CN117049849A

CN117049849A - High-performance anti-radiation mortar and preparation method thereof

Info

Publication number: CN117049849A
Application number: CN202310986300.0A
Authority: CN
Inventors: 何壮科
Original assignee: Hainan Ruichen New Building Materials Co ltd
Current assignee: Hainan Ruichen New Building Materials Co ltd
Priority date: 2023-08-08
Filing date: 2023-08-08
Publication date: 2023-11-14
Anticipated expiration: 2043-08-08
Also published as: CN117049849B

Abstract

The application relates to the technical field of building materials, in particular to high-performance anti-radiation mortar and a preparation method thereof, wherein aggregate crushed stone is ground into sand; mixing and stirring the machine-made sand, the additive and the cementing material for 1-3 min to obtain radiation-resistant mortar; the anti-radiation mortar comprises the following components in parts by mass: 415 to 630 parts of machine-made sand, 7.7 to 28.3 parts of additive and 245 to 390 parts of cementing material. According to the application, the beta radiation and the X radiation can be shielded to a certain extent by adding the alumina cement, the barium cement and the boron-containing cement into the cementing material. The aggregate is added with barite, serpentine, hematite, limonite and magnetite, and the composite use of the materials can enhance the radiation capability of the prepared radiation-resistant mortar to beta radiation and X radiation; and is easier to obtain, simple to prepare and capable of realizing economic gain.

Description

High-performance anti-radiation mortar and preparation method thereof

Technical Field

The application relates to the technical field of building materials, in particular to high-performance anti-radiation mortar and a preparation method thereof.

Background

In military industry, national defense, nuclear power stations, X-ray rooms of hospitals and biochemical laboratories, certain radiation phenomena such as nuclear radiation, X-ray radiation and biochemical source radiation exist. Also, radiation from solar ultraviolet rays, in these building surfaces, the radiation source cannot be effectively shielded by using ordinary mortar, and the effect of the existing mortar on radiation protection is small, and there is an urgent need for a mortar with an effective shielding effect against the above-mentioned radiation phenomenon. The radiation-proof mortar in the existing market has poor performance effect, and cannot meet the wide requirements of more and more environment-required radiation-proof mortars. Therefore, we propose a high-performance anti-radiation mortar and a preparation method thereof.

Disclosure of Invention

The application aims to provide high-performance anti-radiation mortar and a preparation method thereof, so as to solve the problems in the background technology.

In order to solve the technical problems, the application provides the following technical scheme: the preparation method of the high-performance anti-radiation mortar comprises the following preparation processes: grinding aggregate crushed stone into sand, and grinding into machine-made sand; and mixing and stirring the machine-made sand, the additive and the cementing material for 1-3 min to obtain the anti-radiation mortar.

Further, the grain size of the machine-made sand is 8-120 meshes, the water content is below 0.5%, and the powder content is 8% -12%.

Further, the anti-radiation mortar comprises the following components in parts by mass: 415 to 630 parts of machine-made sand, 7.7 to 28.3 parts of additive and 245 to 390 parts of cementing material.

Further, the cementing material comprises the following components in parts by mass: 200-300 parts of 425 ordinary silicate cement, 15-30 parts of alumina cement, 15-30 parts of barium cement and 15-30 parts of boron-containing cement.

Further, the mass ratio of the alumina cement, the barium cement and the boron-containing cement is 1:1:1.

Further, the aggregate comprises the following components in mass percent: 300-400 parts of granite, 50-100 parts of barite, 50-100 parts of serpentine, 5-30 parts of hematite, 5-30 parts of limonite and 5-30 parts of magnetite.

Further, the mass ratio of the hematite, limonite and magnetite is 1:1:1.

Further, barite is derived from mining; the particle size of the hematite and limonite magnetite is 0.5-3 mm.

Further, the additive comprises the following components in parts by mass: 1 to 3 parts of hydroxyethyl methyl cellulose ether, 0.3 to 0.5 part of sodium alkenyl sulfonate, 0.4 to 0.8 part of sodium gluconate, 1 to 4 parts of polyvinyl alcohol and 5 to 20 parts of boron carbide.

The additive is mixed uniformly in advance by a horizontal mixer, and is compounded;

the stone breaking and polishing process of the aggregate is carried out in a centrifugal stone breaking and polishing machine system;

the anti-radiation mortar adopts a tower type dry powder mortar production mode, and an additive, machine-made sand and a cementing material are led into a double-dragon mixing mixer to be mixed for 1-3 min to obtain the anti-radiation mortar; can be transported to a construction site by a filling mode, and can be used after being mixed with water. The preparation method of the anti-radiation mortar is practical and simple, has high production efficiency, and can meet the construction requirements of plastering the inner wall and the outer wall of a building site; the prepared anti-radiation mortar has good workability, does not bleed, is easy to be put on a wall, and does not generate hollowness and falling off.

