CN111320935A

CN111320935A - Emulsified asphalt-cement-based coating and preparation method thereof

Info

Publication number: CN111320935A
Application number: CN201911210405.7A
Authority: CN
Inventors: 吕建福; 汪明军
Original assignee: Harbin Engineering University
Current assignee: Harbin Engineering University
Priority date: 2019-12-02
Filing date: 2019-12-02
Publication date: 2020-06-23

Abstract

The invention relates to an emulsified asphalt-cement-based coating technology for inducing marine periphyton adhesion, in particular to an emulsified asphalt-cement-based coating and a preparation method thereof, belonging to the interdisciplinary field of marine periphyton and marine engineering coatings. The material composition of the invention is: cementing materials, emulsified asphalt, sand, water, biological calcium powder, calcium carbonate powder, trace elements, acrylic emulsion and superplasticizer. The invention can be applied to newly-built ocean engineering, in particular to a great number of active engineering in the ocean. The method can improve the durability of the reinforced concrete structure and simply and economically realize the restoration of the marine ecological environment. The method not only greatly widens the corrosion prevention application of the marine sessile organisms in the serving reinforced concrete structure, but also can be widely applied to marine ecological environment restoration engineering.

Description

Emulsified asphalt-cement-based coating and preparation method thereof

Technical Field

The invention relates to an emulsified asphalt-cement-based coating technology for inducing marine periphyton adhesion, in particular to an emulsified asphalt-cement-based coating and a preparation method thereof, belonging to the interdisciplinary field of marine periphyton and marine engineering coatings.

Background

In marine concrete structure anticorrosion technology, surface coating protection is the most common marine anticorrosion technology due to its economy and practicality. However, for marine concrete structures in a tidal range area and a full immersion area, the general coating cannot meet the requirements because the sea concrete structures are in a wet state or are always immersed in water due to tidal rise and tidal fall. There is therefore a need for a coating which can be applied and cured directly in seawater or in a humid environment. Currently, anticorrosive coatings for underwater and wet interfaces such as polyester resin systems, vinyl resin systems, and epoxy resin systems have been developed. However, the method has the problems of insufficient adhesion with the concrete interface, short service time, high manufacturing cost and the like, and particularly, some plant and microbial films and the like are often adhered to the concrete surface, because the requirement of the anticorrosive paint on the adhesion surface is high, but the surface is difficult to clean to the extent that the anticorrosive paint can be brushed.

At present, researches show that sessile organisms attached to the surface of concrete, such as oysters and barnacles, can improve the impermeability of the concrete and further improve the durability of a marine concrete structure, and the more compact the sessile organisms are attached, the more obvious the protection effect is. The marine periphyton 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. However, in practical engineering, sessile organisms are affected by external environment, and the phenomena of sparse attachment, loose attachment and even no attachment often occur. Recent studies have shown that oyster attachment and growth are associated with the substrate, and concrete is a preferred substrate. The attachment amount of oyster larvae is increased by adding calcium materials such as biological calcium carbonate powder, gypsum powder and the like into cement; oyster is also easier to adhere to dark substrates, and the like. For concrete structures in service, it is not practical to change the substrate by dismantling the reconstruction. The concrete surface is treated and painted to realize the function of inducing attachment of sessile organisms. However, the paint coated on the concrete surface induces the attachment of attachment organisms, and relevant data are not found in the corrosion prevention of the reinforced concrete structure in the marine environment. Therefore, there is a need to develop a coating capable of rapidly increasing the amount of adhesion of marine periphyton on the surface of concrete, particularly a coating capable of rapidly inducing periphyton adhesion and metamorphosis and promoting long-term growth, and having the characteristics of simple construction and easy coating. The application field of marine sessile organisms in the corrosion prevention of reinforced concrete is greatly widened.

