CN111268962A

CN111268962A - Dark portland cement concrete for inducing adhesion of marine periphyton and preparation method thereof

Info

Publication number: CN111268962A
Application number: CN201911210606.7A
Authority: CN
Inventors: 吕建福; 马小兵
Original assignee: Harbin Engineering University
Current assignee: Harbin Engineering University
Priority date: 2019-12-02
Filing date: 2019-12-02
Publication date: 2020-06-12

Abstract

The invention relates to a technology for inducing marine periphyton attachment, in particular to dark portland cement concrete for inducing marine periphyton attachment and a preparation method thereof, and belongs to the cross field of marine periphyton and marine concrete. The material composition of the invention is: portland cement, mineral admixture, broken stone, sand, water, dark pigment, biological calcium powder and a superplasticizer. The strength and permeability of concrete are the two most important properties of concrete. When considering that different substances are added to promote the adhesion, metamorphosis and later growth of oyster larvae, the strength and permeability of the concrete are not greatly influenced by the oyster larvae, and then raw materials are selected according to the compatibility of various raw materials.

Description

Dark portland cement concrete for inducing adhesion of marine periphyton and preparation method thereof

Technical Field

The invention relates to a technology for inducing marine periphyton attachment, in particular to dark portland cement concrete for inducing marine periphyton attachment and a preparation method thereof, and belongs to the cross field of marine periphyton and marine concrete.

Background

Reinforced concrete is widely applied to marine infrastructure construction, such as harbor wharfs, sea-crossing bridges, ocean platforms, submarine tunnels and the like. However, the problem of corrosion of the steel bars caused by corrosion of chloride ions greatly shortens the service life of the reinforced concrete structure, and brings huge economic burden to the society. Representative anticorrosion technologies for reinforced concrete engineering in marine environments include high-performance concrete, surface coatings, FRP bars, reinforcing steel bar corrosion inhibitors, electrochemical protection technologies, and the like. These corrosion protection techniques suffer from one or more of the disadvantages or shortcomings of difficult construction, poor aging durability of the material, long term unpredictability, high cost, etc. In addition, most of the current anti-corrosion technologies are directed to the splash zone, and for the anti-corrosion in the tidal range, the problems of few measures, high cost and poor anti-corrosion effect exist.

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 has the characteristics of initiative, economy and environmental protection, and the limitation of the existing reinforced concrete corrosion prevention technology in a tidal range area and a submarine area is overcome. The method is a cross between the subjects of marine concrete and marine sessile biology, and opens up a new research field of reinforced concrete structure corrosion prevention. 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. Therefore, the key to realizing the anti-corrosion of sessile organisms is to induce the sessile organisms to be rapidly and densely attached to the surface of the concrete.

Meanwhile, as coastal economy develops rapidly in recent decades without paying attention to environmental protection, large-scale damage to coastal ecology is caused, and great influence is caused on coastal ecology and economy in China. At present, a series of relevant policies of China emerge, the ocean engineering construction of China also faces a peak period, and simultaneously, the ocean engineering constructed in a large scale and the breakwater which ensures the stability of the surrounding sea area further destroy the originally fragile ecosystem of the ocean. If proper ecological environment protection is not adopted, a greater disaster must be brought to the ecology along the shore of the ocean. Meanwhile, most coastal infrastructures cannot be dismantled, and the ecology in the sea area needs to be restored, so that people gradually realize the application of ecological technology on a large number of infrastructures, and the ecology in the sea area can be effectively improved or restored. Therefore, it is very important and urgent to construct a concrete project with good ecological effects, or to ecologize the existing concrete project, etc. to improve the offshore ecological environment. However, until now, the ecological technology of projects such as breakwaters at tidal range areas is still in a blank state in China.

Oysters are ecological engineers and are mainly concentrated in a tidal range area and underwater within 30 meters, and the oysters like to be attached to shells of the same kind to form a thick oyster reef, so that the oysters are compactly attached to the breakwater, and the ecology of the breakwater can be realized; in addition, the existing oyster reefs are seriously damaged, and most oysters need to be attached again in a large scale to realize ecological restoration. Therefore, the ecological function of the oysters can be realized through mass propagation of the oysters when the marine ecological engineering construction and the oyster reef restoration are carried out. Therefore, how to make oysters attach, deform and grow rapidly and compactly on the projects is crucial. At present, the relevant research 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 into the cell, resulting in the cellThe rise in pH within the cell subsequently causes depolarization of the neurons of the behavioral pathway, which in turn induces sessile metamorphosis. Although the study on the attachment and metamorphosis of more sessile organisms on the surfaces of different substances such as polyethylene plates, shells, tiles and the like is carried out in solution, the method is not easy to realize or has high cost when being applied to the actual marine concrete engineering.

