CN111499292B

CN111499292B - Oyster attachment base of fiber reinforced cement concrete and preparation method thereof

Info

Publication number: CN111499292B
Application number: CN201911210476.7A
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: 2022-01-14
Anticipated expiration: 2039-12-02
Also published as: CN111499292A

Abstract

The invention relates to an oyster attachment base technology, in particular to an oyster attachment base of fiber reinforced cement concrete and a preparation method thereof, belonging to the crossing field of marine periphyton and marine concrete. The material comprises the components of a cementing material, broken stone, sand, water, a dark pigment, biological calcium powder, chopped fibers and a superplasticizer. The invention can carry out compound doping according to the actually required alkalinity, and can provide proper alkalinity for the adhesion of oyster larvae on the surface; has high sulfate corrosion resistance and has obvious advantages in ocean engineering and projects needing quick repair.

Description

Oyster attachment base of fiber reinforced cement concrete and preparation method thereof

Technical Field

The invention relates to an oyster attachment base technology, in particular to an oyster attachment base of fiber reinforced cement concrete and a preparation method thereof, belonging to the crossing field of marine periphyton and marine concrete.

Background

With the improvement of the living standard of people, the consumption demand of oysters is increasing as healthy food on dining tables. The traditional small-scale cultivation and cultivation method cannot meet the increasing demand of the oysters. Simultaneously, along with the increase of the oyster reef restoration amount and the coming of marine ecological engineering construction of the oyster-like reef, the demand on the oyster attachment base is increasingly large. Common culture methods comprise bamboo-cutting culture, bottom sowing culture, barren rock and vertical rock culture, hanging culture and the like, but have the problems that the oysters need a longer time to reach a satisfactory attachment rate on an attachment base; in addition, due to the increase of the breeding amount of oysters, oyster attaching bases of shells such as chlamys farreri shells and the like can not meet the requirement of oyster breeding far enough, so that the price of the attaching bases of the shells rises, and the like. In addition, in CN106719186 patent invented by china university of ocean recently: the novel oyster attaching base is prepared by doping 15-20% of shell powder and 5-15% of shell fragments of cement slurry, the surface of the attaching base is roughened by the shell fragments, the attaching amount of the oyster is increased, and the novel oyster attaching base is easier to harvest and has a better attaching effect than chlamys farreri shells. However, since the control of the amount of water used and the curing using a water reducing agent are not considered, the water cement ratio and the curing determine the permeability of the concrete. Therefore, a large amount of alkali contained in the attachment base can be released, the alkalinity of the contacted seawater is increased, the attachment of marine periphyton larvae is inhibited, and particularly, oyster larvae can die due to the increase of the pH value of the water body caused by the small water body during the seedling raising in the seedling raising pond; meanwhile, the large amount of shell powder is mixed, so that the color of a cement adhesive base is changed from dark gray to light, and the adhesion of oysters is not facilitated.

The concrete has the advantages of simple processing, easy seedling attachment, easy basal removal, wide supplied materials and low cost, but the problems of immature cement-based material adhesion base research, high pH value and the like cause the death rate of seedlings to be high, and the concrete can be put into use only after being soaked in seawater for more than 1 year. In addition, the ion-induced marine organisms are mainly applied to laboratory tests, and the development and application of the ion-induced marine organism technology are always restricted by the defects of high cost and difficult control. Therefore, the invention discloses a concrete attachment base with low alkalinity and high induction efficiency as a substrate to induce oyster attachment.

Meanwhile, as coastal economy develops rapidly in recent decades without paying attention to environmental protection, coastal ecology is broken down on a large scale, and the coastal ecology and economy in China are greatly influenced. If proper ecological environment protection measures are not taken, a greater disaster is certainly brought to the ecology along the shore of the ocean. Meanwhile, most coastal infrastructures cannot be dismantled, and the ecology in the sea area needs to be restored, so that people gradually realize the application of ecological technologies on a large number of infrastructures, and the ecology in the sea area can be effectively improved or restored. Therefore, it is very important and urgent to construct a concrete project with good ecological effects, or to ecologize the existing concrete project, etc. to improve the offshore ecological environment. However, until now, the ecological technology of projects such as breakwaters in tidal range areas is still in the blank state in China.

