Radiation-proof concrete admixture and preparation method thereof

Abstract

The present application relates to a kind of anti-radiation concrete admixture and its preparation method, and the preparation raw material of anti-radiation concrete admixture includes water-reducing type mother liquor 20.0~40.0 parts, air entraining agent 0.06~0.15 parts, defoaming agent 0.02~0.05 parts, setting regulator 0.5~0.8 parts, water-retaining thickening agent 0.2~0.4 parts, anti-radiation agent 0.5~1.0 parts and water by weight parts.The present application introduces water-retaining thickening agent polyurethane associated thickening agent, modified betaine, seaweed glue in anti-radiation concrete admixture, improves the bleeding and segregation resistance performance of concrete, improves the strength of concrete.The present application improves the anti-radiation ability of concrete by adding nano TiO2 sol and nanoscale barium sulfate.In water-reducing type mother liquor synthesis, add ammonium acrylate, increase the dispersion performance of solution, in addition to enhancing the flow performance of concrete, can also make titanium dioxide sol more evenly dispersed in the entire admixture and concrete.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of concrete admixtures, in particular to a radiation-proof concrete admixture and a preparation method thereof. BACKGROUND

[0002] Radiation refers to the transmission of energy in the form of electromagnetic waves or subatomic particles such as alpha, beta, gamma particles and neutron particles, and the radiation energy is emitted linearly in all directions from the radiation source. The penetration of alpha rays and beta rays is weak, and ordinary walls can block them. However, the penetration of gamma rays and neutron rays is strong, and the damage is great. Human body is more likely to induce cancer, leukemia, malignant tumor, infertility and other symptoms after being irradiated by gamma rays and neutron rays, and may also be complicated by genetic teratogenicity. Plants may cause genetic variation and harm plant growth after being irradiated by gamma rays and neutron rays.

[0003] In scientific research institutions, hospitals and other places where radiation source buildings are located, radiation-proof materials are usually used for construction to prevent radiation from the radiation source from causing harm to humans or plants and animals. Radiation-proof concrete is usually used to build radiation source buildings, which mainly prevents alpha, beta, gamma and neutron rays from penetrating the wall and causing harm to the human body.

[0004] At present, the radiation-proof concrete prepared at home and abroad mainly improves the radiation-proof performance of concrete by adding heavy metal element admixtures. In actual production, ore containing heavy metal elements such as serpentine, barite and limonite is also used to improve the radiation-proof ability of concrete. Due to the strong penetration of gamma rays and neutron rays, the wall thickness usually needs to be increased to prevent gamma rays and neutron rays from penetrating the wall.

[0005] In the use process of radiation-proof concrete, the thickness of the wall usually needs to be increased to slow down the speed of the radiation rays, finally block and absorb the rays, and improve the radiation-proof performance. The increase of the wall thickness increases the construction cost, and also affects the tensile performance of the wall. SUMMARY

[0006] Therefore, it is necessary to provide a radiation-proof concrete admixture and a preparation method thereof to solve the problems of high cost and poor radiation-proof effect of radiation-proof concrete.

[0007] To achieve the above-mentioned purpose, the present application provides a technical solution:

[0008] A radiation-proof concrete admixture, the preparation raw materials of the radiation-proof concrete admixture include, by weight:

[0009]

[0010] Specifically, the air entraining agent includes sodium dodecyl benzene sulfonate, and the defoaming agent includes polyether modified silicone oil.

[0011] Preferably, the radiation shielding agent includes at least one of nano-TiO2 sol and nano-barium sulfate.

[0012] Due to the unique structure of nano-sized titanium dioxide particles, surface effects, volume effects, and quantum size effects are generated on their surfaces. As a result, nano-sized titanium dioxide has a significantly improved resistance to ultraviolet radiation compared to micron-sized titanium dioxide, and its shielding ability is also greatly enhanced. It can effectively defend against electromagnetic radiation, light radiation, thermal radiation, and gamma and beta rays in nuclear radiation.

[0013] Nanoscale barium sulfate, due to its nanostructure properties, not only has excellent X-ray radiation protection performance, but also has strong defense capabilities against visible or invisible light such as ultraviolet and infrared light, which have even weaker X-ray penetration.

[0014] Preferably, the preparation steps of nano-TiO2 sol are as follows:

[0015] Tetrabutyl titanate and an alcohol solution are mixed to obtain a tetrabutyl titanate mixed solution;

[0016] Under magnetic stirring, dilute hydrochloric acid was added dropwise to adjust the tetrabutyl titanate mixture to acidity, and ethanol solution was slowly added dropwise to the tetrabutyl titanate mixture. After the addition was completed, a light yellow solution was obtained.

[0017] Specifically, alcohol solutions include anhydrous ethanol and acetylacetone.

[0018] The hydrolysis of tetrabutyl titanate under acidic conditions in ethanol medium proceeds in steps. The overall hydrolysis reaction is expressed as follows, and the hydrolysis product is a titanium ion-containing sol. The specific reaction formula is as follows:

[0019] Ti(O-C4H9)4+4H2O→Ti(OH)4+4C4H9OH;

[0020] The pale yellow solution was transferred to a three-necked flask and stirred in a 40°C water bath. After 1 hour, a white sol was obtained. In the titanium ion-containing solution, titanium ions interact with hydroxide ions to form complex water and Ti-O-Ti three-dimensional network groups. Finally, after natural cooling, a stable TiO2 sol was obtained by ultrasonic degellation.