In the technical scheme, the bauxite cement, the barium cement and the boron-containing cement are added into the cementing material, so that beta radiation and X radiation can be shielded to a certain extent. The aggregate is added with barite, serpentine, hematite, limonite and magnetite, and the composite use of the materials can enhance the radiation capability of the prepared radiation-resistant mortar to beta radiation and X radiation; and is easier to obtain, simple to prepare and capable of realizing economic gain. The prepared mortar can effectively shield solar ultraviolet radiation, artificial nuclear radiation, beta radiation, X-ray radiation and biochemical source radiation, and is suitable for plastering the inner and outer walls of buildings such as military industry, national defense, nuclear power plants, hospital X-ray rooms, biochemical laboratories and the like. The prepared anti-radiation mortar has good workability, does not bleed, is easy to be put on a wall, and does not fall off when empty; the preparation method is simple and practical and has high production efficiency.

Further, the polyvinyl alcohol is modified polyvinyl alcohol fiber, and specifically comprises the following processes:

dispersing lignin in deionized water, regulating the pH of the system to 10-12 by using sodium hydroxide solution, slowly adding 2, 6-tetramethyl piperidine amine, heating to 70-120 ℃, and stirring and refluxing for reaction for 6-12 h; slowly adding formaldehyde, finishing adding within 30min, heating to 85-95 ℃, and reacting for 3h at a temperature; cooling to room temperature after the reaction, precipitating at 0-5 ℃, vacuum filtering, washing with water, and drying at 65 ℃ for 24 hours to obtain modified lignin;

under the protection of nitrogen atmosphere, mixing absolute ethyl alcohol and toluene to obtain a mixed solution, sequentially adding modified lignin and polyvinyl alcohol, and stirring and mixing for 12-18 min; regulating the pH value of the system to 7.8-8.5 by using sodium hydroxide solution, slowly adding KH570, and stirring for 30min at room temperature; heating to 58-62 ℃ and stirring for reaction for 120-180 min; adding phenylboronic acid, and stirring and reacting for 30-60 min; cooling to room temperature, centrifuging, taking and washing the precipitate, and drying for 12 hours at 60-80 ℃ to obtain modified polyvinyl alcohol;

mixing dimethyl sulfoxide with modified polyvinyl alcohol, stirring at 82-90 deg.c for 230-270 min, and letting stand at 65-68 deg.c for 230-270 min to obtain spinning liquid; extruding, primary coagulating bath, pre-drawing, secondary coagulating bath and drawing to obtain the modified polyvinyl alcohol fiber.

Further, the proportion of lignin, 2, 6-tetramethyl piperidine amine, formaldehyde and deionized water is 10g (1.0-3.0 g) (0.20-0.58 g) 100mL;

the mass concentration of the sodium hydroxide solution is 30%;

formaldehyde is added in the form of an aqueous solution having a concentration of 10% by weight.

Further, the mass ratio of the modified lignin to the polyvinyl alcohol to the KH570 to the phenylboronic acid is (5-20) 100 (2-4) 0.08-0.16;

the ratio of the modified lignin to the mixed solution is (0.5-2.0) 100mL;

the volume ratio of the absolute ethyl alcohol to the toluene is 1:3;

the polyvinyl alcohol is added in the form of 40 ℃ solution with the concentration of 5%;

further, the ratio of the modified polyvinyl alcohol to the dimethyl sulfoxide is 10g to 100mL;

the primary coagulation bath is an acetone-methanol mixed solution with the temperature of 0-5 ℃, and the volume ratio of the acetone to the methanol is 85:15;

the extrusion process conditions are as follows: the extrusion temperature is 65-68 ℃, and the spinning diameter is 0.7mm;

the pre-draft is room temperature draft with draft ratio of 3.0-4.0;

the temperature of the secondary coagulating bath is-25 to-21 ℃;

the drafting comprises four times of hot drafting, the primary drafting temperature is 83-130 ℃, and the drafting ratio is 1.7-2.0; the secondary drafting temperature is 178-183 ℃, and the drafting ratio is 1.4-1.8; the temperature of the three times of drafting is 188-205 ℃, and the drafting ratio is 1.2-1.3; the four-time drafting temperature is 218-223 ℃, and the drafting ratio is 1.2-1.3;

lignin: corn stalk enzymolysis lignin with phenolic hydroxyl content of 12.9% and is from Shandong Longli biotechnology Co., ltd;

polyvinyl alcohol: the relative molecular weight is 146000-186000g/mol, the alcoholysis degree is 99%, and the product is obtained from Shanghai sigma Aldrich trade company.

In the technical scheme, the hydroxyethyl methyl cellulose ether has the solubility, salt resistance, water retention and the like, so that the uniformity of the anti-radiation mortar can be improved, the prepared concrete is easier to coat, and the anti-sagging capability of the concrete is improved; the fluidity is enhanced, the working time of the concrete is prolonged, the working efficiency can be improved, and the formation of high mechanical strength of the prepared concrete in the solidification period is facilitated. As an anionic surfactant, the sodium alkenyl sulfonate can reduce the viscosity of concrete prepared from mortar slurry, promote hydration and improve the strength of the prepared concrete 3d and 28 d. The addition of the sodium gluconate can effectively delay the initial setting time and the final setting time of the concrete and increase the operability of the mortar slurry; meanwhile, the plasticizer is used, so that the toughness of the prepared concrete can be improved; the water adding amount can be reduced when the concrete is prepared, and the shrinkage and heat of the concrete are relieved. The addition of the polyvinyl alcohol can enhance the compression resistance, the fracture resistance and the splitting tensile strength of the prepared concrete to a certain extent, and inhibit the formation and the development of cracks of the prepared concrete. Boron carbide has neutron absorption properties, can absorb a large amount of neutrons without forming any radioisotope, and has excellent performances in the aspects of wear resistance, hardness, thermoelectric properties, thermal stability, chemical stability and the like.

