh fence is adopted above a medium tide line, and the lower part of the fence is connected with the surrounding barrier in a sealing way and is tightly connected with a screen on the upper part of the fence. And (4) putting the oyster eyespot larvae which are filtered and collected in the step (II) and then are transported to a construction site into a fence at 5-7 pm, wherein the seedling amount is 3/10 mL.

(5) Monitoring larva attachment and management: monitoring the attachment density of oyster larvae on the surface of concrete to reach 45/100 cm²Stopping the oysterAttaching larvae, cleaning and collecting the rest larvae; and meanwhile, the type and the number of plankton in the sea area are monitored, and whether bait is continuously thrown or not and the enclosure is dismantled or not is determined.

Concrete used for casting in examples 1 and 2 was as follows:

1: the common portland cement concrete comprises the following components in parts by weight: 17.1%, 46.67%, 29.0%, 7.2%, 0.03%.

Wherein the mother rock of the macadam is one of basalt and diabase, the maximum grain diameter is not more than 50mm, and the grading is good; the sand is one or more of river sand, machine-made sand (mother rock is one of granite and basalt) or desalted sea sand, and the grading is good. The water meets the concrete water standard (JGJ63-2006), the Cl-content is less than 1000mg/L, the PH value is more than 4.5, and the influence on the initial setting time difference, the final setting time, the strength and the permeability of the cement is small. And the materials selected in the embodiments 1-22 are the same.

2: the reference concrete has the following weight proportions of ordinary portland cement, silica fume, blast furnace slag powder, broken stone, sand, water and polycarboxylic acid water reducer powder: 10.26%, 0.86%, 5.98%, 46.67%, 29.0%, 7.2%, 0.03%.

The above examples show that the blast furnace slag powder and the silica fume are doped into the concrete, so that the gaps among cement particles and the like can be filled, and the volcanic ash reaction can also occur, so that the interface microstructure of the transition zone is improved, the basic strength of the concrete is ensured, and the alkalinity and the permeability of the concrete are reduced. The low permeability can control the release rate of alkali while achieving the effect of reducing the alkalinity difference between the concrete and the seawater contacted with the concrete, and finally, the oyster larvae are easier to attach to the surface of the concrete.

3: the weight proportions of the unmodified dark pigment, the ordinary Portland cement, the silica fume, the blast furnace slag powder, the broken stone, the sand, the water and the polycarboxylic acid water reducer powder are as follows in sequence: 0.51%, 10.26%, 0.79%, 5.54%, 46.67%, 29.0%, 7.2%, 0.03%.

4: the weight proportions of the unmodified dark pigment, the ordinary Portland cement, the silica fume, the blast furnace slag powder, the broken stone, the sand, the water and the polycarboxylic acid water reducer powder are as follows in sequence: 0.86%, 10.26%, 0.75%, 5.23%, 46.67%, 29.0%, 7.2%, 0.03%.

5: the weight proportions of the unmodified dark pigment, the ordinary Portland cement, the silica fume, the blast furnace slag powder, the broken stone, the sand, the water and the polycarboxylic acid water reducer powder are as follows in sequence: 1.37%, 10.26%, 0.68%, 4.79%, 46.67%, 29.0%, 7.2%, 0.03%.

6: the modified dark pigment (the mass ratio of iron oxide black to aniline black mixture is 1:1), ordinary portland cement, silica fume, blast furnace slag powder, broken stone, sand, water and polycarboxylic acid water reducing agent powder are sequentially prepared from the following components in parts by weight: 0.51%, 10.26%, 0.79%, 5.54%, 46.67%, 29.0%, 7.2%, 0.03%.

7: the modified dark pigment (the mass ratio of iron oxide black to aniline black mixture is 1:1), ordinary portland cement, silica fume, blast furnace slag powder, broken stone, sand, water and polycarboxylic acid water reducing agent powder are sequentially prepared from the following components in parts by weight: 0.86%, 10.26%, 0.75%, 5.23%, 46.67%, 29.0%, 7.2%, 0.03%.

8: the modified dark pigment (the mass ratio of iron oxide black to aniline black mixture is 1:1), ordinary portland cement, silica fume, blast furnace slag powder, broken stone, sand, water and polycarboxylic acid water reducing agent powder are sequentially prepared from the following components in parts by weight: 1.37%, 10.26%, 0.68%, 4.79%, 46.67%, 29.0%, 7.2%, 0.03%.

The modified dark color pigment is prepared by mixing 196 transparent resin, 3% of curing agent and 1.5% of accelerator with the pigment, wherein the volume ratio of the pigment to the resin is as follows: 1: 0.2; curing at normal temperature for 4h, curing at 60 deg.C for 4h, then breaking, and grinding with vibration mill to obtain the final product with fineness greater than 400 mesh.

The black pigment has a great influence on the permeability of concrete, and the adhesion of oyster larvae decreases as the amount of the admixture increases. On the one hand, the permeability of the concrete is increased, and the alkali seepage of the concrete is increased, on the other hand, the ferrite in the concrete is converted into iron ions, so that the concentration of the iron ions is increased, and the adhesion of oyster larvae is inhibited. Aiming at the problem, the anti-permeability of the concrete can be greatly improved by adopting the resin to coat the pigment and then grinding the pigment into powder, and particularly, when the mixing amount is 1.37 percent, the electric flux is only increased by 3.2 percent. Meanwhile, with the increase of the dark pigment, the attachment of the oyster is continuously increased, which is different from the prior addition of 1.37 percent before modification, and is reflected in that the attachment rate of the oyster larvae is reduced.