Oysters are ecological engineers and are mainly concentrated in a tidal range area and underwater within 30 meters, and the oysters like to be attached to shells of the same type to form a thick oyster reef, so that the oysters are attached to the breakwater compactly, and the ecology of the breakwater can be realized; in addition, the existing oyster reefs are seriously damaged, and most oysters need to be attached again in a large scale to realize ecological restoration. The ecological function of the oysters can be realized through the massive attachment 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 many studies on attachment and metamorphosis of fixed organisms on the surfaces of different substances such as polyethylene plates, shells, tiles and the like are carried out in solution, the method is not easy to realize or has high cost when applied to the actual marine concrete engineering.

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

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

At present, portland cement concrete is almost adopted in ocean concrete engineering, and has high alkalinity (the pH value of a pore solution is generally 12.0-13.0), and the pH value of seawater is generally 7.9-8.4. 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 the fixed 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 adhesion effect, and the aluminate cement and fly ash silicate cement have good biological adhesion effect, and have lower alkalinity compared with common silicate 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, in particular 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 using cement with lower alkalinity to prepare concrete, biomass (mainly marine plants) sensitive to alkali can be effectively increased, but the adhesion amount and the adhesion density of the cement to oysters are limited.

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

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

Recently, in addition to conventional substrates, studies have been made on the adhesion of oyster larvae by adding calcium to cement-based materials and increasing the content of calcium in concrete. In the literature, 80-mesh cattle bone powder, calcium carbonate powder and gypsum powder (the mixing amount is 62.5 percent and 375 percent of the weight of cement) are singly mixed into mortar to carry out an oyster attachment experiment, and the sequence of the inducing capacity of the calcium excipient for the adhesion of oyster larvae under the same condition is obtained: the bovine bone meal is calcium carbonate which is calcium sulfate; the calcium carbonate powder is 5-60 percent of the weight of the mortar (41.7-500.0 percent of the weight of the cement), and the effect is best when the calcium carbonate powder is 20 percent of the weight of the mortar (166.7 percent of the weight 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 the calcium substances on the basic performance of the concrete is not considered, so that the calcium substances cannot be applied to the 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). And the alkalinity of the surface of the concrete artificial fish reef is reduced, so that microorganisms and algae are easier to attach, the biomass and the population quantity are increased, and the fish collecting effect is better. The biological calcium carbonate cement mortar coating layer educt is harmless to the environment and the organism. Although the biological calcium carbonate powder, the oyster shell fragments and the like are mixed 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, and the dissolution of calcium carbonate needs longer time. Therefore, it was confirmed that incorporation of calcium carbonate material into concrete promotes adhesion of oyster larvae, Ca²⁺Not as a primary guide.

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 ensure that the impermeability of the concrete is not reduced or better, the excessive amount of calcium carbonate material can reduce the sulfuric acid (salt) corrosion resistance of the concrete 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 poor concrete performance caused by excessive doping of the calcium substances, mildewing caused by doping of the bovine bone meal and the like.

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

The color of the substrate has certain influence on the attachment, metamorphosis and growth of the larvae of the marine periphyton. Overseas has reported that in a sea area with a low temperature, a dark substrate can promote the growth of oysters. Domestic research shows that oyster larvae have certain selectivity on color. The color selectivity of the crassostrea hongkongensis larvae on the plastic anchoring base is as follows: black > white > red. Crassostrea gigas larvae prefer to attach to black and gray plastic plates and it is believed that black and gray may be a protective color for oyster larvae to avoid natural enemy attacks. Barnacles prefer to adhere to red substrates. Pearl oyster also prefers dark (black, red), non-reflective substrates, showing non-photosensitive behavior. In addition, 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 of the concrete on the attachment amount of sessile organism larvae is not referred to related data.

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

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

In summary, while the above studies have been conducted, such as different substrates, and the effects of color and roughness on marine periphyton attachment, the effect of incorporating calcareous materials into concrete on marine periphyton attachment has recently been studied. However, due to the knowledge of related subjects such as marine organisms, marine microorganisms, marine chemistry, marine concrete engineering materials and structures and the like, the subject directions are different greatly, so that the problems of serious concrete durability and easy mildew of the doped bovine bone meal are caused by the unclear water cement ratio of the cement-based materials, unclear mechanism of inducing oyster adhesion by calcium carbonate materials, excessive calcium powder doped in cement and the like, and in addition, the professional knowledge required by marine sessile organism adhesion is lacked by the professional technicians of the marine concrete engineering materials and the structures, so that the problems can be solved by the cooperative cooperation of the professional technicians of multiple subjects.