The polyvinyl alcohol is modified polyvinyl alcohol fiber, and the components and the preparation process of the polyvinyl alcohol fiber are modified on the basis of the polyvinyl alcohol fiber. The lignin contains active hydrogen atoms in the molecular structure, and can perform Mannich reaction with aldehyde substances and amine substances under the action of base catalysis; in the application, 2, 6-tetramethyl piperidine amine and formaldehyde are subjected to nucleophilic addition to form carbon positrons, and then nucleophilic substitution is carried out on the carbon positrons and lignin, so that the tetramethyl piperidine amine structure and lignin are grafted, and modified lignin is obtained. Mixing the prepared modified lignin with polyvinyl alcohol, reacting the modified lignin with a hydrolysate of KH570 (gamma-methacryloxypropyl trimethoxy silane) and crosslinking, adding phenylboronic acid, reacting unreacted silicon hydroxyl groups completely, and introducing boron element into a modified polyvinyl alcohol structure to obtain modified polyvinyl alcohol; and (3) placing the modified polyvinyl alcohol into dimethyl sulfoxide solvent, spinning, and passing through coagulation bath to obtain the modified polyvinyl alcohol fiber. Lignin in the prepared modified polyethylene fiber contains polyphenol which can capture free radicals and cooperate with free radicals generated by the degradation of an epoxy structure when the tetramethyl piperidine amine structure is used for fixing radiation, so that the structure is kept stable; and a ring structure with stability such as benzene ring, piperidine and the like is introduced into a polyethylene fiber system, and the electron cloud has the function of gamma-ray radiation activation resistance and is not easy to degrade during radiation; the introduced boron element can improve the neutron radiation-proof effect of the prepared modified polyvinyl alcohol, further increase the crosslinking density and improve the mechanical property of the modified polyvinyl alcohol; so that the modified polyethylene fiber has certain radiation resistance and can maintain good mechanical properties after radiation; improving the anti-collapsibility and strength of the prepared concrete before and after radiation.

Compared with the prior art, the application has the following beneficial effects:

1. according to the high-performance anti-radiation mortar and the preparation method thereof, the bauxite cement, the barium cement and the boron-containing cement are added into the cementing material, so that beta radiation and X radiation can be shielded to a certain extent. The aggregate is added with barite, serpentine, hematite, limonite and magnetite, and the composite use of the materials can enhance the radiation capability of the prepared radiation-resistant mortar to beta radiation and X radiation; and is easier to obtain, simple to prepare and capable of realizing economic gain. The prepared mortar can effectively shield solar ultraviolet radiation, artificial nuclear radiation, beta radiation, X-ray radiation and biochemical source radiation, and is suitable for plastering the inner and outer walls of buildings such as military industry, national defense, nuclear power plants, hospital X-ray rooms, biochemical laboratories and the like. The prepared anti-radiation mortar has good workability, does not bleed, is easy to be put on a wall, and does not fall off when empty; the preparation method is simple and practical and has high production efficiency.

2. According to the high-performance anti-radiation mortar and the preparation method thereof, the modified polyethylene fiber is prepared by grafting the tetramethyl piperidine amine modified lignin in the polyethylene fiber through the siloxane and the phenylboronic acid, wherein the lignin contains polyphenol, can capture free radicals, and cooperates with the free radicals generated by the degradation of an epoxy structure when the tetramethyl piperidine amine structure is used for fixing radiation, so that the structure is kept stable; and a ring structure with stability such as benzene ring, piperidine and the like is introduced into a polyethylene fiber system, and the electron cloud has the function of gamma-ray radiation activation resistance and is not easy to degrade during radiation; the introduced boron element can improve the neutron radiation-proof effect of the prepared modified polyvinyl alcohol, further increase the crosslinking density and improve the mechanical property of the modified polyvinyl alcohol; so that the modified polyethylene fiber has certain radiation resistance and can maintain good mechanical properties after radiation; improving the anti-collapsibility and strength of the prepared concrete before and after radiation.

Detailed Description

The following description of the technical solutions in the embodiments of the present application will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.