9: the weight proportions of the unmodified bovine bone meal, the ordinary portland cement, the silica fume, the blast furnace slag powder, the broken stone, the sand, the water and the polycarboxylic acid water reducing agent powder are as follows in sequence: 0.51%, 10.26%, 0.79%, 5.54%, 46.67%, 29.0%, 7.2%, 0.03%.

10: the weight proportions of the unmodified bovine bone meal, the ordinary portland cement, the silica fume, the blast furnace slag powder, the broken stone, the sand, the water and the polycarboxylic acid water reducing agent powder are as follows in sequence: 0.86%, 10.26%, 0.75%, 5.23%, 46.67%, 29.0%, 7.2%, 0.03%.

11: the weight proportions of the unmodified bovine bone meal, the ordinary portland cement, the silica fume, the blast furnace slag powder, the broken stone, the sand, the water and the polycarboxylic acid water reducing agent powder are as follows in sequence: 1.37%, 10.26%, 0.68%, 4.79%, 46.67%, 29.0%, 7.2%, 0.03%.

12: the modified bovine bone meal, the ordinary portland cement, the silica fume, the blast furnace slag powder, the broken stone, the sand, the water and the polycarboxylic acid water reducing agent powder are sequentially prepared from the following components in percentage by weight: 0.51%, 10.26%, 0.79%, 5.54%, 46.67%, 29.0%, 7.2%, 0.03%.

13: the modified bovine bone meal, the ordinary portland cement, the silica fume, the blast furnace slag powder, the broken stone, the sand, the water and the polycarboxylic acid water reducing agent powder are sequentially prepared from the following components in percentage by weight: 0.86%, 10.26%, 0.75%, 5.23%, 46.67%, 29.0%, 7.2%, 0.03%.

14: the modified bovine bone meal, the ordinary portland cement, the silica fume, the blast furnace slag powder, the broken stone, the sand, the water and the polycarboxylic acid water reducing agent powder are sequentially prepared from the following components in percentage by weight: 1.37%, 10.26%, 0.68%, 4.79%, 46.67%, 29.0%, 7.2%, 0.03%.

Adding 100-mesh bovine bone meal into 2% phosphoric acid solution, wherein the weight ratio of the bovine bone meal to the phosphoric acid solution is 1:3, the temperature is 20-30 ℃, the mixture is stirred for 30 minutes in a stirrer with the rotating speed of 200-500 rpm, a centrifugal machine with the rotating speed of 3000-5000 rpm is adopted for centrifugation for 3 minutes, supernatant is poured off, solid matters of the centrifuged solid matters are washed for 2-3 times by water, and washing water does not show acidity any more; vacuum drying the centrifuged solid substance at 40 deg.C, mixing the dried Os bovis Seu Bubali powder and slag powder at a ratio of 1:4, and grinding with vibration mill to fineness of more than 200 meshes.

Note: grinding the modified bovine bone meal to 200-300 meshes

Aiming at the problem that the grinding of the bovine bone powder is difficult, the bovine bone powder is difficult to grind again generally about 100 meshes, the 100-mesh bovine bone powder is chemically modified by adopting 2% dilute phosphoric acid, then the dried bovine bone powder and the slag powder are mixed according to the ratio of 1:4, and the mixture is ground to the fineness of more than 200 meshes by using a vibration mill. The modified bovine bone meal increases the contact with alkaline substances in the concrete, and simultaneously, the microstructure in the concrete is more compact without the previous mildewing phenomenon. And after the modification, the impermeability of the concrete is improved under the condition of low doping amount. Even if the mixing amount reaches 1.37%, the electric flux is increased by only 4.2%, and the attachment change rate of oyster larvae is increased from 205% to 400%.

15: the modified bovine bone meal, the modified dark pigment (black iron oxide: nigrosine mixture mass ratio is 1:1), the oyster shell powder, the ordinary portland cement, the silica fume, the blast furnace slag powder, the broken stone, the sand, the water and the polycarboxylic acid water reducing agent powder are sequentially mixed according to the weight ratio: 0.51%, 0.86%, 0.51%, 10.26%, 0.62%, 4.34%, 46.67%, 29.0%, 7.2%, 0.03%.

16: the modified bovine bone meal, the modified dark pigment (black iron oxide: nigrosine mixture mass ratio is 1:1), the oyster shell powder, the ordinary portland cement, the silica fume, the blast furnace slag powder, the broken stone, the sand, the water and the polycarboxylic acid water reducing agent powder are sequentially mixed according to the weight ratio: 0.86%, 0.51%, 0.86%, 10.26%, 0.58%, 4.03%, 46.67%, 29.0%, 7.2%, 0.03%.

The example is characterized in that on the basis of the reference concrete, the deep color pigment, the oyster shell powder and the bovine bone powder are compounded and doped, and the reference concrete provides necessary Ca for adhesion and metamorphosis of the oysters²⁺And has a lower alkalinity; meanwhile, the dark pigment darkens the color of the concrete, almost all visible light is absorbed, the surface of the concrete is blackened, and a dark environment is provided; HCO necessary for providing attachment by mixing shell powder and bovine bone powder₃ ^-、PO₄ ^3-And various trace elements are used for promoting the adhesion of the oysters together, so that the adhesion change rate of the oyster larvae can reach 317% when the dark color pigment is 0.86%, the oyster shell powder is 0.51% and the bovine bone meal is 0.51%, and the adhesion change rate is increased by 517% when the dark color pigment is 0.86%, the oyster shell powder is 0.51% and the bovine bone meal is 0.86%.