Disclosure of Invention

The invention aims to solve the problems that at present, because the control of water consumption and the maintenance (the water cement ratio and the maintenance determine the permeability of concrete) are not considered, a large amount of alkali contained in an adhesive base is released, the alkalinity of seawater in contact with the adhesive base is increased, the adhesion of larvae of marine sessile organisms is inhibited, and simultaneously, because a large amount of shell powder is mixed, the color of a cement adhesive base is changed from dark gray to light, and the adhesion of oysters is not facilitated, and provide a concrete adhesive base which can induce sessile organisms to quickly and densely adhere to the surface of concrete and has good durability.

The purpose of the invention is realized as follows: the invention selects proper cement type by reducing the cement dosage in the adhesive base, simultaneously controls the water cement ratio of the adhesive base concrete, controls the release rate of the adhesive base concrete, and adds dark pigment and biological calcium powder capable of inducing the adhesion of oysters according to the favorite adhesion color of the oysters, thereby promoting the early adhesion, metamorphosis and later growth of the oysters and simultaneously carrying out the configuration design of the adhesive base. In addition, the attaching base can be directly attached to seedlings in the culture pond, is not required to be placed in seawater for a long time and can have the life expectancy of more than 50 years without violent collision or smashing.

The invention also includes such structural features:

the material components are as follows: the adhesive comprises a cementing material, macadam, sand, water, a dark pigment, biological calcium powder, chopped fiber and a superplasticizer in sequence by weight: 12.5% -22.0%, 39.4% -49.8%, 24.9% -37.3%, 6.2% -8.7%, 0.2% -1.7%, 0.15% -1.0%, 0.1% -1.0% and 0.02% -0.1%.

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: 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 bovine bone powder and the biological calcium carbonate 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 100-500 mesh bovine bone powder with one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid.

Preferably, the sand is: one or more of river sand, machine-made sand (mother rock is basalt or granite) or desalted sea sand, and the grading is good.

Preferably, the chopped fibers are: inorganic fiber (length 12-20 mm), such as one or more of basalt fiber, alkali-resistant glass fiber and carbon fiber.

Preferably, the cementing material is one of sulphoaluminate cement and alkali-activated cementing material; the sulphoaluminate cement comprises one or two of quick-hardening sulphoaluminate cement, high-strength sulphoaluminate cement and expansion sulphoaluminate cement; the alkali-activated gelling material is alkali-activated slag, alkali-activated slag and fly ash.

The preparation method of the oyster attaching base of the fiber reinforced cement concrete is characterized by comprising the following steps:

s1: designing different roughness according to the characteristics of the oyster larvae which favor to attach to rough surfaces, and then manufacturing forming templates with different roughness;

s2: accurately weighing a cementing material, crushed stone, sand, water, a dark pigment, biological calcium powder, chopped fibers and a superplasticizer;

s3: firstly, placing broken stone and sand into a concrete mixer to be mixed for 0.5-1 minute; then adding a cementing material, a dark color pigment and biological calcium powder, and continuing stirring for 1-2 minutes; then adding chopped fibers, water and a superplasticizer and stirring for 2-6 minutes; after being stirred evenly, pouring and vibrating are carried out; standard curing 28d is then performed or curing is performed as appropriate.

Thus obtaining the oyster attaching base of the fiber reinforced cement concrete.

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

the alkalinity of cement concrete is regulated and controlled by adopting the compounding of low-alkalinity sulphoaluminate cement, and 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, which require a large amount of calcium ions. And because the alkalinity of the sulphoaluminate cement is low, and the alkalinity of the quick-hardening sulphoaluminate cement, the high-strength sulphoaluminate cement and the expansion sulphoaluminate cement is different, the compound addition can be carried out according to the actually required alkalinity, and the proper alkalinity can be provided for the adhesion of the oyster larvae on the surface of the oyster. Meanwhile, the sulphoaluminate cement has the characteristics of early strength and high strength, can realize the rapid construction of engineering, has high impermeability and corrosion resistance, particularly has high sulfate corrosion resistance, and has remarkable advantages in ocean engineering and projects needing rapid repair.