In the following embodiments, the source manufacturer and parameters of all the raw materials according to the present application include, by way of example, without any particular limitation:

425 Portland cement: specific surface area 380m2/kg, initial setting time 180min, final setting time 230min, SO ₃ 1.95 percent of the content, 2.45 percent of loss on ignition, and is derived from Ji Linshi Jidong cement plant;

alumina cement: CA-50A700 aluminate cement, the alumina content of which is 52 percent, is from Zhengzhou Jianai characteristic aluminate Co., ltd;

barium cement, boron-containing cement: derived from the scientific and technological company of the new material of the comet;

granite: apparent density 2710kg/m ³ Bulk density 1590kg/m3, void ratio 41.3%, stone powder content 11.6%, MB value 1.3, fineness modulus 2.9, crushing value 17%, clay content 0%, water absorption 1.1%From the company of Meissu county Marble materials;

barite: the natural barium sulfate used for mining Yunnan mine has the advantages of 3.2 Mohs hardness, 4.3 specific gravity, 48.4 percent of silicon dioxide content, 1.1 percent of ferric oxide, 35.1 percent of aluminum oxide, 0.2 percent of calcium oxide, 0.1 percent of magnesium oxide and 2.3 percent of titanium dioxide;

serpentine: purity 95.6%, from Jiangsu Longteng chemical industry Co., ltd;

hematite: iron content 64.7% from Wang Gutan iron ore of Kunming iron and Steel Co;

limonite is: 57.9% of iron, 2.4% of ferric oxide, 0.2% of calcium oxide, 4.5% of silicon dioxide, 2.2% of aluminum oxide and 0.1% of magnesium oxide, which are derived from Australian FMG;

magnetite: 54.5% of iron, 32.2% of ferric oxide, 0.4% of calcium oxide, 3.8% of silicon dioxide, 3.5% of aluminum oxide and 3.7% of magnesium oxide, which are sourced from Pan Steel group Co Ltd;

hydroxyethyl methyl cellulose ether, sodium alkenyl sulfonate, sodium gluconate: from Shanghai Ala Biotechnology Co., ltd;

polyvinyl alcohol fibers: density 1.28g/cm ³ Average diameter 0.12mm, average length 6.0mm, tensile strength 1540MPa, elastic modulus 31.2GPa, elongation 7.4% from Guangzhou anti-crack fiber company;

boron carbide: particle diameter of 75-250 mu m, boron content of 77-80% and density of 1500kg/m ³ Derived from Zhongzhixin shield alloy;

The "parts" described below are all parts by mass, and the mass of the components in the embodiments can be expanded in equal proportion.

Example 1: the preparation method of the high-performance anti-radiation mortar comprises the following preparation processes:

mixing 300 parts of 425 ordinary silicate cement, 15 parts of alumina cement, 15 parts of barium cement and 15 parts of boron-containing cement to obtain a cementing material;

330 parts of granite, 100 parts of barite, 100 parts of serpentine, 5 parts of hematite, 5 parts of limonite and 5 parts of magnetite are taken as aggregate;

taking 1.2 parts of hydroxyethyl methyl cellulose ether, 0.35 part of sodium alkenyl sulfonate, 0.4 part of sodium gluconate, 1 part of polyvinyl alcohol fiber and 10 parts of boron carbide, and uniformly mixing in advance by a horizontal mixer, and compounding to obtain an additive;

grinding aggregate crushed stone into grinding machine-made sand with the grain diameter of 8-120 meshes, the water content of below 0.5% and the powder content of 8%; and (3) introducing the additive, the machine-made sand and the cementing material into a double-dragon mixing stirrer by adopting a tower type dry powder mortar production mode, and stirring for 1min to obtain the radiation-resistant mortar.

Example 2: the preparation method of the high-performance anti-radiation mortar comprises the following preparation processes:

mixing 300 parts of 425 ordinary silicate cement, 20 parts of alumina cement, 20 parts of barium cement and 20 parts of boron-containing cement to obtain a cementing material;

grinding aggregate crushed stone into grinding machine-made sand with the grain diameter of 8-120 meshes, the water content of below 0.5% and the powder content of 8%; and (3) introducing the additive, the machine-made sand and the cementing material into a double-dragon mixing stirrer by adopting a tower type dry powder mortar production mode, and stirring for 2min to obtain the radiation-resistant mortar.

Example 3: the preparation method of the high-performance anti-radiation mortar comprises the following preparation processes:

mixing 300 parts of 425 ordinary silicate cement, 25 parts of alumina cement, 25 parts of barium cement and 25 parts of boron-containing cement to obtain a cementing material;

grinding aggregate crushed stone into grinding machine-made sand with the grain diameter of 8-120 meshes, the water content of below 0.5% and the powder content of 8%; and (3) introducing the additive, the machine-made sand and the cementing material into a double-dragon mixing stirrer by adopting a tower type dry powder mortar production mode, and stirring for 3min to obtain the radiation-resistant mortar.