17: the weight proportions of the calcium carbonate powder, the ordinary portland cement, the silica fume, the blast furnace slag powder, the broken stone, the sand, the water and the polycarboxylic acid water reducer powder are as follows in sequence: 0.51%, 10.26%, 0.79%, 5.54%, 46.67%, 29.0%, 7.2%, 0.03%.

18: the weight proportions of the calcium carbonate powder, the ordinary portland cement, the silica fume, the blast furnace slag powder, the broken stone, the sand, the water and the polycarboxylic acid water reducer powder are as follows in sequence: 0.86%, 10.26%, 0.75%, 5.23%, 46.67%, 29.0%, 7.2%, 0.03%.

19: the weight proportions of the calcium carbonate powder, the ordinary portland cement, the silica fume, the blast furnace slag powder, the broken stone, the sand, the water and the polycarboxylic acid water reducer powder are as follows in sequence: 1.37%, 10.26%, 0.68%, 4.79%, 46.67%, 29.0%, 7.2%, 0.03%.

This example replaces mineral admixtures by using equal amounts of 600 mesh calcium carbonate powder in different admixtures. The anti-permeability performance of the concrete is weakened along with the increase of the content of the calcium carbonate powder, but the electric flux of the concrete is lower than the reference value, and the anti-permeability performance of the concrete is better than that of the reference group even if the mixing amount is 1.37%. Along with the increase of the doping amount of the calcium carbonate powder, the dissolution probability of the calcium carbonate in the concrete is increased, so that the attachment change rate is increased, which is specifically shown in that the doping amount is 0.51%, 0.86% and 1.37%, and the attachment change rate of oyster larvae is respectively improved by 20%, 40% and 50%.

20: the weight ratio of zinc sulfate, modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), modified bovine bone meal, calcium carbonate powder, ordinary portland cement, silica fume, blast furnace slag powder, broken stone, sand, water and polycarboxylic acid water reducing agent powder is as follows: 0.3%, 0.86%, 0.51%, 10.26%, 0.54%, 3.77%, 46.67%, 29.0%, 7.2%, 0.03%.

21: the weight ratio of zinc sulfate, modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), modified bovine bone meal, calcium carbonate powder, ordinary portland cement, silica fume, blast furnace slag powder, broken stone, sand, water and polycarboxylic acid water reducing agent powder is as follows: 0.6%, 0.86%, 0.51%, 10.26%, 0.50%, 3.51%, 46.67%, 29.0%, 7.2%, 0.03%.

The method for modifying the zinc sulfate comprises the following steps: selecting diatomite SiO₂Adding 150g of water and 100g of zinc sulfate into diatomite with the content of more than 90 percent and the fineness of 600 meshes in a stirrer at the temperature of 60 ℃, and stirring until the mixture is completely dissolved for later use; and then 150g of the diatomite is heated to 60 ℃, added into the solution, stirred for 10 minutes in a stirrer with the rotating speed of 200-500 rpm, and then dried in a drying box with the drying temperature of 100 ℃ to obtain the modified zinc sulfate.

Note: the dark pigment is modified iron oxide black and aniline black, and the mass ratio is 2:1

The example provides necessary Ca for adhesion and metamorphosis of oysters by compounding and doping zinc sulfate, bovine bone meal, calcium carbonate powder and dark pigment on the basis of the reference concrete²⁺And has a lower alkalinity; meanwhile, the deep color pigment deepens the color of the concrete, almost all visible light is absorbed, the surface of the concrete becomes black, and a dark environment is provided; adding Os bovis Seu Bubali powder and calcium carbonate powder to provide HCO necessary for attachment₃ ^-、PO₄ ^3-Zn provided by various trace elements and zinc sulfate in the bovine bone meal²⁺The oyster shell larva adhesion promoting agent can promote early adhesion of oyster larva, and has excellent effect of inducing adhesion and metamorphosis of oyster larva to obtain required ions and dark color, wherein the adhesion change rate can reach 580% when the content of dark color pigment is 0.86%, the content of bovine bone powder is 0.51%, the content of calcium carbonate powder is 0.51%, and the content of zinc sulfate is 0.3%, and the adhesion change rate can reach 652% when the content of dark color pigment is 0.86%, the content of bovine bone powder is 0.86%, the content of calcium carbonate powder is 0.51%, and the content of zinc sulfate is 0.6%.

22: the weight ratio of zinc sulfate, modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), modified bovine bone meal, calcium carbonate powder, ordinary portland cement, silica fume, blast furnace slag powder, broken stone, sand, water, short-cut fiber and polycarboxylic acid water reducing agent powder is as follows in sequence: 0.6%, 0.86%, 0.51%, 10.26%, 0.50%, 3.51%, 46.42%, 28.85%, 7.2%, 0.4%, 0.03%.