CN104938384 is to mix 150-200 mesh biological calcium carbonate powder (fishbone, coral, egg shell and shell are 1:1:1:1) and shell fragment which are 10-20% of the cement mass into the artificial fish reef, which shows that the induced biomass is gradually increased along with the increase of the calcium carbonate mixing amount, and the biomass (marine plant and marine organism) induced by the biological calcium carbonate is the most when the mixing amount is the maximum (20% of the cement weight). In order to reduce the alkalinity of the surface of the concrete artificial fish reef, microorganisms and algae are easier to attach, the biomass and the population quantity are increased, and the fish collecting effect is better. The biological calcium carbonate cement mortar coating layer educt is harmless to the environment and the organism. Although the biological calcium carbonate powder, the oyster shell fragments and the like are doped into concrete for artificial fish reef manufacturing and biological attachment experiments, the biological calcium carbonate powder indeed enhances the biological enrichment effect, but mainly enriches marine plants and microorganisms.

Meanwhile, as coastal economy develops rapidly in recent decades without paying attention to environmental protection, 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 measures are not taken, a greater disaster is certainly brought to the ecology along the shore of the ocean. Meanwhile, most coastal infrastructures cannot be dismantled, and the ecology in the sea area needs to be restored, so that people gradually realize the application of ecological 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. 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, a concrete oyster attaching base would be in great demand. At present, relevant researches on oyster attachment at home and abroad are as follows:

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

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

At present, with the great application of concrete in ocean engineering, particularly recent oyster reef repair engineering and the like, the concrete becomes a substrate material which is most commonly attached by marine periphyton. 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 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 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 better the ecological effect is. The ecological concrete engineering for building the United states adopts low-alkalinity cement concrete, such as aluminate cement, particularly slag portland cement, wherein the replacement amount of slag powder reaches 50 percent, and the ecological effect of enriching marine plants, animals and the like is better. By adopting cement with lower alkalinity to prepare concrete, biomass (mainly marine plants) sensitive to alkali can be effectively improved, but the improvement of the attachment amount and the attachment density of oysters is limited.

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

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. Although the enrichment effect of organisms is enhanced by adding oyster shell fragments, the organisms are mainly enriched by 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; dissolution of calcium carbonateThe solubility is very small, and is only 9.5 × 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, it was confirmed that incorporation of calcium carbonate material into concrete promotes adhesion of oyster larvae, Ca²⁺Not the dominant role.

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

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

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

The color of the substrate has certain influence on the attachment, metamorphosis and growth of the larvae of the marine periphyton. 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.

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 repairing oyster reefs, building artificial ecological engineering and preventing corrosion of marine reinforced concrete at present, and the influence of the color on the attachment amount of sessile organism larvae is not referred to related data

Although the above studies are currently carried out, such as the effect of different substrates and colors on marine periphyton attachment, the effect of incorporating calcareous materials into concrete on marine periphyton attachment has recently been studied. But no relevant research for inducing marine periphyton coating exists at present. The in-service concrete engineering, waste concrete and the like can realize the ecological environment restoration of ocean engineering by surface treatment and coating of coatings for inducing adhesion of sessile organisms, is a research direction of engineering ecology with great potential, and is particularly used for oyster reef restoration, artificial ecological engineering construction and corrosion prevention of ocean reinforced concrete currently carried out. The knowledge of related subjects such as marine organisms, marine microorganisms, marine chemistry, marine concrete engineering materials and structures is involved, and the subject directions are different greatly, so that the problems are more encountered in cross research, such as the problems that the cement-based materials are not clear in water-cement ratio, the mechanism of oyster adhesion induced by calcium carbonate materials is unclear, the concrete durability is seriously insufficient due to excessive calcium powder added into cement, the added bovine bone meal is easy to mildew, and the like.

Disclosure of Invention

The invention aims to invent a coating capable of being directly brushed and cured in a humid environment, which can induce sessile organisms to be quickly and compactly attached to the surface of concrete, achieve the biological anti-corrosion effect by utilizing the fixation characteristic of oysters, and achieve the aims of purifying water bodies and restoring ecology by virtue of large-scale attachment of the sessile organisms. The problems of limited effect, short service time, high manufacturing cost and the like of corrosion prevention measures in tidal range areas and underwater areas of marine concrete engineering are solved, and marine ecological restoration is urgently needed for ecological deterioration.