Example 4: the preparation method of the high-performance anti-radiation mortar comprises the following preparation processes:

mixing 300 parts of 425 ordinary silicate cement, 30 parts of alumina cement, 30 parts of barium cement and 30 parts of boron-containing cement to obtain a cementing material;

Example 5: the preparation method of the high-performance anti-radiation mortar comprises the following preparation processes:

mixing 70 parts of alumina cement, barium cement and boron-containing cement (the mass ratio is 1:1:1) with 250 parts of 425 ordinary Portland cement to obtain a cementing material;

330 parts of granite, 50 parts of barite, 50 parts of serpentine, 30 parts of hematite, 30 parts of limonite and 30 parts of magnetite are taken as aggregate;

taking 1.5 parts of hydroxyethyl methyl cellulose ether, 0.4 part of sodium alkenyl sulfonate, 0.6 part of sodium gluconate, 2 parts of polyvinyl alcohol fiber and 15 parts of boron carbide, and uniformly mixing in advance by a horizontal mixer, and compounding to obtain an additive;

Example 6: the preparation method of the high-performance anti-radiation mortar comprises the following preparation processes:

mixing 200 parts of 425 ordinary silicate cement, 30 parts of alumina cement, 30 parts of barium cement and 30 parts of boron-containing cement to obtain a cementing material;

495 parts of granite, 70 parts of barite, 60 parts of serpentine, 30 parts of hematite, 30 parts of limonite and 30 parts of magnetite are taken as aggregate;

taking 2.5 parts of hydroxyethyl methyl cellulose ether, 0.5 part of sodium alkenyl sulfonate, 0.8 part of sodium gluconate, 4 parts of polyvinyl alcohol fiber and 5 parts of boron carbide, and uniformly mixing in advance by a horizontal mixer, and compounding to obtain an additive;

Example 7: the preparation method of the high-performance anti-radiation mortar comprises the following preparation processes:

taking 2.5 parts of hydroxyethyl methyl cellulose ether, 0.5 part of sodium alkenyl sulfonate, 0.8 part of sodium gluconate, 4 parts of polyvinyl alcohol fiber and 10 parts of boron carbide, and uniformly mixing in advance by a horizontal mixer, and compounding to obtain an additive;

Example 8: the preparation method of the high-performance anti-radiation mortar comprises the following preparation processes:

taking 2.5 parts of hydroxyethyl methyl cellulose ether, 0.5 part of sodium alkenyl sulfonate, 0.8 part of sodium gluconate, 4 parts of polyvinyl alcohol fiber and 15 parts of boron carbide, and uniformly mixing in advance by a horizontal mixer, and compounding to obtain an additive;

Example 9: the preparation method of the high-performance anti-radiation mortar comprises the following preparation processes:

taking 2.5 parts of hydroxyethyl methyl cellulose ether, 0.5 part of sodium alkenyl sulfonate, 0.8 part of sodium gluconate, 4 parts of polyvinyl alcohol fiber and 20 parts of boron carbide, and uniformly mixing in advance by a horizontal mixer, and compounding to obtain an additive;

Example 10: the preparation method of the high-performance anti-radiation mortar comprises the following preparation processes:

(1) Preparation of modified polyvinyl alcohol fibers:

dispersing 10g of lignin in 100mL of deionized water, regulating the pH of the system to 10 by using 30wt% sodium hydroxide solution, slowly adding 1.0g of 2, 6-tetramethylpiperidine amine, heating to 70 ℃, stirring and refluxing for reaction for 12 hours; slowly adding 0.20g formaldehyde (the concentration of the formaldehyde aqueous solution is 10 wt%) in a form of aqueous solution, and heating to 85 ℃ after finishing the addition within 30min, and preserving heat for 3h; cooling to room temperature after the reaction, precipitating at 5 ℃, vacuum filtering, washing with water, and drying at 65 ℃ for 24 hours to obtain modified lignin;

under the protection of nitrogen atmosphere, 333mL of absolute ethyl alcohol and 667mL of toluene are taken and mixed to obtain a mixed solution, 5g of modified lignin and 100g of polyvinyl alcohol (added in the form of 40 ℃ solution with the concentration of 5%) are sequentially added, and stirring and mixing are carried out for 12min; regulating the pH of the system to 7.8 by using sodium hydroxide solution, slowly adding 2gKH570, and stirring for 30min at room temperature; heating to 58 ℃ and stirring for reaction for 120min; 0.08g of phenylboronic acid is added and stirred for reaction for 30min; cooling to room temperature, centrifuging, taking and washing the precipitate, and drying for 12 hours at 60 ℃ to obtain modified polyvinyl alcohol;

mixing 100mL of dimethyl sulfoxide with 10g of modified polyvinyl alcohol, stirring at 82 ℃ for 230min, and standing at 65 ℃ for 230min to obtain spinning solution; the extrusion process conditions are as follows: extrusion temperature is 65 ℃, and spinning diameter is 0.7mm; primary coagulation bath, pre-drawing, room temperature drawing and drawing ratio of 3.0; a secondary coagulating bath, drawing, wherein the drawing comprises four times of hot drawing, the primary drawing temperature is 83 ℃, and the drawing ratio is 1.7; the secondary draft temperature was 178, the draft ratio was 1.4; the temperature of the three times of drafting is 188 ℃, and the drafting ratio is 1.2; the four-time drafting temperature is 218 ℃, and the drafting ratio is 1.2; obtaining modified polyvinyl alcohol fibers;

step (2): preparation of radiation-resistant mortar the same as in example 6 was used to obtain radiation-resistant mortar.