At present, with the great application of concrete in ocean engineering, particularly recent oyster reef repair engineering and the like, the concrete becomes a substrate material which is most commonly attached by marine periphyton. But the concrete material is different from the traditional seashells, 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. Because of the 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 a 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 the biological adhesion effect, the aluminate cement and the fly ash portland cement have good biological adhesion effect, and the alkalinity is lower than that of common portland cement concrete^[1]. Similarly, the cement concrete has better ecological effect by adding 40-60% of fly ash and slag powder. In addition, the type and the quantity of attachment organisms on the travertine gelled material concrete are more than those on the cement concrete, and the higher the content of the travertine gelled material is, the ecological effect of the travertine gelled material concrete isThe better the result. The ecological concrete engineering for building the American land adopts cement concrete with low alkalinity, such as aluminate cement, in particular slag portland cement, wherein the replacement amount of slag reaches 50 percent, and has good ecological effect of enriching marine plants, animals and the like^[2,3]. 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

The research at home and abroad shows 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 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 5-60% of the mortar (41.7-500.0% of the cement), and the effect is best when the calcium carbonate powder is 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 shell cement is not suitable for being used in concrete engineering in 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 to mix 150-200 mesh biological calcium carbonate powder (fishbone, coral, egg shell and shell are 1:1:1:1) and shell fragment which are 10-20% of the cement mass into the artificial fish reef, which shows that the induced biomass is gradually increased along with the increase of the calcium carbonate mixing amount, and the biomass (marine plant and marine organism) induced by the biological calcium carbonate is the most when the mixing amount is the maximum (20% of the cement weight). In order to reduce the alkalinity of the surface of the concrete artificial fish reef, microorganisms and algae are easier to attach, the biomass and the population quantity are increased, and the fish collecting effect is better. The biological calcium carbonate cement mortar coating layer educt is harmless to the environment and the organism. Although the biological calcium carbonate powder, the oyster shell fragments and the like are doped into concrete for artificial fish reef manufacturing and biological attachment experiments, the biological calcium carbonate powder indeed enhances the biological enrichment effect, but mainly enriches marine plants and microorganisms.

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 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, while the dissolution of calcium carbonate takes longer. Therefore, the temperature of the molten metal is controlled,it was confirmed that calcium carbonate material was added to concrete to promote adhesion of oyster larvae, Ca²⁺Not the dominant role.

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

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

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

The color of the substrate has certain influence on the attachment, metamorphosis and growth of the larvae of the marine periphyton. In foreign countries, it has been reported that in sea areas with low temperature, dark bottom substances 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 that participates 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 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 of greater area and potentially greater abundance and diversity than a smooth surface. Recent studies have shown that textured concrete surfaces adhere to 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 settlement metamorphosis of larvae.

In summary, while the above studies have been conducted, such as different substrates, and the effect of color and roughness on marine periphyton attachment, the effect of incorporating calcareous materials into concrete on marine periphyton attachment has recently been investigated. 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 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, the calcium powder doped in cement is too much and the durability of concrete is seriously insufficient, the doped bovine bone meal is easy to mildew and the like, and in addition, professional technicians of marine concrete engineering materials and structures lack the professional knowledge required for marine sessile organism adhesion, so that the cooperation of the professional technicians of multiple subjects is required to solve many problems.

Disclosure of Invention

The invention aims to solve the problems that the existing concrete substrate adopting a singly-doped calcareous material has overlarge doping amount, serious and poor concrete durability and low adhesion efficiency of inducing oyster larvae, and provides the concrete with high durability for inducing fast and compact adhesion of sessile organisms

The purpose of the invention is realized as follows: the invention uses low alkalinity silicate cement mixed with mineral admixture, adds dark color pigment and biological calcium powder into concrete and controls the permeability of concrete, so that the concrete has high capability of inducing adhesion and metamorphosis of oyster larvae.

The invention also includes such structural features:

the material components are as follows: the silicate cement, the mineral admixture, the broken stone, the sand, the water, the dark pigment, the biological calcium powder and the superplasticizer are prepared into the components in sequence by weight ratio: 8.5% -16.0%, 3.5% -11.0%, 39.4% -49.8%, 24.9% -37.3%, 6.2% -8.7%, 0.2% -1.7% and 0.02% -0.1%.