The concrete performance test method for pouring comprises the following steps:

3 cylindrical test pieces with the diameter of 100 multiplied by 50mm and 5 cuboid test pieces with the diameter of 200 multiplied by 30mm are prepared and are respectively used for testing the chloride ion permeability resistance of the concrete for 28d and the adhesion and metamorphosis of oyster larvae in a laboratory after standard curing for 28 d. The specific operation steps are as follows:

(I) test piece Forming

1. Calculating and accurately weighing the common portland cement, the mineral admixture, the crushed stone, the sand, the water, the calcium carbonate powder, the trace elements, the dark pigment, the biological calcium powder, the chopped fibers and the polycarboxylic acid water reducing agent powder according to the mass.

2. Firstly, placing broken stone and sand into a concrete mixer to be mixed for 0.5-1 minute; then adding portland cement, mineral blending materials, calcium carbonate powder, trace elements, biological calcium powder and dark color pigment, and continuing stirring for 0.5-1 minute; then adding chopped fibers, water and a superplasticizer and stirring for 2-6 minutes; after uniformly stirring, pouring, vibrating and removing a mould to obtain 3 cylindrical test pieces with the diameter of 100 multiplied by 50mm and 5 cuboid test pieces with the diameter of 200 multiplied by 30 mm; finally, the oyster shell larvae are placed in a standard curing room for 28 days, corresponding permeability evaluation is carried out at each age, and oyster larva attachment and metamorphosis experiments in a laboratory are carried out after 28 days.

(II) the rapid chloride ion permeation experiment comprises the following specific steps:

according to the Standard Test Method for electric Indication of Concrete's resistance to resistance Chloride Ion networking (ASTM1202-2017), in Standard curing for 28d, 3 cylindrical Test pieces with a diameter of 100X 50mm were taken out from a curing chamber, and the surface moisture and impurities were cleaned, and after the surface was dried, a thin layer of epoxy resin was coated on the side of the cylindrical Test piece. The test piece is then placed in a vacuum water saturation machine for 20 to 24 hours. Then taking out the test piece to clean the surface, placing the test piece into an organic glass mold, and respectively filling sodium chloride solution (electrode connected with the negative electrode of a power supply) with the mass concentration of 3% and sodium hydroxide solution (electrode connected with the positive electrode of the power supply) with the molar concentration of 0.3mol/L into the molds at the two sides after the tightness between the test piece and the molds is detected. The laboratory instrument was then started and the experimental data were recorded after 6h, and the latter two test pieces repeated the above procedure. And finally, calculating the intensity according to the standard.

(III) the indoor oyster larva settlement and metamorphosis experiment comprises the following specific steps:

after standard maintenance for 28 days, respectively taking out cuboid test pieces of 200 multiplied by 30mm from a maintenance room, cleaning the surface moisture and impurities, then putting the cuboid test pieces into a test pool, wherein the seawater in the pool is sand-filtered yellow sea water, the salinity is about 32% -34%, and after the seawater level is higher than that of the concrete test piece, uniformly spreading oxygen pipes in the test pool to prepare for throwing in the oyster larvae.

And after the oyster adhesion inducing test is started, the seawater in the test pool is changed every day, the water changing amount is 1/3 of the total capacity of the test pool, a screen (more than or equal to 200 meshes) is used for blocking a water outlet, the unattached oyster seedlings are prevented from running off along with water, the seedlings on the screen are put into the test pool again, then the chlorella is fed by using a rubber head dropper at regular time and quantity at 9 and 19 times every day, and the oyster adhesion condition is observed.

And (4) after the test lasts for 30d, draining water in the test pool, taking out the test piece, carrying out statistical record analysis on the number of oysters on the surface of the test piece and the survival rate of the oysters, and taking a smooth bottom surface when the concrete is poured and molded during statistics.

Compared with the prior art, the invention has the beneficial effects that:

compared with the comparison document 1 (a novel concrete artificial fish reef and a preparation method thereof CN104529286A), the differences are that:

the purpose in the present invention is different from the comparison document: comparative document 1 is directed to waste utilization, repair and improvement of artificial fish reefs, although oyster shell powder is added to concrete. The aim of the invention is to induce sessile organism attachment, mainly oyster, and consider barnacle attachment when the reinforced concrete in the tidal range area is corrosion-resistant.

Compared with the comparison document 2 (a bionic concrete artificial fish reef and a preparation method 2015CN104938384A), the differences are that:

(1) the object in the present invention is different from comparative document 2: in comparison document 2, although oyster shell or oyster shell powder is added to concrete, its purpose is mainly achieved by surface bionic property, fish, microorganism and algae are collected, the number of microorganisms is increased, and the water environment is improved, and no oyster is mentioned. The aim of the invention is to induce sessile organism attachment, mainly oyster, and consider barnacle attachment when the reinforced concrete in the tidal range area is corrosion-resistant.

(2) The comparison document 2 indicates that the biological calcium carbonate powder (150-200 meshes) with the cement mixing amount of less than 10% is not obvious in induced adhesion. However, in the research process, the modified bovine bone powder and the biological calcium carbonate powder (with the fineness of 100-1000 meshes) are adopted, so that the optimal mixing amount of the bovine bone powder and the biological calcium carbonate powder is within 10 percent of the cementing material.

(3) By modifying bovine bone powder and biological calcium carbonate powder, specifically, egg shell powder, coral powder, oyster shell powder and fishbone powder of 100-500 meshes are treated by the following acids, including one or two of acetic acid, silicic acid and sulfurous acid; the 100-500 mesh bovine bone powder is treated by one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid.