Example 11: the preparation method of the high-performance anti-radiation mortar comprises the following preparation processes:

(1) Preparation of modified polyvinyl alcohol fibers:

dispersing 10g of lignin in 100mL of deionized water, regulating the pH of the system to 11 by using 30wt% sodium hydroxide solution, slowly adding 2.0g of 2, 6-tetramethylpiperidine amine, heating to 145 ℃, stirring and refluxing for reaction for 9 hours; slowly adding 0.39g formaldehyde (the concentration of the formaldehyde aqueous solution is 10 wt%) in a form of aqueous solution, and heating to 90 ℃ after finishing the addition within 30min, and preserving heat for 3h; cooling to room temperature after the reaction, precipitating at the temperature of 2 ℃, vacuum filtering, washing with water, and drying at the temperature of 65 ℃ for 24 hours to obtain modified lignin;

under the protection of nitrogen atmosphere, 333mL of absolute ethyl alcohol and 667mL of toluene are taken and mixed to obtain a mixed solution, 12g of modified lignin and 100g of polyvinyl alcohol (added in the form of 40 ℃ solution with the concentration of 5%) are sequentially added, and stirring and mixing are carried out for 15min; regulating the pH of the system to 8.2 by using sodium hydroxide solution, slowly adding 3gKH570, and stirring for 30min at room temperature; heating to 60 ℃ and stirring for reaction for 150min; adding 0.12g of phenylboronic acid, and stirring and reacting for 45min; cooling to room temperature, centrifuging, taking and washing the precipitate, and drying for 12 hours at 70 ℃ to obtain modified polyvinyl alcohol;

mixing 100mL of dimethyl sulfoxide with 10g of modified polyvinyl alcohol, stirring at 86 ℃ for 250min, and standing at 67 ℃ for 250min to obtain spinning solution; the extrusion process conditions are as follows: extrusion temperature 67 ℃ and spinning diameter 0.7mm; primary coagulation bath, pre-drawing, room temperature drawing and drawing ratio of 3.5; a secondary coagulating bath, drawing, wherein the drawing comprises four times of hot drawing, the primary drawing temperature is 106 ℃, and the drawing ratio is 1.8; the secondary drafting temperature is 180 ℃, and the drafting ratio is 1.6; the temperature of the three times of drafting is 196 ℃, and the drafting ratio is 1.25; the four-time drafting temperature is 220 ℃, and the drafting ratio is 1.25; obtaining modified polyvinyl alcohol fibers;

Example 12: the preparation method of the high-performance anti-radiation mortar comprises the following preparation processes:

(1) Preparation of modified polyvinyl alcohol fibers:

dispersing 10g of lignin in 100mL of deionized water, regulating the pH of the system to 12 by using 30wt% sodium hydroxide solution, slowly adding 3.0g of 2, 6-tetramethylpiperidine amine, heating to 120 ℃, stirring and refluxing for reaction for 6 hours; slowly adding 0.58g formaldehyde (the concentration of the formaldehyde aqueous solution is 10 wt%) and heating to 95 deg.C for 3 hr; cooling to room temperature after the reaction, precipitating at 0 ℃, vacuum filtering, washing with water, and drying at 65 ℃ for 24 hours to obtain modified lignin;

under the protection of nitrogen atmosphere, 333mL of absolute ethyl alcohol and 667mL of toluene are taken and mixed to obtain a mixed solution, 20g of modified lignin and 100g of polyvinyl alcohol (added in the form of 40 ℃ solution with the concentration of 5%) are sequentially added, and stirring and mixing are carried out for 18min; adjusting the pH of the system to 8.5 by using sodium hydroxide solution, slowly adding 4gKH570, and stirring for 30min at room temperature; heating to 62 ℃ and stirring for reaction for 180min; 0.16g of phenylboronic acid is added and stirred for reaction for 60min; cooling to room temperature, centrifuging, taking and washing the precipitate, and drying for 12 hours at 80 ℃ to obtain modified polyvinyl alcohol;

mixing 100mL of dimethyl sulfoxide with 10g of modified polyvinyl alcohol, stirring at 90 ℃ for 270min, and standing at 68 ℃ for 270min to obtain spinning solution; the extrusion process conditions are as follows: extrusion temperature is 68 ℃, and spinning diameter is 0.7mm; primary coagulation bath, pre-drawing, room temperature drawing and drawing ratio of 4.0; a secondary coagulating bath, drawing, wherein the drawing comprises four times of hot drawing, the primary drawing temperature is 130 ℃, and the drawing ratio is 2.0; the secondary drawing temperature is 183 ℃, and the drawing ratio is 1.8; the temperature of the three drafting is 205 ℃, and the drafting ratio is 1.3; the four-time drafting temperature is 223 ℃, and the drafting ratio is 1.3; obtaining modified polyvinyl alcohol fibers;

Comparative example 1: the preparation method of the high-performance anti-radiation mortar comprises the following preparation processes:

taking 300 parts of 425 ordinary Portland cement as a cementing material;

Comparative example 2: the preparation method of the high-performance anti-radiation mortar comprises the following preparation processes:

taking 330 parts of granite and 50 parts of barite as aggregate;