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 are modified according to the influence degree on the performance of concrete, and one of transparent resin, organic silicon, dimethyl siloxane and super-hydrophobic materials is adopted for modification treatment.

Preferably, the biological calcium powder is bovine bone powder and 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 powder is 100-1000 meshes.

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

Preferably, the portland cement is ordinary portland cement with the strength grade being more than 32.5, and the mineral admixture comprises one or more of silica fume, slag powder and fly ash.

Preferably, the sand is one or more of river sand, machine-made sand or desalted sea sand, and the grading is good.

A preparation method of green concrete for inducing marine periphyton attachment comprises the following steps:

s1: accurately weighing portland cement, mineral admixture, broken stone, sand, water, dark pigment, biological calcium powder and a superplasticizer;

s2: firstly, placing broken stone and sand into a concrete mixer to be mixed for 0.5-1 minute; then adding portland cement, mineral admixture, biological calcium powder and dark pigment, and continuing stirring for 0.5-1 minute; then adding water and a superplasticizer, and stirring for 2-6 minutes; and after the mixture is uniformly stirred, pouring and vibrating, and then carrying out standard curing for 28d or curing according to actual conditions to obtain the deep-color portland cement concrete with good induction effect and attached marine sessile organisms.

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

the strength and permeability of concrete are the two most important properties of concrete. When considering that different substances are added to promote the adhesion, metamorphosis and later growth of oyster larvae, the strength and permeability of the concrete are not greatly influenced by the oyster larvae, and then raw materials are selected according to the compatibility of various raw materials.

Drawings

FIG. 1 shows the mildew on the surface of concrete mixed with 10% of bovine bone meal in different mixing ratios.

FIG. 2 shows different mixing ratios of modified 10% bovine bone meal with fineness greater than 200 meshes.

FIG. 3 is a schematic diagram of a sea adhesion experiment 200 d.

FIG. 4 is a schematic diagram of a sea adhesion experiment 300 d.

Detailed Description

The present invention is described in detail below with reference to examples, which are provided only for illustrating the present invention and do not limit the scope of the present invention. The concrete mixing ratio of the concrete is as follows:

example 1: the mixing proportion of the ordinary portland cement concrete refers to the weight proportion of ordinary portland cement, broken stone, sand, water and polycarboxylic acid water reducer powder in sequence: 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), Cl^-The content is less than 1000mg/L, the PH value is more than 4.5, and the cement mortar has small influence on initial setting time difference, final setting time, strength and permeability of cement. The materials selected in examples 1 to 16 are the same.

Example 2: the reference concrete mixing proportion is as follows: the weight ratio of 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 is as follows in sequence: 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 reducing the effect of alkalinity difference between concrete and seawater contacted with the concrete, and finally, oyster larvae are easier to attach to the surface of the concrete.

Example 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%.

Example 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%.

Example 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%.

Example 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%.

Example 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%.

Example 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 alkali exudation of the concrete is increased due to the increase of the permeability of the concrete, and on the other hand, the concentration of iron ions is increased probably due to the conversion of iron oxides into iron ions, which can inhibit the attachment of oyster larvae. 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.

Example 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%.

Example 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%.

Example 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%.

Example 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%.

Example 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%.

Example 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 to grind, the bovine bone powder is difficult to grind again generally about 100 meshes, wherein the bovine bone powder of 80 meshes is chemically modified by adopting dilute phosphoric acid with the concentration of 2 percent, and then the dried bovine bone powder and 1:4 slag powder are ground into powder with 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 the oyster larvae is increased from 205% to 400%.

Example 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%.

Example 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%, 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 ^2-、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 content of the dark pigment is 0.86%, the content of the oyster shell powder is 0.51% and the content of the bovine bone powder is 0.51%, and the adhesion change rate is increased by 517% when the content of the dark pigment is 0.86%, the content of the oyster shell powder is 0.51% and the content of the bovine bone powder is 0.86%.