Drawings

FIG. 1 shows the mildew on the surface of concrete doped with 10% bovine bone powder in different mixing ratios;

FIG. 2 is a graph showing different mixing ratios of 10% modified bovine bone powder with fineness greater than 200 meshes;

FIG. 3 is a schematic diagram of a concrete oyster anchorage;

FIG. 4 is a schematic illustration of a concrete oyster anchorage;

fig. 5 is a schematic diagram of a concrete oyster attachment base.

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.

These examples are intended to illustrate the invention and do not limit the scope of the invention. The concrete mixing ratio of the concrete is as follows:

example 1: the weight ratio of the ordinary Portland cement, the broken stone, the sand, the water and the polycarboxylic acid water reducing agent powder is as follows in sequence: 17.1%, 46.67%, 29.0%, 7.2%, 0.03%.

The crushed stone has the maximum grain size of less than 20mm, can be one or more of basalt, granite and diabase crushed stone, and has good gradation; the sand has the grain size of 0.16 mm-5.0 mm, wherein the sand can be one or more of river sand, machine-made sand (mother rock can be basalt or granite) and sea sand, and the grading is good; the water meets the concrete water standard (JGJ63-2006), the Cl-content is less than 1000mg/L, the PH value is more than 4.5, and the influence on the initial setting time difference, the final setting time, the strength and the permeability of the cement is small. The materials selected in examples 1 to 16 are the same.

Example 2: the weight ratio of the sulphoaluminate cement, the broken stone, the sand, the water and the polycarboxylic acid water reducing agent powder is as follows: 17.1%, 46.67%, 29.0%, 7.2%, 0.03%.

By comparing the above implementation, it can be seen that the electric flux of the sulphoaluminate cement concrete is smaller under the condition of the same mixing amount, which indicates that the concrete has good anti-permeability performance, and meanwhile, compared with silicate, the adhesion rate of oyster larvae is obviously improved

Example 3: the weight ratio of the unmodified dark pigment, the sulphoaluminate cement, the broken stone, the sand, the water and the polycarboxylic acid water reducing agent powder is as follows in sequence: 0.51%, 16.59%, 46.67%, 29.0%, 7.2%, 0.03%.

Example 4: the weight ratio of the unmodified dark pigment, the sulphoaluminate cement, the broken stone, the sand, the water and the polycarboxylic acid water reducing agent powder is as follows in sequence: 0.86%, 16.24%, 46.67%, 29.0%, 7.2%, 0.03%.

Example 5: the weight ratio of the unmodified dark pigment, the sulphoaluminate cement, the broken stone, the sand, the water and the polycarboxylic acid water reducing agent powder is as follows in sequence: 1.37%, 15.73%, 46.67%, 29.0%, 7.2%, 0.03%.

Example 6: the modified dark pigment (iron oxide black: nigrosine mixture mass ratio is 1:1), sulphoaluminate cement, macadam, sand, water and polycarboxylic acid water reducing agent powder are sequentially mixed according to the following weight ratio: 0.51%, 16.59%, 46.67%, 29.0%, 7.2%, 0.03%.

Example 7: the modified dark pigment (iron oxide black: nigrosine mixture mass ratio is 1:1), sulphoaluminate cement, macadam, sand, water and polycarboxylic acid water reducing agent powder are sequentially mixed according to the following weight ratio: 0.86%, 16.24%, 46.67%, 29.0%, 7.2%, 0.03%.

Example 8: the modified dark pigment (iron oxide black: nigrosine mixture mass ratio is 1:1), sulphoaluminate cement, macadam, sand, water and polycarboxylic acid water reducing agent powder are sequentially mixed according to the following weight ratio: 1.37%, 15.73%, 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, and the volume ratio of the pigment to the resin is as follows: 1: 0.2; curing at normal temperature for 4h, curing at 60 deg.C for 4h, then breaking, and grinding with vibration mill to obtain the final product with fineness greater than 400 mesh.