The invention aims to realize that the prepared emulsified asphalt-cement-based coating has high capability of inducing adhesion and metamorphosis of oyster larvae by using a low-alkalinity cementing material, acrylic emulsion and a superplasticizer and adding emulsified asphalt, modified biological calcium powder, calcium carbonate powder and trace elements into the coating, and simultaneously has the capability of directly brushing and curing in a humid environment, thereby realizing the effect of uniform and compact adhesion of oysters, ensuring the durability of a concrete structure by utilizing the fixation characteristic of the oysters, and not polluting the marine environment.

The invention also includes such structural features:

the material components are as follows: the adhesive comprises a cementing material, emulsified asphalt, sand, water, biological calcium powder, calcium carbonate powder, trace elements, acrylic emulsion and a superplasticizer, wherein the weight ratio is 1: (0.4-0.8), (0.5-1.3), (0.10-0.30), (0.02-0.10), (0.01-0.08), (0.08-0.15) and (0.001-0.008).

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

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

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

Preferably, the acrylic emulsion is a polyurethane modified emulsion.

Preferably, the emulsified asphalt is one of cationic emulsified asphalt and anionic emulsified asphalt. The performance indexes are that the content of evaporation residues is more than 55 percent, the stability of 5 days is less than or equal to 5 percent, and the residue on a sieve (a sieve with 1.18 mm) is less than or equal to 0.1 percent.

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

Preferably, the sand is one or more of river sand with the particle size of 0.16-2.36 mm, machine-made sand (mother rock can be limestone, basalt or granite) and sea sand.

Preferably, the superplasticizer is, for example, one of polycarboxylic acids and naphthalene series.

A preparation method of an emulsified asphalt-cement-based coating comprises the following steps:

s1: weighing emulsified asphalt, a cementing material, sand, water, biological calcium powder, calcium carbonate powder, trace elements, acrylic emulsion and a superplasticizer;

s2: placing the cementing material, the biological calcium powder, the calcium carbonate powder, the trace elements and the powdery superplasticizer into a mixer, wherein the rotating speed is 1000-1500 rpm, and the mixing time is 4-8 minutes;

s3: then placing the sand into the sand, adjusting the rotating speed to be 500-;

s4: mixing the acrylic emulsion, the emulsified asphalt and water uniformly, and placing the mixture and the uniformly mixed materials into a 200-fold high-speed stirrer with the rotation speed of 500 rpm for stirring for 5-10 minutes. The emulsified asphalt-cement-based coating with good induction effect for inducing sessile organisms on the surface of ocean engineering can be prepared

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

at present, no matter the durability of the marine concrete or the ecological engineering of the marine concrete, a green and economic method is lacked. The oyster is used as an ecological engineer of the sea, and has the functions of densifying the surface of a concrete structure, improving the ecological environment and the like. The sessile organism inducing emulsified asphalt-cement-based paint provided by the invention has the characteristics of rapidly inducing attachment and metamorphosis of sessile organisms and promoting long-term growth, and also has the characteristics of simple construction and easy painting. Can be applied to newly-built ocean engineering, in particular to a great number of active engineering in the ocean. The method can improve the durability of the reinforced concrete structure and simply and economically realize the restoration of the marine ecological environment. The method not only greatly widens the corrosion prevention application of the marine sessile organisms in the serving reinforced concrete structure, but also can be widely applied to marine ecological environment restoration engineering.

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 coating mix proportions of the examples are as follows:

example 1: emulsified asphalt, a cementing material, sand, water, modified biological calcium powder (modified bovine bone powder: oyster shell powder: 2:1), calcium carbonate powder, zinc sulfate, acrylic emulsion and a superplasticizer in sequence by weight: 0.6:1:1:0.20:0.03:0.03:0.02:0.12:0.005.

Example 2: the emulsified asphalt, a cementing material, sand, water, modified biological calcium powder (modified bovine bone powder: oyster shell powder: 2:1), calcium carbonate powder, zinc sulfate, acrylic emulsion and a superplasticizer are sequentially prepared from the following components in percentage by weight: 0.6:1:1:0.20:0.05:0.05:0.04:0.12:0.005.