(4) The contrast document is difficult to construct by embedding oyster shells on the concrete surface, and the feasibility is low because the method can not be adopted on each engineering surface. According to the invention, the shell powder is added into the concrete to induce anchorage attachment, and the doping amount of the shell powder accounts for less than 10% of the mass of the cementing material, so that the construction is simple, and the oyster attachment amount can be greatly increased.

(5) In the marine environment, the phenomenon that the artificial fish reef is seriously corroded for many times in recent years appears, and the serious corrosion is mainly caused by the combined action of biological sulfuric acid secreted by anaerobic microorganism thiobacillus, acid substances secreted by other bacteria and the like. Calcium carbonate is weak against acid corrosion, and thus, too high a calcium carbonate content having a large fineness causes severe acid corrosion.

Compared to reference 3 (Vanreilin. influence of matrix type on oyster attachment, growth, population establishment and reef development [ D ]), the difference is:

(1) in comparison document 3, 80-mesh bovine bone powder, calcium powder and gypsum powder were used, each separately added to concrete. The fineness of all the calcium materials in the invention is more than 100 meshes and more than that of the materials in the comparison document 3. The bovine bone meal is also added, modified and the concrete grain composition and the induction capability thereof are considered.

(2) Grinding the bovine bone powder by using a vibration mill at normal temperature, wherein when the fineness is more than 80 meshes, the bovine bone powder contains a large amount of collagen and is seriously agglomerated, so that the bovine bone powder cannot be continuously ground. The invention adopts dilute acid modification technology and is compounded with other substances and ground to obtain the modified biological calcium powder with small particle size and fineness of more than 200 meshes. The prepared biological calcium powder retains the original substances of the biological calcium, increases the release rate of substances which induce oyster larvae to adhere to the biological calcium powder, and reduces the doping amount of the biological calcium powder, thereby reducing the influence on the performance of cement concrete.

(3) Because the bovine bone meal contains rich organic substances such as collagen, the great amount of the substances can cause the strength and the impermeability of concrete to be reduced, particularly after the content of the organic substances exceeds 5 percent, the mixing amount is increased, the strength of the concrete is rapidly reduced, the impermeability is obviously reduced, and mildew grows on the surface of the concrete under standard curing conditions. FIG. 2 shows the mildew formation of a concrete specimen. FIG. 3 shows the surface condition of the modified concrete.

As can be seen from FIG. 2, the mold on the concrete surface appeared white flocculent, covering almost the entire concrete surface; the concrete surface in figure 3 has no mildew due to the same amount of bovine bone meal, age and curing conditions.

The invention fully exerts the induction capability of the bovine bone meal by controlling and adopting the dilute acid modification and composite grinding technology, greatly reduces the mixing amount of the bovine bone meal, carries out anti-corrosion treatment and modification, realizes the composite inducer mainly comprising the bovine bone meal, has small mixing amount, hardly influences the strength and permeability of concrete, simultaneously has strong oyster larva attachment capability, and solves the problem of mildew of the concrete. Compared with concrete without the inducer, the number of the larvae attached to the concrete with the inducer is obviously increased, and particularly, the method is shown in fig. 4 and 5.

The comparison documents and the reference documents show that: the calcium content is important for the attachment of oyster larvae, and the addition of a proper amount of calcium carbonate substances into the cement-based material is also proved by some current experimental results to promote the attachment and growth of the oyster larvae. However, cement concrete contains a large amount of calcium ions, the pH value of the pore solution is generally more than 12.5, and the pH value of the saturated calcium hydroxide solution is about 12 at normal temperature, so the concreteThe calcium ion concentration in the pore solution is about 5 mmol/L; the solubility of calcium carbonate is very low, and is only 9.5X 10 at 25 DEG C^-5mol/L(9.5×10^-2mmol/L). At present, the optimal range of calcium ion concentration for inducing oyster attachment is considered to be 10-25 mmol/L, and even if oyster larvae are placed in saturated calcium carbonate solution, enough Ca is not available²⁺The concentration provides a suitable ionic concentration for adhesion of the oysters. Further, Ca (OH) in the inside of the cement concrete₂Can be released more quickly, while the dissolution of calcium carbonate takes longer. Thus, it was determined that incorporation of a calcium carbonate material into concrete promotes adhesion of oyster larvae, Ca²⁺Not the dominant role. Early attachment, metamorphosis and HCO of oyster₃ ^-Related to Ca in allergy²⁺Together generating a secondary shell of calcium carbonate. After calcium carbonate is added, the calcium carbonate is mixed with CO₂Reacting with water to form Ca (HCO)₃)₂The later participation in the attachment is the fundamental mechanism for promoting the attachment of oyster larvae.

The calcium carbonate doping amount in the cement-based material has an optimal doping amount, which can be explained from the following three aspects:

1) for equivalent substituted cement, as the calcium carbonate content is increased, the alkali in the concrete is diluted, the total alkalinity is reduced, but as the calcium carbonate content is increased, the dissolution probability of the calcium carbonate in the concrete is increased, and the HCO in the solution is increased₃ ^-The content is increased, so that the attachment and metamorphosis of oysters are promoted; when the addition amount is too large, the permeability of concrete is increased rapidly, alkali and carbonate in the concrete are exuded rapidly, so that the negative effect of the alkali is obvious, and the critical or negative effect of the carbonate is obvious, so that the adhesion amount is reduced;