The black pigment has a great influence on the permeability of concrete, and the adhesion of oyster larvae decreases as the amount of the admixture increases. On the one hand, the permeability of the concrete is increased, and the alkali seepage of the concrete is increased, on the other hand, the ferrite in the concrete is converted into iron ions, so that the concentration of the iron ions is increased, and the adhesion of oyster larvae is inhibited. Aiming at the problem, the anti-permeability of the concrete can be greatly improved by adopting the resin to coat the pigment and then grinding the pigment into powder, and particularly, when the mixing amount is 1.37 percent, the electric flux is only increased by 2.5 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 sulphoaluminate cement, the broken stone, the sand, the water and the polycarboxylic acid water reducer powder are as follows: 0.51%, 16.59%, 46.67%, 29.0%, 7.2%, 0.03%.

Example 10: the weight proportions of the unmodified bovine bone meal, the sulphoaluminate cement, the broken stone, the sand, the water and the polycarboxylic acid water reducer powder are as follows: 0.86%, 16.24%, 46.67%, 29.0%, 7.2%, 0.03%.

Example 11: the weight proportions of the unmodified bovine bone meal, the sulphoaluminate cement, the broken stone, the sand, the water and the polycarboxylic acid water reducer powder are as follows: 1.37%, 15.73%, 46.67%, 29.0%, 7.2%, 0.03%.

Example 12: the modified bovine bone meal, the sulphoaluminate cement, 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%, 16.59%, 46.67%, 29.0%, 7.2%, 0.03%.

Example 13: the modified bovine bone meal, the sulphoaluminate cement, 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%, 16.24%, 46.67%, 29.0%, 7.2%, 0.03%.

Example 14: the modified bovine bone meal, the sulphoaluminate cement, 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%, 15.73%, 46.67%, 29.0%, 7.2%, 0.03%.

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

Example 15: the modified dark pigment (iron oxide black: aniline black mixture mass ratio is 1:1), sulphoaluminate cement, biological calcium powder, macadam, sand, water, chopped fiber and polycarboxylic acid water reducing agent powder are sequentially prepared from the following components in parts by weight: 0.86%, 15.38%, 0.86%, 46.49%, 28.88%, 7.2%, 0.3%, 0.03%.

Example 16: the concrete oyster attachment base adopts the concrete and is designed into concrete oyster attachment bases with different shapes, which are shown in figures 3-5.

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

according to the preparation method of the oyster attaching base of the fiber reinforced cement concrete, 3 phi 100X 50mm cylindrical test pieces and 5 200X 30mm cuboid test pieces are prepared and are respectively used for testing 28d chlorine ion permeability resistance of the concrete and the attaching and metamorphosis conditions 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 sulphoaluminate cement, broken stone, sand, water, dark pigment, biological calcium powder, short-cut fiber and polycarboxylic acid water reducer powder according to the mass;

2. sand paper with different surface roughness (including 20 meshes, 60 meshes and 200 meshes) is stuck in a mould of a cuboid concrete test piece for standby;

3. firstly, placing broken stone and sand into a concrete mixer to be mixed for 0.5-1 minute; then adding sulphoaluminate cement, biological calcium powder and dark color pigment, and continuing stirring for 0.5-1 minute; then adding chopped fibers, water and a superplasticizer and stirring for 2-6 minutes; after uniformly stirring, pouring, vibrating and removing a mould to obtain 3 cylindrical test pieces with the diameter of 100 multiplied by 50mm and 5 cuboid test pieces with the diameter of 200 multiplied by 30 mm;

4. immediately placing the concrete sample after the mold stripping in 10 atmospheric pressures for CO₂Maintaining in a maintenance box for 2h, reducing the alkalinity of the cement test piece, and then performing standard maintenance for 28 d; and corresponding permeability evaluation is carried out at each age, and experiments of oyster larva attachment and metamorphosis in a laboratory are carried out after 28 days.