Example 3: the emulsified asphalt, a cementing material, sand, water, modified biological calcium powder (modified bovine bone powder: oyster shell powder: 2:1), calcium carbonate powder, zinc sulfate, acrylic emulsion and a superplasticizer are sequentially prepared from the following components in percentage by weight: 0.6:1:1:0.20:0.08:0.08:0.06:0.12:0.005.

Example 4: the emulsified asphalt, a cementing material, sand, water, modified biological calcium powder (modified bovine bone powder: oyster shell powder: 2:1), calcium carbonate powder, zinc sulfate, acrylic emulsion and a superplasticizer are sequentially prepared from the following components in percentage by weight: 0.6:1:1:0.20:0.08:0.08:0.02:0.12:0.005.

Example 5: the emulsified asphalt, a cementing material, sand, water, modified biological calcium powder (modified bovine bone powder: oyster shell powder: 2:1), calcium carbonate powder, zinc sulfate, acrylic emulsion and a superplasticizer are sequentially prepared from the following components in percentage by weight: 0.6:1:1:0.20:0.03:0.03:0.06:0.12:0.005.

Example 6: emulsified asphalt, a cementing material, sand, water, modified biological calcium powder (modified bovine bone powder: oyster shell powder: 2:1), calcium carbonate powder, zinc sulfate, acrylic emulsion and a superplasticizer in sequence by weight: 0.6:1:1:0.20:0.03:0.03:0.04:0.12:0.005.

Example 7: the emulsified asphalt, a cementing material, sand, water, modified biological calcium powder (modified bovine bone powder: oyster shell powder: 2:1), calcium carbonate powder, zinc sulfate, acrylic emulsion and a superplasticizer are sequentially prepared from the following components in percentage by weight: 0.6:1:1:0.20:0.05:0.05:0.02:0.12:0.005.

Example 8: the emulsified asphalt, a cementing material, sand, water, modified biological calcium powder (modified bovine bone powder: oyster shell powder: 2:1), calcium carbonate powder, zinc sulfate, acrylic emulsion and a superplasticizer are sequentially prepared from the following components in percentage by weight: 0.6:1:1:0.20:0.08:0.08:0.04:0.12:0.005.

Example 9: the emulsified asphalt, a cementing material, sand, water, modified biological calcium powder (modified bovine bone powder: oyster shell powder: 2:1), calcium carbonate powder, zinc sulfate, acrylic emulsion and a superplasticizer are sequentially prepared from the following components in percentage by weight: 0.6:1:1:0.20:0.08:0.08:0.06:0.12:0.005.

Example 10: the emulsified asphalt, a cementing material, sand, water, modified biological calcium powder (modified bovine bone powder: oyster shell powder: 2:1), calcium carbonate powder, zinc sulfate, acrylic emulsion and a superplasticizer are sequentially prepared from the following components in percentage by weight: 0.6:1:1:0.20:0.03:0.05:0.02:0.12:0.005.

The method for modifying the bovine bone meal comprises the following steps: adding 100-mesh bovine bone meal into 2% phosphoric acid solution, wherein the weight ratio of the bovine bone meal to the phosphoric acid solution is 1:3, the temperature is 20-30 ℃, the mixture is stirred for 30 minutes in a stirrer with the rotating speed of 200-500 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; and (3) drying the centrifuged solid substance in vacuum at 40 ℃, mixing the dried bovine bone meal and the slag powder according to the weight ratio of 1:4, and grinding the mixture by using a vibration mill until the fineness is more than 200 meshes for later use.

The modification method of zinc sulfate comprises the following steps: selecting diatomite SiO₂Adding 150g of water and 100g of zinc sulfate into diatomite with the content of more than 90 percent and the fineness of 600 meshes in a stirrer at the temperature of 60 ℃, and stirring until the mixture is completely dissolved for later use; and then 150g of the diatomite is heated to 60 ℃, 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.