The specific operation steps of the implementation method of the embodiment 1-16 are as follows:

according to the preparation method of the deep-color portland cement concrete for inducing marine periphyton attachment, 3 phi 100X 50mm cylindrical test pieces and 10 200X 30mm cuboid test pieces are prepared and are respectively used for testing the chloride ion permeability resistance of the concrete for 28d and the attachment 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 ordinary portland cement, the mineral admixture, the broken stone, the sand, the water, the dark pigment, the biological calcium powder and the polycarboxylic acid water reducer 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 admixture, biological calcium powder and dark pigment, and continuing stirring for 0.5-1 minute; then adding 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 stability to resistance Chloride Ion agriculture (ASTM1202-2017), in Standard curing for 28d, 3 cylindrical Test pieces with a diameter of 100X 50mm are taken out from a curing room respectively, the surface moisture and sundries are cleaned, and after the surface is dried, a thin layer of epoxy resin is coated on the side surface 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, the experimental data were recorded after 6h, and the latter two test pieces were repeated. 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 curing for 28 days, respectively taking out cuboid test pieces of 200X 30mm from a curing room, cleaning the surface moisture and impurities, then putting the cuboid test pieces into a test pool, and preparing the test pool in the laboratory, wherein the abundance of oyster larvae is 0.85ind/ml³And the seawater in the pond is yellow sea seawater after sand filtration, the salinity is about 32% -34%, and after the seawater level is higher than the concrete sample, oxygen pipes are uniformly dispersed in the test pond to prepare for throwing the oyster larvae. Slowly stirring Concha Ostreae larva in water bucket, and accurately weighing Concha Ostreae larva in beakerThen evenly distributed in the test cell.

And after the oyster adhesion induction test is started, replacing seawater in the test pool every day, wherein the water replacement amount is 1/3 of the total volume of the test pool, blocking a water outlet by using a screen (not less than 200 meshes) to prevent the unattached oyster seedlings from losing along with water, putting the seedlings on the screen into the test pool again, feeding chlorella regularly and quantitatively by using a rubber head dropper at 9 and 19 days every day, and observing the oyster adhesion condition.

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, and taking out the smooth bottom surface of the concrete when the concrete is poured and molded when the statistics is carried out.

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 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 into concrete, the purpose is mainly achieved by surface bionic property, fish, microorganisms and algae are collected, the number of microorganisms is increased, and the water environment is improved, and oyster is not mentioned. The 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 obtained bovine bone powder and the biological calcium carbonate powder is within 10 percent of the cementing material.

(3) By modifying the bovine bone powder and the biological calcium carbonate powder, in particular to egg shell powder, coral powder, oyster shell powder and fishbone powder of 100 meshes to 500 meshes which 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 with 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 method can not be adopted on the surface of each project, so that the feasibility is low. 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 in acid corrosion resistance, and therefore, excessive calcium carbonate with 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 differences are:

(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. Similarly, bovine bone powder is mixed with biological calcium carbonate powder, such as one or more of oyster shell powder, egg shell powder, fishbone powder and coral powder. The aim is to give full play to the induction capability of concrete while considering the grading of concrete particles.

(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 keeps 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 reduction of the strength and the impermeability of the concrete, 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 the surface of the concrete grows mildewed under the standard curing condition. FIG. 1 shows the mildew formation of a concrete specimen. FIG. 2 shows the surface condition of the modified concrete.

As can be seen from FIG. 1, the mold on the concrete surface appeared white flocculent, covering almost the entire concrete surface; the concrete surface in figure 2 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.

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 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 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). It is currently believed to induceThe optimal range of calcium ion concentration attached to Concha Ostreae is 10-25 mmol/L, and even if Concha Ostreae larva is placed in saturated calcium carbonate solution, there is not enough Ca²⁺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. Therefore, it was confirmed that incorporation of 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 the oyster reaches the maximum value; as the doping amount continues to increase, the calcium ions decrease greatly, carbonate ions may decrease, and the concentration of the calcium ions can limit the attachment of oyster larvae, which is expressed as the decrease of the attachment amount;

3) for an equal amount of substituted mineral admixture, the permeability is increased along with the increase of the admixture,and the addition of calcium carbonate can make the oyster adhere to the required HCO₃ ^-The concentration reaches a proper range, which is shown as the attachment of oyster larvae is increased; as the amount of the mineral admixture continues to increase, the amount 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:

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 adhesion, 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 adhesion and metamorphosis of oysters, so that two kinds of concrete look the same and are greatly different. Fig. 3 and 4 are comparison results of biological adhesion after the comparison document 4 passes through the real sea adhesion experiment of about 210d and the real sea adhesion experiment of 300d according to the present invention, respectively.

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 inside the concrete is higher. 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.

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 features of the present invention that closely relate the balance between the concrete alkalinity reduction and the calcium ion concentration to the attachment of marine periphyton through the comparison of document 1.