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

according to the Standard Test Method for electric Indication of Concrete's resistance to resistance Chloride Ion networking (ASTM1202-2017), in Standard curing for 28d, 3 cylindrical Test pieces with a diameter of 100X 50mm were taken out from a curing chamber, and the surface moisture and impurities were cleaned, and after the surface was dried, a thin layer of epoxy resin was coated on the side of the cylindrical Test piece. The test piece is then placed in a vacuum water saturation machine for 20 to 24 hours. Then taking out the test piece, cleaning the surface of the test piece, placing the test piece in an organic glass mold, simultaneously detecting the tightness between the test piece and the 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 two side molds of the test piece. The laboratory instrument was then started and the experimental data were recorded after 6h, and the latter two test pieces repeated the above procedure. And finally, calculating the intensity according to the standard.

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

after standard curing for 28 days, respectively taking out the rectangular blocks of 200X 30mm from the curing chamberCleaning the surface water and impurities of the sample, placing the sample into a test cell, and preparing the test cell in a laboratory, wherein the abundance of oyster larvae is 0.85ind/ml³The 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 test piece, oxygen pipes are uniformly distributed in the test pond to prepare for throwing in the oyster larvae. After the oyster larvae are slowly and uniformly stirred in the bucket, the quality of the seawater containing the oyster larvae is accurately weighed by using a beaker, and then the seawater is uniformly distributed in the test pool.

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

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

the purpose in the present invention is different from the comparison document: comparative document 1 is directed to waste utilization, repair and improvement of artificial fish reefs, although oyster shell powder is added to concrete. The present invention is directed to inducing adhesion of oyster larvae.

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 that of comparative document 2. In comparison document 2, although oyster shell or oyster shell powder is added to concrete, its purpose is mainly achieved by surface bionic property, fish, microorganism and algae are collected, the number of microorganisms is increased, and the water environment is improved, and no oyster is mentioned. The present invention is directed to inducing adhesion of oyster larvae.

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

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

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

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

Compared to reference 3 (Vanreilin. influence of matrix type on oyster attachment, growth, population establishment and reef development [ D ]), the 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 retains the original substances of the biological calcium, increases the release rate of substances which induce oyster larvae to adhere to the biological calcium powder, and reduces the mixing amount of the biological calcium powder, thereby reducing the influence on the performance of cement concrete.

(3) Because the bovine bone meal contains rich organic substances such as collagen, the great amount of the substances can cause the strength and the impermeability of concrete to be reduced, particularly after the content of the organic substances exceeds 5 percent, the mixing amount is increased, the strength of the concrete is rapidly reduced, the impermeability is obviously reduced, and mildew grows on the surface of the concrete under standard curing conditions. FIG. 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 the dilute acid modification and the 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 mildewing 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. But cement concreteThe pH value of the pore solution is generally more than 12.5, and the pH value of the saturated calcium hydroxide solution is about 12 at normal temperature, so that the concentration of 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 oyster attachment is considered to be 10-25 mmol/L, and even if oyster larvae are placed in saturated calcium carbonate solution, enough Ca is not available²⁺The concentration provides a suitable ionic concentration for adhesion of the oysters. Further, Ca (OH) in the inside of the cement concrete₂The release is faster, 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.

Chopped fibers are used, and the fibers can enhance the strength, particularly the tensile strength, of the concrete. According to the invention, the alkali-resistant fibers are combined with the ecological concrete, so that the cracking resistance, the impact resistance and the breaking resistance of the concrete are enhanced, the conditions of collision in the process of seedling culture or cultivation, breakage and breakage after falling from a high place can be reduced, the loss rate of the concrete in use is reduced, the weight capable of being borne by each attachment base is increased, and the retention rate is greatly increased in extreme weather.

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

color yield

The light-resistant characteristic of oyster eyespot larvae is utilized, dark color pigments (one or two of black iron oxide, nigrosine, carbon black, antimony sulfide, red iron oxide and organic pigment red) are adopted and are doped into the concrete after modification, the color of the concrete is changed, the color of the concrete is deepened, the oyster larvae are considered to be in a dark environment, the oyster larvae are induced to arrive at the dark color of the surface of the concrete, the contact probability of the larvae and the surface of the concrete 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 the 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⁺At equal permeation rate, releasedThe alkali can affect the attachment, metamorphosis and growth of sessile organism larva, and when the mixing amount is more than a certain value, the larva attachment amount is reduced. The impermeability of the concrete is designed and controlled, and the main measures are as follows: the selection of the type of the dark color pigment, the control of the addition amount and the modification. The attachment rate of the larvae is increased along with the increase of the doped amount of the dark substance, and when the doped amount is 0.5-6% of the cementing material, the attachment amount of the larvae is maximum, but then the attachment amount is slightly increased or kept unchanged.