Compared with the comparative document 1 (a bionic concrete artificial fish reef and a preparation method 2015CN104938384A), the differences are that:

(1) the object in the present invention is different from comparative document 1: in comparison document 1, although a layer of cement mortar mixed with ground oyster shells is coated on the surface of concrete, the purpose is mainly achieved by surface bionic property, fish, microorganisms and algae are collected, the number of microorganisms is increased, and the water environment is improved, and oyster is not mentioned. The emulsified asphalt-cement-based coating aims at inducing attachment of sessile organisms, mainly oysters, and considering the attachment of barnacles when reinforced concrete is used for corrosion prevention in a tidal range.

(2) The comparison document 1 indicates that in cement mortar, the biological calcium carbonate powder (150-200 meshes) with the cement mass of less than 10% is not obvious in induced adhesion. In the research process, the modified bovine bone meal and biological calcium carbonate powder are mixed to form the emulsified asphalt-cement-based coating (the fineness is 100-1000 meshes), so that the optimal mixing amount of the bovine bone meal and the biological calcium carbonate powder is within 10% of that 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 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 method can not be adopted on the surface of each project, so that the feasibility is low. The invention can achieve the effect of inducing sessile organisms by coating a layer of emulsified asphalt-cement-based paint on the surface of concrete, does not need to be embedded with oyster shells, has simple construction and can also greatly increase the attachment of the oysters.

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

Compared to reference 2 (Vanreilin. influence of matrix type on oyster attachment, growth, population establishment and reef development [ D ]), the differences are:

(1) in comparison document 2, 80-mesh bovine bone powder, calcium powder and gypsum powder were used, each separately blended in concrete. The fineness of all the calcium materials in the invention is more than 100 meshes and more than that of the materials in the comparison document 3. And the modified bovine bone meal is added, and the grain composition and the induction capability thereof in the coating are considered.

(2) Grinding the bovine bone powder by using a vibration mill at normal temperature, wherein when the fineness is more than 80 meshes, the bovine bone powder contains a large amount of collagen and is seriously agglomerated, so that the bovine bone powder cannot be continuously ground. The invention adopts dilute acid modification technology and is compounded with other substances and ground to obtain the modified biological calcium powder with small particle size and fineness of more than 200 meshes. The prepared biological calcium powder 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 the coating.

(3) Because the bovine bone meal contains rich organic substances such as collagen, the great amount of the substances causes the strength and the impermeability of the coating to be reduced, particularly, after the content of the organic substances exceeds 5 percent, the addition amount is increased, the strength of the coating is rapidly reduced, the impermeability is obviously reduced, and the coating grows mildewed under standard 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 performance of the coating, simultaneously has strong oyster larva attachment capability, and solves the problem of mildew of the coating after being coated. Compared with the coating without the inducer, the number of the oyster larvae attached to the concrete coated with the inducer-doped coating is obviously increased.

The comparison documents and the literature data found show that the calcium content is crucial to the attachment of oyster larvae, and the experimental results also show that the cement-based material is doped with a proper amount of calcium carbonate to promote the attachment and growth of oyster larvae, but the cement-based coating has a large amount of calcium ions, the pH value of a pore solution is generally more than 12.5, the pH value of a saturated calcium hydroxide solution is about 12 at normal temperature, the concentration of the calcium ions in the pore solution is about 5mmol/L, the solubility of calcium carbonate is very small, and the calcium carbonate is only 9.5 × 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 of the oyster powder can provide proper adhesion to the oysterPreferably the ion concentration. Further, Ca (OH) in the interior of the dope₂Can be released more quickly, while the dissolution of calcium carbonate takes longer. Therefore, it was confirmed that calcium carbonate material, Ca, was incorporated in the paint to promote adhesion of oyster larvae²⁺Not the dominant role. Early attachment, metamorphosis and HCO of oyster₃ ^-Related to Ca in allergy²⁺Together generating a secondary shell of calcium carbonate. After calcium carbonate is added, the calcium carbonate is mixed with CO₂Reacting with water to form Ca (HCO)₃)₂The later participation in the attachment is the fundamental mechanism for promoting the attachment of oyster larvae.