Comparative example 3: the preparation method of the high-performance anti-radiation mortar comprises the following preparation processes:

taking 330 parts of granite, 50 parts of barite and 50 parts of serpentine as aggregate;

Comparative example 4: the preparation method of the high-performance anti-radiation mortar comprises the following preparation processes:

330 parts of granite, 50 parts of barite, 50 parts of serpentine and 30 parts of hematite are taken as aggregate;

Comparative example 5: the preparation method of the high-performance anti-radiation mortar comprises the following preparation processes:

(1) Preparation of modified polyvinyl alcohol fibers:

under the protection of nitrogen atmosphere, 333mL of absolute ethyl alcohol and 667mL of toluene are taken and mixed to obtain a mixed solution, 5g of lignin and 100g of polyvinyl alcohol (added in the form of 40 ℃ solution with the concentration of 5%) are sequentially added, and stirring and mixing are carried out for 12min; regulating the pH of the system to 7.8 by using sodium hydroxide solution, slowly adding 2gKH570, and stirring for 30min at room temperature; heating to 58 ℃ and stirring for reaction for 120min; 0.08g of phenylboronic acid is added and stirred for reaction for 30min; cooling to room temperature, centrifuging, taking and washing the precipitate, and drying for 12 hours at 60 ℃ to obtain modified polyvinyl alcohol;

Comparative example 6: the preparation method of the high-performance anti-radiation mortar comprises the following preparation processes:

(1) Preparation of modified polyvinyl alcohol fibers:

mixing 100mL of dimethyl sulfoxide with 5g of lignin and 10g of polyvinyl alcohol, stirring at 82 ℃ for 230min, and standing at 65 ℃ for 230min to obtain spinning solution; the extrusion process conditions are as follows: extrusion temperature is 65 ℃, and spinning diameter is 0.7mm; primary coagulation bath, pre-drawing, room temperature drawing and drawing ratio of 3.0; a secondary coagulating bath, drawing, wherein the drawing comprises four times of hot drawing, the primary drawing temperature is 83 ℃, and the drawing ratio is 1.7; the secondary draft temperature was 178, the draft ratio was 1.4; the temperature of the three times of drafting is 188 ℃, and the drafting ratio is 1.2; the four-time drafting temperature is 218 ℃, and the drafting ratio is 1.2; obtaining modified polyvinyl alcohol fibers;

Experiment

Mixing the anti-radiation mortar obtained in examples 1-12 and comparative examples 1-6 with 30wt% of water of gel material, adding into a flat plate mold, vibrating for 60s, trowelling the surface, covering with preservative film, curing for 1d, and removing the mold; curing for 28 days under curing conditions of humidity of 65RH and temperature of 22 ℃ to prepare a sample, respectively detecting the performance of the sample and recording the detection result:

mechanical property test, namely, using GB/T17671 as a reference standard, and adopting a compression-resistant and bending-resistant testing machine to test the compression resistance and bending resistance of a sample, wherein the size of the sample is 160 multiplied by 40mm;

shielding test: using spontaneous fission neutron sources ²⁵² Cf, total neutron emissivity of 9.078x10 ³ S ^-1 The average energy of the emitted neutrons is 2.28MeV; the experimental system is 1.2m away from the ground, 2.8m away from the wall, and the distance between the sample and the source is 10cm;

radiation resistance test: mixing the anti-radiation mortar with 30wt% of water of a gel material, adding the mixture into a flat plate mold, vibrating for 60 seconds, trowelling the surface, covering with a preservative film, curing for 1d, and removing the mold; curing for 28 days under the curing conditions of humidity 65RH%, temperature 22 ℃ and ultraviolet radiation (wavelength 340 nm); and then the mechanical properties are tested.

Table 1:

	flexural strength (MPa)	Compressive strength (MPa)	Radioactivity shielding rate (%)
				Example 1	6.81	45.0	60
Example 2	6.90	47.0	68
				Example 3	7.02	48.9	70
Example 4	7.20	52.0	73
				Comparative example 1	5.80	39.0	50

Table 2:

table 3:

	flexural strength (MPa)	Compressive strength (MPa)	Radioactivity shielding rate (%)
				Example 6	6.38	46.0	65
Example 7	6.30	45.0	68
				Example 8	6.18	44.0	71
Example 9	6.10	43.2	76

Table 4:

	flexural strength (MPa)	Radiation flexural strength (MPa)	Compressive strength (MPa)	Radioactivity shielding rate (%)
					Example 6	6.38	6.19	46.0	65
Example 10	6.48	6.40	46.2	66
					Example 11	7.20	7.13	46.5	68
Example 12	6.80	6.49	47.8	69
					Comparative example 5	6.30	5.97	45.0	62
Comparative example 6	6.20	5.84	44.0	60

From the data in the above table, the following conclusions can be clearly drawn:

the radiation-resistant mortars obtained in examples 1 to 12 were compared with the radiation-resistant mortars obtained in comparative examples 1 to 6, and the results of the tests revealed that,

1. as is clear from Table 1, the radiation-resistant mortars obtained in examples 1 to 4 were better in strength and shielding ability data against radiation than comparative example 1. The addition of the alumina cement improves the heat-resistant stability of the mortar, and can optimize the defect of poor heat stability of the barium cement; the combination of the boron-containing cement and the barium cement increases the radiation capturing range of thermal neutrons, X rays and the like, and improves the radioactive shielding rate.