Permeability of concrete

The strength and permeability of concrete are the two most important properties of concrete. When considering that different substances are added to promote the adhesion, metamorphosis and later-stage growth of oyster larvae, the strength and permeability of the concrete are controlled from the whole without great influence, then raw materials are selected according to the compatibility of various raw materials, and when the performance of the raw materials cannot meet the actual requirements, the raw materials are added after being modified, so that the expected effect is achieved. However, in the related research, although the influence of the calcium content on the adhesion of the oyster larvae is considered, the concrete performance is not 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 likely to 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 concrete to ensure that the impermeability of the concrete is changed within a controllable range, such as the change is not more than 10%. These induction effects can only be compared, otherwise the influence of the single or complex 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.

Roughness of

The rough surface provides better touch stimulation and increased adhesive force for the crawling and attachment of the oyster larvae, and the residence time of the oyster larvae on the substrate is increased; the existing cracks and pits can protect larvae, and the invasion probability of predators is reduced; and a larger adherable area than a smooth adherable base, thereby promoting increased adhesion of oyster larvae onto rough surface adherends.

Therefore, since this part of knowledge relates to the intersection of marine periphytons, marine plants and marine concrete engineering disciplines, no matter the concrete and engineering fields or the technical personnel in the marine life field, the technical characteristics of the present invention of color change by incorporating dark color pigments into concrete, bovine bone meal modification and grinding technology and control of concrete permeability closely related to concrete with high efficiency of inducing oyster attachment ability and high durability can be obtained by comparing documents 1 to 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 oyster adhesion base of fiber reinforced cement concrete is characterized in that: the bio-calcium composite material is prepared from a cementing material, broken stone, sand, water, a dark color pigment, bio-calcium powder, chopped fiber and a superplasticizer, wherein the cementing material, the broken stone, the sand, the water, the dark color pigment, the bio-calcium powder, the chopped fiber and the superplasticizer are sequentially prepared from the following components in parts by weight: 12.5% -22.0%, 39.4% -49.8%, 24.9% -37.3%, 6.2% -8.7%, 0.2% -1.7%, 0.15% -1.0%, 0.1% -1.0% and 0.02% -0.1%;

the dark pigment is one or two of iron oxide black, aniline black, carbon black, antimony sulfide, iron oxide red and organic pigment red;

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 and super-hydrophobic material;

the biological calcium carbonate powder is formed by compounding one or more of oyster shell powder, fishbone powder, egg shell powder and coral powder, and the fineness of the biological calcium carbonate powder is 100-1000 meshes;

the biological calcium powder 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 100-500 mesh bovine bone powder with one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid;

the cementing material is one of sulphoaluminate cement and alkali-activated cementing material; the sulphoaluminate cement comprises one or two of quick-hardening sulphoaluminate cement, high-strength sulphoaluminate cement and expansion sulphoaluminate cement; the alkali-activated cementing material is alkali-activated slag, alkali-activated slag and fly ash.

2. The oyster attachment base for fiber cement concrete according to claim 1, wherein: the chopped fibers are inorganic fibers, and the inorganic fibers are one or more of basalt fibers, alkali-resistant glass fibers and carbon fibers.

3. The method for preparing the oyster attachment base for fiber cement concrete according to claim 1, comprising the steps of:

s1: designing different roughness according to the characteristics of the oyster larvae which favor to attach to the rough surface, and then manufacturing forming templates with different roughness;

s3: firstly, placing broken stone and sand into a concrete mixer to be mixed for 0.5-1 minute; then adding a cementing material, a dark color pigment and biological calcium powder, and continuing stirring for 1-2 minutes; then adding chopped fibers, water and a superplasticizer and stirring for 2-6 minutes; after uniform stirring, pouring and vibrating in an S1 rough die; then standard curing is carried out for 28d or curing is carried out according to actual conditions; thus obtaining the oyster attaching base of the fiber reinforced cement concrete.