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

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

2) for the same amount of substituted aggregate, the permeability of the cement-based material is reduced along with the increase of the mixing amount, which can cause calcium ions and OH^-The bleeding of (2) is reduced, but the permeation rate of carbonate ions is gradually increased, and when reaching a certain value, the adhesion of the oyster reaches the maximum value; as the doping amount continues to increase, the calcium ions decrease greatly, carbonate ions may decrease, and the concentration of the calcium ions can limit the attachment of oyster larvae, which is expressed as the decrease of the attachment amount;

3) for the same amount of mineral-substituted admixtures, the permeability is increased along with the increase of the admixture, and the HCO required for oyster adhesion 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 minerals are blendedThe blending amount of the mineral admixture is continuously increased and reduced, so that the amount of alkali exuded is increased, carbonate is increased, but excessive alkali and HCO are generated₃ ^-The ions inhibit adhesion of oyster larvae.

Compared with the comparison document 3 (plum true, public, green, heavy, et. bio-adhesion effect of concrete artificial fish reef of different cement types [ J ] fishery science progress, 2017,38(5):57-63.), the difference is that:

in comparison document 3, composite portland cement, slag portland cement, pozzolanic portland cement, fly ash portland cement, and aluminate cement are used: the invention adopts the composite doping of ordinary portland cement and mineral admixture to realize low-alkalinity cement; the silica fume is one of mineral admixtures, has high activity, has obvious effect of improving the durability of reinforced concrete in the marine environment by proper mixing amount, and can obtain low-alkalinity cement with excellent strength and durability through optimized design and experiments. Meanwhile, by utilizing the characteristic of high impermeability of the silica fume concrete, a large amount of oyster larvae are attached, distorted and grown even if the alkalinity inside the concrete is higher. And the alkalinity of the emulsified asphalt-cement-based coating is regulated and controlled by adopting the composition of the low-alkalinity sulphoaluminate cement, so that a proper pH value is provided for adhesion of oyster larvae. In addition, marine plants and sessile organisms such as oysters and barnacles have different alkali resistance and different environments required in the attachment period and later period, such as the attachment, metamorphosis and later growth of barnacles and oysters, need a large amount of calcium ions.

The concrete in the comparison document 3 is used for enriching marine organisms, mainly in view of the size and diversity of attached biomass, and the main attached organisms are various algae and the like. The aim of research in the invention is to induce oyster attachment, but the tolerance of oysters and barnacles to alkalinity is higher than that of algae, and a large amount of calcium ions are needed for oyster attachment and metamorphosis, so that two cement-based materials look the same and are greatly different.

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

dark substance

Utilize oyster eyespot larva's light-resistant characteristic, mix the coating with emulsified asphalt in, change the colour of coating, make the colour of coating deepen, let the oyster larva think be the dark environment, induced oyster larva arrives dark concrete surface by oneself, increases the contact probability on larva and concrete surface, realizes that the induced attachment rate of oyster larva increases. The method specifically comprises the following steps:

the researchers of marine organisms, in order to breed and proliferate or in order to eliminate undesirable populations, consider the study of the adhesion of marine periphyton with different colored substrates, belonging to the subject of marine biology. The discipline of marine concrete engineering or concrete materials is quite different and is two big disciplines. By crossing the marine sessile organisms with the concrete discipline, the oyster larva induced attachment by adopting the dark-color coating is obtained. The invention adopts the addition of emulsified asphalt to deepen the color of the coating to promote the attachment of oyster larvae. The incorporation of other materials into the coating can affect its performance. The invention considers the paint of different cement, which has different colors. Therefore, the amount of the dark color substance is determined according to the type and amount of the cement. Emulsified asphalt can also affect the properties of the coating. Most importantly, when the emulsified asphalt is added, alkali and Ca in the coating are not controlled²⁺When the permeation rate is equal, the released alkali can influence the attachment, metamorphosis and growth of sessile organism larvae, and when the mixing amount is more than a certain value, the attachment amount of the larvae is reduced. The invention designs and controls the impermeability of the emulsified asphalt-cement-based coating, and the main measures are as follows: controlling the addition amount and modifying. The attachment rate of the larvae is increased along with the increase of the doped amount of the dark substance, and when the doped amount is 0.5-6% of the cementing material, the attachment amount of the larvae is maximum, but then the attachment amount is slightly increased or kept unchanged.