2) for the same amount of substituted aggregate, the permeability of concrete is reduced along with the increase of the mixing amount, and calcium ions and OH are caused^-The bleeding of (2) is reduced, but the permeation rate of carbonate ions is gradually increased, and when reaching a certain value, the adhesion of oyster reaches the maximum value; as the doping amount continues to increase, the calcium ion decline is large, the carbonate is likely to decrease, and the calcium ion concentration limit appearsThe attachment of oyster larva shows that the attachment amount is reduced;

3) for the same amount of mineral-substituted admixtures, the permeability is increased along with the increase of the admixture, and the HCO required for the oyster adhesion requirement is increased due to the increase of calcium carbonate₃ ^-The concentration reaches a proper range, which is shown as the attachment of oyster larvae is increased; as the addition of the mineral admixture continues to increase, the addition of the mineral admixture is reduced, so that the amount of alkali exuded increases, carbonate increases, but excess alkali and HCO₃ ^-The ions inhibit adhesion of oyster larvae.

Compared with a comparison document 4 (Li Zhen, Neigai, Yongtao, et al. the biological adhesion effect of concrete artificial fish reefs of different cement types [ J ] fishery science progress, 2017,38(5):57-63.), the differences are that:

in comparative document 4, composite portland cement, slag portland cement, pozzolanic portland cement, fly ash portland cement, and aluminate cement were used: the invention adopts the composite doping of ordinary portland cement and mineral admixture to realize low-alkalinity cement; the silica fume is one of mineral admixtures, has high activity, has obvious effect of improving the durability of reinforced concrete in the marine environment by proper mixing amount, and can obtain low-alkalinity cement with excellent strength and durability through optimized design and experiments. Meanwhile, by utilizing the characteristic of high impermeability of the silica fume concrete, a large amount of oyster larvae are attached, distorted and grown even if the alkalinity of the interior of the concrete is higher. And the alkalinity of the cement concrete is regulated and controlled by adopting the composition of the low-alkalinity sulphoaluminate cement, so that a proper pH value is provided for the adhesion of oyster larvae. In addition, marine plants and sessile organisms such as oysters and barnacles have different alkali resistance and different environments required in the attachment period and later period, such as the attachment, metamorphosis and later growth of barnacles and oysters, need a large amount of calcium ions.

The concrete in the comparison document 4 is used for enriching marine organisms, mainly in view of the size and diversity of attached biomass, and the main attached organisms are various algae and the like. The aim of the research in the invention is to induce oyster attachment, but the tolerance of oysters and barnacles to alkalinity is higher than that of algae, and a large amount of calcium ions are needed for oyster attachment and metamorphosis, so that two kinds of concrete look the same and are greatly different. Fig. 6 and 7 are comparison results of biological adhesion between the comparison document 4 after the experiment of the real sea adhesion about 210d and the experiment of the present invention after the experiment of the real sea adhesion about 300 d.

Therefore, since this part of knowledge relates to marine periphyton, the intersection of marine plants with the engineering discipline of marine concrete, and those skilled in the concrete and engineering fields or the field of marine life cannot obtain the technical feature of the present invention that the balance between the concrete alkalinity reduction and the calcium ion concentration is closely related to the attachment of marine periphyton by comparing document 1.

In addition, the unique characteristics and the beneficial effects of the invention are as follows:

deep colour pigment

By utilizing the light-resistant characteristic of oyster eyespot larvae, dark pigments (one or two of black iron oxide, nigrosine, carbon black, antimony sulfide, red iron oxide and organic pigment red) are doped into the concrete, the color of the concrete is changed, the color of the concrete is darkened, the oyster larvae are considered as a dark environment, the oyster larvae are induced to arrive at the dark concrete surface, the contact probability of the larvae and the concrete surface is increased, and the oyster larva induced attachment rate is increased. The method specifically comprises the following steps:

the researchers of marine organisms, in order to breed and proliferate or in order to eliminate undesirable populations, consider the study of the adhesion of marine periphyton with different colored substrates, belonging to the subject of marine biology. The discipline of marine concrete engineering or concrete materials is quite different and is two big disciplines. By crossing the marine sessile organisms with the concrete discipline, the oyster larva induced attachment by adopting dark concrete is obtained. According to the invention, the addition of dark pigment is adopted to deepen the color of the surface of concrete so as to promote the attachment of oyster larvae. The concrete is mixed with other materials, and the performance of the concrete is influenced. The invention considers that the concrete with different cement has different surface colors. Thus, according to the cementThe type and the doping amount of the dark substance. Dark pigments also affect the properties of the concrete. Most importantly, the deep color pigment is added, and alkali and Ca in the concrete are not controlled²⁺When the permeation rate is equal, the released alkali can influence the attachment, metamorphosis and growth of sessile organism larvae, and when the mixing amount is more than a certain value, the attachment amount of the larvae is reduced. The impermeability of the concrete is designed and controlled, and the main measures are as follows: the selection of the type of the dark color pigment, the control of the addition amount and the modification. The attachment rate of the larvae is increased along with the increase of the doped amount of the dark substance, and when the doped amount is 0.5-6% of the cementing material, the attachment amount of the larvae is maximum, but then the attachment amount is slightly increased or kept unchanged.