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

dark 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. Therefore, the amount of the dark color substance is determined according to the type and amount of the cement. Dark pigments also affect the properties of the 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 affect the attachment, metamorphosis and growth of sessile organism larva, and when the mixing amount is greater than a certain value, the larva attachmentThe amount of deposits is reduced. The impermeability of the concrete is designed and controlled, and the main measures are as follows: selecting the type of the dark pigment, controlling the adding amount and modifying. The attachment rate of the larvae is increased along with the increase of the doped amount of the dark substance, and when the doped amount is 0.5-6% of the cementing material, the attachment amount of the larvae is maximum, but then the attachment amount is slightly increased or kept unchanged.

And (3) concrete permeability:

the strength and permeability of concrete are the two most important properties of concrete. When considering that different substances are added to promote the adhesion, metamorphosis and later growth of oyster larvae, the strength and permeability of the concrete are not greatly influenced by the oyster larvae, and then raw materials are selected according to the compatibility of various raw materials. 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 alkali and ion leakage rate in the concrete is changed due to the change of the concrete permeability, and the lower the impermeability of the concrete is, the larger the alkali and ion leakage rate in the concrete is, and the increase of the alkali and ion leakage rate in the concrete is probably exponential. Thus, these released alkalis and ions have a great influence on the larvae, and there may be cases where the adhesion is promoted to be inhibited, which is more serious particularly when the cement is contained in a large amount. Therefore, the inducer is added into the 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 these can only be compared, otherwise the influence of the single or compound addition of the 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.

Therefore, since this part of knowledge relates to the intersection of marine periphytons, marine plants and marine concrete engineering disciplines, no matter those skilled in the concrete and engineering fields or marine life fields, the technical features of the present invention of color change by incorporating a dark pigment into concrete, bovine bone meal modification and milling technology and control of concrete permeability closely linked to concrete having high efficiency of inducing oyster attachment ability and high durability could be obtained by comparing 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 deep-color portland cement concrete for inducing adhesion of marine periphyton is characterized in that: the paint is prepared from portland cement, a mineral admixture, crushed stone, sand, water, a dark color pigment, biological calcium powder and a superplasticizer, wherein the portland cement, the mineral admixture, the crushed stone, the sand, the water, the dark color pigment, the biological calcium powder and the superplasticizer are sequentially prepared from the following components in parts by weight: 8.5% -16.0%, 3.5% -11.0%, 39.4% -49.8%, 24.9% -37.3%, 6.2% -8.7%, 0.2% -1.7% and 0.02% -0.1%.

2. The dark portland cement concrete for inducing adhesion of marine periphyton according to claim 1, wherein: the dark pigment is one or two of iron oxide black, aniline black, carbon black, antimony sulfide, iron oxide red and organic pigment red.

3. The dark portland cement concrete for inducing adhesion of marine periphyton according to claim 2, wherein: the deep color pigment is modified according to the influence degree on the performance of concrete, and is modified by adopting one of transparent resin, organic silicon, dimethyl siloxane and super-hydrophobic materials.

4. The dark portland cement concrete for inducing adhesion of marine periphyton according to claim 1, wherein: the biological calcium powder is one or a plurality of compounds of ox bone powder and biological calcium carbonate powder including oyster shell powder, fishbone powder, egg shell powder and coral powder, and the fineness of the biological calcium powder is 100-1000 meshes.

5. The dark portland cement concrete for inducing adhesion of marine periphyton according to claim 4, wherein: the biological calcium powder is prepared by treating 100-500 mesh oyster shell powder, egg shell powder, coral 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.

6. The dark portland cement concrete for inducing adhesion of marine periphyton according to claim 1, wherein: the Portland cement is ordinary Portland cement, the strength grade is more than 32.5, and the mineral admixture comprises one or more of silica fume, slag powder and fly ash.

7. The dark portland cement concrete for inducing adhesion of marine periphyton according to claim 1, wherein: the sand is one or more of river sand, machine-made sand or desalted sea sand.

8. A preparation method of dark portland cement concrete for inducing marine periphyton adhesion is characterized by comprising the following steps:

s2: firstly, placing broken stone and sand into a concrete mixer to be mixed for 0.5-1 minute; then adding portland cement, mineral admixture, biological calcium powder and dark pigment, and continuing stirring for 0.5-1 minute; then adding water and a superplasticizer, and stirring for 2-6 minutes; and after uniformly stirring, pouring and vibrating, and then performing standard curing for 28d or curing according to actual conditions, thereby obtaining the deep-color portland cement concrete with good induction effect and attached marine sessile organisms.