Trace elements

According to the enrichment of a large amount of zinc in the oyster body, the zinc is far higher than the seawater where the oyster lives, and meanwhile, the oyster body also contains more Fe, P and K elements. At the same time, the appropriate Zn in the solution²⁺，K⁺The concentration can promote early stage attachment and metamorphosis of oyster larva. Therefore, zinc sulfate, potassium nitrate and sulfuric acid are adoptedIron, zinc phosphate, ammonium nitrate, potassium phosphate, ammonium phosphate, iron phosphate and calcium phosphate are used as trace elements to be doped into the coating, and the strength and the impermeability of the coating are basically kept unchanged by 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 discipline of marine concrete engineering or concrete materials is quite different and is two big disciplines. Through the crossing of marine sessile organisms and concrete disciplines, the method is obtained by adding corresponding substances into the coating to induce the adhesion of oyster larvae on the surface of concrete. Because the soluble salts greatly affect the performance of the coating, such as the early workability, the setting time and the later strength and impermeability, the invention adopts the diatomite as the carrier, fixes the inorganic salts in the diatomite, reduces the influence of the soluble salts on the performance of the coating, and simultaneously utilizes the function of the diatomite to improve the performance of the emulsified asphalt-cement-based coating to realize that the good performance of the emulsified asphalt-cement-based coating can still be maintained when the inducing substances are added. In addition, the diatomite has a slow release effect as a carrier, so that the soluble salt is slowly released, and particularly, after the diatomite is soaked in seawater for a certain time, the release rate is maintained at a small rate. Therefore, this part of knowledge also relates to the intersection of marine periphyton, chemistry and marine concrete engineering disciplines, and no one skilled in the concrete and engineering fields or marine biology could obtain the technical characteristics of the present invention of incorporating trace elements into concrete, changing the ion content of trace elements on the surface of paint and controlling the permeability of paint in close relation to paint with high ability to induce oyster larvae attachment, by means of the existing background.

Permeability of paint

The strength and permeability of the coating are critical. When considering that different substances are added to promote adhesion, metamorphosis and later growth of oyster larvae, the performance of the coating is greatly influenced by the substances, the raw materials are selected according to the compatibility of various raw materials, and when the performance of the raw materials cannot meet the actual requirement, the raw materials are added after being modified, so that the expected functions are achieved. However, in the related researches, although the influence of the calcium content on the adhesion of the oyster larvae is considered, the water-cement ratio, the calcium content, the curing and the like are not considered in the performance of the coating, and the rate of alkali and ion leakage in the coating is changed due to the change of the permeability of the coating, so that the poorer the impermeability of the coating, the larger the leakage rate of alkali and ion in the coating is, and the increase of the permeability rate can be exponential. Thus, these released alkalis and ions have a great influence on the larvae, and there may be cases where the adhesion is promoted to be inhibited, which is more serious particularly when the cement is contained in a large amount. Therefore, the inducer is added into the coating, and the property change of the coating is ensured to be within a controllable range, such as the change is not more than 10%. The induction effects 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 adhesion, metamorphosis and later growth of the marine periphyton is mastered, and the coating can be designed based on the high impermeability of the coating, rather than neglecting the impermeability change of the coating due to the consideration of the mixing amount of various raw materials. Therefore, this part of knowledge also relates to the intersection of marine periphyton, chemistry and marine concrete engineering disciplines, and no one skilled in the concrete and engineering fields or marine life fields can obtain the technical characteristics of the present invention that the overall control of the impermeability of the coating and the close association of the inducer to the ability of the inducer to promote the efficient induced adhesion of oysters by the existing background.

Therefore, since this part of knowledge relates to the intersection of marine sessile organisms, 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 coating permeability in the emulsified asphalt of the present invention, which are closely related to the coating with high efficiency of inducing oyster attachment and high durability, can be obtained by comparing documents 1-2. And the technical feature of the present invention that the balance between the reduction in alkalinity of the coating and the concentration of calcium ions is closely linked to the adhesion of marine periphyton cannot be obtained by comparison with document 3.