Trace elements

According to the enrichment of a large amount of zinc in the oyster body, the zinc is far higher than the seawater where the oyster lives, and meanwhile, the oyster body also contains more Fe, P and K elements. At the same time, the appropriate Zn in the solution²⁺，K⁺The concentration can promote early stage attachment and metamorphosis of oyster larva. Therefore, zinc sulfate, potassium nitrate, ferric sulfate, zinc phosphate, ammonium nitrate, potassium phosphate, ammonium phosphate, iron phosphate and calcium phosphate are adopted as trace elements to be doped into the concrete, and the strength and the impermeability of the concrete are basically kept unchanged through modifying the substances, so that the induced attachment rate of oyster larvae is greatly increased. The method specifically comprises the following steps:

the marine organism researchers, in order to clarify the oyster attachment mechanism and the purpose of breeding and proliferation, research the attachment and metamorphosis of different ions to marine periphyton, belong to the marine biology subject. The method is different from the science of marine concrete engineering or concrete materials, and is completely two large disciplines. Through the crossing of marine sessile organisms and the concrete discipline, the method is obtained by adding corresponding substances into the concrete to induce the adhesion of oyster larvae on the surface of the concrete. Because the soluble salts greatly affect the performance of the concrete, such as the early workability, the setting time and the later strength and impermeability, the invention adopts the diatomite as the carrier, fixes the inorganic salts in the diatomite, reduces the effect of the soluble salts on the performance of the concrete, and simultaneously utilizes the effect of the diatomite on improving the performance of the concrete to realize that the good mechanical property and impermeability of the concrete can be still maintained when the inducing substances are added. In addition, because the diatomite has a slow release effect as a carrier, the soluble salt is released slowly, and particularly, after the diatomite is soaked in seawater for a certain time, the release rate is maintained at a very low rate. Therefore, this part of knowledge also relates to the intersection of marine periphyton, chemistry and marine concrete engineering disciplines, and no one skilled in the concrete and engineering fields or marine biology field can obtain the technical characteristics of the present invention of incorporating trace elements into concrete, changing the ion content of trace elements on the surface of concrete and controlling the concrete permeability in close association with concrete with high ability to induce oyster larva attachment by means of the existing background.

Permeability of concrete

The strength and permeability of concrete are the two most important properties of concrete. When considering that different substances are added to promote the attachment, metamorphosis and later-stage growth of oyster larvae, the strength and permeability of the concrete are controlled from the whole without great influence, then raw materials are selected according to the compatibility of various raw materials, and when the performance of the raw materials cannot meet the actual requirements, the raw materials are added after being modified, so that the expected functions are achieved. However, in the related research, although the influence of the calcium content on the adhesion of the oyster larvae is considered, the water cement ratio, the calcium content, the curing and the like are not considered, the permeability of the concrete changes the alkali and ion leakage rate inside the concrete, and the poorer the impermeability of the concrete, the larger the alkali and ion leakage rate inside the concrete is, and the increase of the alkali and ion leakage rate may be exponential. Thus, the released alkali and ions have a great influence on the larvae, and there may be a change from adhesion promotion to adhesion inhibition, which is more serious especially when the cement is present in a large amount. Therefore, the inducer is added into the concrete to ensure that the impermeability of the concrete is changed within a controllable range, such as the change is not more than 10%. The induction effects of the above-mentioned ingredients can be compared, otherwise, the influence of the single-doped inducer or the compound-doped inducer on the induction effect of the oyster larvae cannot be evaluated.

Only the optimum environment required by the attachment, metamorphosis and later growth of marine periphyton is mastered, and the concrete can be designed based on the high impermeability of the concrete, rather than only considering the mixing amount of various raw materials and neglecting the impermeability change of the concrete. Therefore, this part of knowledge also relates to the intersection of marine periphyton, chemistry and marine concrete engineering disciplines, and no one skilled in the concrete and engineering fields or marine organism fields can obtain the technical characteristics of the present invention that the overall control of concrete impermeability and the close correlation of the ability of the inducer to promote efficient induced adhesion of oysters by the inducer by the existing background.

Furthermore, the fibres may enhance the strength, in particular the tensile strength, of the concrete. The invention combines the alkali-resistant fiber with the concrete with ecological property, thereby enhancing the characteristics of crack resistance, bending resistance and fatigue resistance of the concrete. The concrete breakwater can reduce early cracking of concrete when applied to a breakwater member, reduce the damage rate of the member during transportation and fixing at sea edge, and particularly increase the capability of resisting extreme loads such as typhoons.

Therefore, since this part of knowledge relates to the intersection of marine periphytons, marine plants and marine concrete engineering disciplines, no matter the concrete and engineering fields or the technical personnel in the marine organism field, the technical characteristics of color change, bovine bone meal modification, grinding technology and control of concrete permeability in the concrete with close correlation to the concrete with high-efficiency oyster adhesion-inducing ability and high durability in the case of the deep color pigment incorporated in the concrete of the present invention can be obtained by comparing the documents 1 to 3. And the technical feature of the present invention that the balance between the concrete alkalinity decrease and the calcium ion concentration is closely linked to the attachment of marine periphyton cannot be obtained by comparison with document 4.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims

1. A method for building an ecological high-durability concrete structure in a marine environment is characterized by comprising the following steps: the method comprises the following steps:

surveying the sea area of the building position of the concrete structure: investigating the species of the oyster in the sea area and whether the oyster is attached, and performing temperature, seawater temperature, dissolved oxygen, plankton, total dissolved inorganic nitrogen, active phosphate, active silicate and Ca in different seasons on the sea area²⁺、Zn²⁺、K⁺The like, and the times, the intensity and the like of typhoon in the past year;

culturing oyster eyespot larvae: collecting mature oyster parent shells in local sea areas, obtaining sperms and ova through an anatomical method, performing artificial insemination, and culturing the sperms and the ova indoors until the eyespot larvae stage; the seawater is filtered by sand in the cultivation process, the density is 2-10/mL, the water is changed once every two days, the chrysophyceae or diatom concentrated bait is fed, and the feeding amount is gradually increased from 2 ten thousand cells/mL to 9 ten thousand cells/mL according to the larval development condition;

construction of concrete structure: pouring the fiber-reinforced ecological concrete which is highly induced to adhere to and deform the marine periphyton and promotes growth into a prepared template by adopting a cast-in-place method, and maintaining for more than 14 d;

field attachment: in the concentrated attaching and metamorphosis period of the oyster planktonic larvae, a fixing frame is additionally arranged on the structure, a part below a low tide line is sealed and enclosed, the upper part of the oyster planktonic larvae is tightly connected with the sealed enclosure below the low tide line by adopting a 80-200-mesh screen, then the oyster eyespot larvae in the step (2) are filtered, collected and then transported to a construction site in low-temperature dry exposure mode, and are placed in the enclosure, and the seedling placing amount is 1-5 per 10 mL;

monitoring larva attachment and management: monitoring the adhesion condition of the oyster larvae on the surface of the concrete, and taking corresponding measures according to the actual condition.

2. The method for constructing an ecological high-durability concrete structure in a marine environment according to claim 1, wherein: the fiber-reinforced ecological concrete is prepared from a cementing material, broken stone, sand, water, a dark pigment, biological calcium powder, calcium carbonate powder, trace elements, a short-cut fiber and a superplasticizer, wherein the cementing material, the broken stone, the sand, the water, the dark pigment, the biological calcium powder, the calcium carbonate powder, the trace elements, the short-cut fiber and the superplasticizer are sequentially prepared from the following components in parts by weight: 12.5% -22.0%, 39.4% -49.8%, 24.9% -37.3%, 6.2% -8.7%, 0.2% -1.7%, 0.15% -1.0%, 0.1% -1.0% and 0.02% -0.1%.

3. The method for constructing an ecological high-durability concrete structure in a marine environment according to claim 2, wherein: the raw materials in the fiber reinforced ecological concrete comprise:

the dark color pigment is as follows: one or two of iron oxide black, aniline black, carbon black, antimony sulfide, iron oxide red and organic pigment red; according to the influence degree on the performance of concrete, the pigments are modified by adopting one of transparent resin, organic silicon, dimethyl siloxane and super-hydrophobic materials;

the biological calcium powder comprises: the bovine bone powder, the biological calcium carbonate powder comprises one or more of oyster shell powder, fishbone powder, egg shell powder and coral powder, and the fineness of the biological calcium carbonate powder is 100-1000 meshes;

the biological calcium powder modification method comprises the following steps: treating 100-500 mesh egg shell powder, coral powder, oyster shell powder and fishbone powder with acid selected from one or two of acetic acid, silicic acid and sulfurous acid; and treating the 100-500-mesh bovine bone powder by using one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid;

the calcium carbonate powder is as follows: calcite, chalk, limestone, marble, aragonite, travertine powder, and one or more of light calcium carbonate, activated calcium carbonate, calcium carbonate whisker and superfine light calcium carbonate after processing treatment, wherein the fineness is more than 200 meshes;

the trace elements are as follows: zinc, iron, potassium and phosphorus, which can be selected from natural minerals, industrial products or chemical reagents, including one or more of zinc sulfate, calcium phosphate, zinc phosphate, potassium sulfate, potassium nitrate, ferric sulfate, ammonium nitrate, potassium phosphate, ammonium phosphate and iron phosphate, and are modified to realize the slow release of corresponding ions and reduce or eliminate the adverse effect on the performance of concrete; however, nitrogen and phosphorus elements are not selected for eutrophic areas;

the chopped fibers are as follows: inorganic fibers, such as one or more of basalt fibers, glass fibers and carbon fibers;

the cementing material is as follows: one of silicate cement, sulphoaluminate cement and alkali-activated cementing material which are mixed with mineral admixture; wherein the mineral admixture in the silicate cement doped with the mineral admixture comprises one or more of silica fume, slag powder and fly ash; the sulphoaluminate cement comprises one or two of quick-hardening sulphoaluminate cement, high-strength sulphoaluminate cement and expansion sulphoaluminate cement; the alkali-activated cementing material is one of alkali-activated slag, alkali-activated slag and fly ash;

the sand is as follows: one or more of river sand, machine-made sand or desalinated sea sand.

4. The method for constructing the ecological high-durability concrete structure in the marine environment as claimed in claim 1, wherein the method for preparing the fiber reinforced ecological concrete comprises the following steps:

5. The method for constructing an ecological high-durability concrete structure in a marine environment according to claim 1, wherein: the oyster planktonic larvae are intensively attached for a metamorphosis period of 5-10 months.

6. The method for constructing an ecological high-durability concrete structure in a marine environment according to claim 1, wherein: the oyster field attachment fixing frame additionally installed adopts a keel-skeleton form which is of an upper structure and a lower structure, the lower part of the oyster field attachment fixing frame adopts a high-strength and light-weight sealing enclosure, the upper part of the oyster field attachment fixing frame adopts a double-layer screen, and the mesh opening of an external screen is 80-200 meshes.