2. As is clear from Table 2, the radiation-resistant mortars obtained in comparative examples 2 to 4 and example 5 were compared, and as the amount of the radiation-resistant material such as barite, serpentine, hematite, limonite, magnetite, etc. combined in the mortar was increased, the radiation shielding rate of the mortar against beta-radiation and X-radiation was effectively improved.

3. As is clear from Table 3, the radiation shielding rates of the beta-radiation and the x-radiation in the mortars were effectively improved as the amount of the powdery boron carbide material in the mortars was increased, with the same amounts of the other materials in the radiation-resistant mortars obtained in examples 6 to 9.

4. As can be seen from Table 4, comparative examples 5 to 6, examples 6, 10 to 12 are compared; the radiation-resistant mortar obtained in examples 10-12 has better data of strength, radiation shielding capability and flexural strength after radiation curing, and the application can promote the improvement of the strength and the radiation resistance of the radiation-resistant mortar by setting the polyvinyl alcohol fiber modification process and the required components thereof.

It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.

Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present application, and the present application is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present application has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. A preparation method of high-performance anti-radiation mortar is characterized by comprising the following steps: the preparation method comprises the following preparation processes: grinding aggregate crushed stone into sand, and grinding into machine-made sand; mixing and stirring the machine-made sand, the additive and the cementing material for 1-3 min to obtain radiation-resistant mortar;

the anti-radiation mortar comprises the following components in parts by mass: 415 to 630 parts of machine-made sand, 7.7 to 28.3 parts of additive and 245 to 390 parts of cementing material.

2. The method for preparing high-performance anti-radiation mortar according to claim 1, wherein the method comprises the following steps: the cementing material comprises the following components in mass percent: 200-300 parts of 425 ordinary silicate cement, 15-30 parts of alumina cement, 15-30 parts of barium cement and 15-30 parts of boron-containing cement.

3. The method for preparing high-performance anti-radiation mortar according to claim 2, wherein the method comprises the following steps: the mass ratio of the alumina cement to the barium cement to the boron-containing cement is 1:1:1.

4. The method for preparing high-performance anti-radiation mortar according to claim 1, wherein the method comprises the following steps: the aggregate comprises the following components in parts by mass: 300-400 parts of granite, 50-100 parts of barite, 50-100 parts of serpentine, 5-30 parts of hematite, 5-30 parts of limonite and 5-30 parts of magnetite.

5. The method for preparing high-performance anti-radiation mortar according to claim 4, wherein the method comprises the following steps: the mass ratio of the hematite to the limonite to the magnetite is 1:1:1.

6. The method for preparing high-performance anti-radiation mortar according to claim 1, wherein the method comprises the following steps: the additive comprises the following components in parts by mass: 1 to 3 parts of hydroxyethyl methyl cellulose ether, 0.3 to 0.5 part of sodium alkenyl sulfonate, 0.4 to 0.8 part of sodium gluconate, 1 to 4 parts of polyvinyl alcohol and 5 to 20 parts of boron carbide.

7. The method for preparing high-performance anti-radiation mortar according to claim 6, wherein the method comprises the following steps: the polyvinyl alcohol is modified polyvinyl alcohol fiber, and specifically comprises the following processes:

dispersing lignin in deionized water, regulating the pH of the system to 10-12 by using sodium hydroxide solution, slowly adding 2, 6-tetramethyl piperidine amine, heating to 70-120 ℃, and stirring and refluxing for reaction for 6-12 h; slowly adding formaldehyde, finishing adding within 30min, heating to 85-95 ℃, and reacting for 3h under heat preservation to obtain modified lignin;

under the protection of nitrogen atmosphere, mixing absolute ethyl alcohol and toluene to obtain a mixed solution, sequentially adding modified lignin and polyvinyl alcohol, and stirring and mixing for 12-18 min; regulating the pH value of the system to 7.8-8.5 by using sodium hydroxide solution, slowly adding KH570, and stirring for 30min at room temperature; heating to 58-62 ℃ and stirring for reaction for 120-180 min; adding phenylboronic acid, and stirring and reacting for 30-60 min to obtain modified polyvinyl alcohol;

8. The method for preparing high-performance anti-radiation mortar according to claim 7, wherein the method comprises the following steps: the mass ratio of lignin, 2, 6-tetramethyl piperidine amine and formaldehyde is 10 (1.0-3.0) to 0.20-0.58.

9. The method for preparing high-performance anti-radiation mortar according to claim 7, wherein the method comprises the following steps: the mass ratio of the modified lignin to the polyvinyl alcohol to the KH570 to the phenylboronic acid is (5-20) 100 (2-4) and 0.08-0.16.

10. A high performance radiation resistant mortar produced by the method according to any one of claims 1 to 9.