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

Claims

1. An emulsified asphalt-cement-based coating is characterized in that: the adhesive is prepared from a cementing material, emulsified asphalt, sand, water, biological calcium powder, calcium carbonate powder, trace elements, an acrylic emulsion and a superplasticizer, wherein the cementing material, the emulsified asphalt, the sand, the water, the biological calcium powder, the calcium carbonate powder, the trace elements, the acrylic emulsion and the superplasticizer are sequentially prepared from the following components in parts by weight:

1:(0.4～0.8):(0.5～1.3):(0.10～0.30):(0.02～0.10):(0.02～0.10):(0.01～0.08):(0.08～0.15):(0.001～0.008)。

2. the emulsified asphalt-cement-based paint as claimed in claim 1, wherein: the biological calcium carbonate powder is one or a plurality of compounds of oyster shell powder, fishbone powder, egg shell powder and coral powder, and the fineness of the biological calcium carbonate powder is 100-1000 meshes.

3. The emulsified asphalt-cement-based paint as set forth in claim 2, wherein: the biological calcium powder is prepared by treating 100-500 mesh egg shell powder, coral powder, oyster shell powder and fishbone powder with acid including one or two of acetic acid, silicic acid and sulfurous acid; and treating the 100-500-mesh bovine bone powder with one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid.

4. The emulsified asphalt-cement-based paint as claimed in claim 1, wherein: the calcium carbonate powder is calcite, chalk, limestone, marble, aragonite, travertine powder, and one or more of light calcium carbonate, activated calcium carbonate, calcium carbonate whisker and superfine light calcium carbonate which are processed, and the fineness is more than 200 meshes.

5. The emulsified asphalt-cement-based paint as claimed in claim 1, wherein: the trace elements of zinc, iron, potassium and phosphorus are selected from natural minerals, industrial products or chemical reagents, including one or more of zinc sulfate, calcium phosphate, zinc phosphate, potassium sulfate, potassium nitrate, ferric sulfate, ammonium nitrate, potassium phosphate, ammonium phosphate and iron phosphate, and are modified to realize slow release of corresponding ions and reduce or eliminate adverse effects on the performance of concrete, and substances containing nitrogen and phosphorus elements are not selected for eutrophication areas.

6. The emulsified asphalt-cement-based paint as claimed in claim 1, wherein: the emulsified asphalt is one of cation emulsified asphalt and anion emulsified asphalt; the performance indexes are that the content of evaporation residues is more than 55 percent, the stability of 5d is less than or equal to 5 percent, and the residue on a sieve is less than or equal to 0.1 percent.

7. The emulsified asphalt-cement-based paint as claimed in claim 1, wherein: the cementing material is one of silicate cement, sulphoaluminate cement and alkali-activated cementing material which are mixed with mineral admixture; wherein the mineral admixture in the silicate cement doped with the mineral admixture comprises one or more of silica fume, slag powder and fly ash; the sulphoaluminate cement comprises one or two of quick-hardening sulphoaluminate cement, high-strength sulphoaluminate cement and expansion sulphoaluminate cement; the alkali-activated cementing material comprises one of alkali-activated slag, alkali-activated slag and fly ash.

8. The emulsified asphalt-cement-based paint as claimed in claim 1, wherein: the sand is one or more of river sand, machine-made sand and sea sand with the particle size of 0.16-2.36 mm.

9. The emulsified asphalt-cement-based paint as claimed in claim 1, wherein: the superplasticizer comprises one of polycarboxylic acid and naphthalene series.

10. The preparation method of the emulsified asphalt-cement-based coating is characterized by comprising the following steps:

s4: uniformly mixing the acrylic emulsion, the emulsified asphalt and water, and putting the mixture and the uniformly mixed materials into a 200-fold high-speed stirrer with the rotation speed of 500 rpm for stirring for 5-10 minutes; the emulsified asphalt-cement-based coating with good induction effect for inducing sessile organisms on the surface of ocean engineering can be prepared.