[0021] Ti(OH)4+Ti(O-C4H9)4=2TiO2+4C4H9OH;

[0022] Ti(OH)4 + Ti(OH)4 = 2TiO2 (sol) + 4H2O.

[0023] After natural cooling, a transparent TiO2 sol was prepared by ultrasonic degellation.

[0024] Preferably, the preparation raw materials of the water-reducing mother liquor include, in parts by weight:

[0025]

[0026] Specifically, the mass concentration of the ferrous sulfate solution is 1%.

[0027] Preferably, the unsaturated acid monomer includes at least one of acrylic acid and methacrylic acid, which are sourced from Satellite Chemical Co., Ltd.

[0028] Preferably, the preparation step of the water-reducing mother liquor is as follows:

[0029] The starting dropwise addition temperature of the reaction is 10-15°C, the polyethylene glycol macromonomer, the acrylamide, and the oxidizing agent are mixed to obtain a first mixed solution;

[0030] A liquid and a B liquid are added dropwise to the first mixed solution, and after the dropwise addition is completed, the reaction is kept for 1-3 h to obtain a second mixed solution; the A liquid includes an unsaturated acid monomer and water, and the B liquid includes a reducing agent, a chain transfer agent, and water;

[0031] The time for dropwise addition of the A liquid and the B liquid is 30-50 min.

[0032] The pH of the second mixed solution is adjusted to 5-6 to obtain the water-reducing mother liquor.

[0033] The structural formula of the water-reducing mother liquor is as follows:

[0034]

[0035] wherein the ratio of a and b is 1:(3-5), and n is an integer of 68-113.

[0036] Preferably, the oxidizing agent includes at least one of hydrogen peroxide and ammonium persulfate.

[0037] The reducing agent includes one of ascorbic acid and ascorbic acid, which is sourced from Guangdong Guangzhou Guangdong Osmann Biological Technology Co., Ltd.

[0038] The chain transfer agent includes at least one of sodium hypophosphite, mercaptoacetic acid, mercaptopropionic acid, and mercaptoethanol, which is sourced from Nanjing Qicheng New Material Co., Ltd.

[0039] The ferrous sulfate solution and the acrylamide are both of analytical purity, which are sourced from Xilong Scientific Co., Ltd.

[0040] Preferably, the coagulation regulator includes at least one of disodium phosphate, trisodium phosphate, tetrasodium phosphate, disodium hydrogen phosphate, sodium pyrophosphate, and alkyl phosphoric acid ester.

[0041] The setting retarder slows down the setting time of the concrete and enhances the construction performance of the concrete over time.

[0042] Preferably, the water-retaining thickening agent comprises a polyurethane associated thickening agent, modified betaine and seaweed glue.

[0043]

[0044] In the above formula, R1 is a hydrophobic end-capping group, R is an alkane, m is an integer of 10-40, and n is an integer of 2-10.

[0045] The modified betaine is obtained by taking coconut oil as a raw material, condensing with N, N dimethylpropylene diamine to generate PKO, and then quaternizing with sodium chloroacetate through two-step reactions.

[0046] The polyurethane associated thickening agent and the modified betaine jointly enhance the viscosity and rheological properties of water in the concrete, reduce the bleeding segregation state of the concrete, the seaweed glue is dispersed and filled in the concrete system to form a network structure, the cohesiveness of the concrete is enhanced, the internal void gap of the concrete is reduced, and the strength of the concrete is enhanced.

[0047] The application also provides a preparation method of the anti-radiation concrete admixture.

[0048] The water-reducing mother liquor and water are stirred and mixed, the air entraining agent, the defoaming agent, the setting retarder, the water-retaining thickening agent are added while stirring, and finally the anti-radiation agent is added to obtain the anti-radiation concrete admixture.

[0049] The application has the following beneficial effects:

[0050] The polyurethane associated thickening agent, the modified betaine and the seaweed glue are introduced into the anti-radiation concrete admixture, the bleeding and segregation resistance performance of the concrete is improved, and the strength of the concrete is improved.

[0051] The application improves the anti-radiation capability of the concrete by adding nano TiO2 sol and nano barium sulfate.

[0052] In the synthesis of the water-reducing mother liquor, ammonium acrylate is added to increase the dispersion performance of the solution, which can not only enhance the flow performance of the concrete, but also make the titanium dioxide sol more uniformly dispersed in the entire admixture and the concrete. DETAILED DESCRIPTION

[0053] In order to better illustrate the purpose, technical scheme and advantages of the application, the application will be further described below in combination with specific embodiments.

[0054] In the examples, the test methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are commercially available unless otherwise specified.

[0055] Example 1

[0056] Put 200 kg of water-reducing mother liquor into the stirred kettle, then put in 1600 kg of water, while stirring, put in 0.6 kg of air entraining agent sodium dodecyl benzene sulfonate, 0.2 kg of defoaming agent polyether modified silicone oil, 5 kg of disodium phosphate, 0.8 kg of polyurethane associated thickener, 0.8 kg of modified betaine, 0.4 kg of seaweed glue, then put in 4.5 kg of nano titanium dioxide sol, finally put in 0.5 kg of nano barium sulfate powder two hours before the admixture test, and keep stirring to form a suspension, to obtain a radiation-proof concrete admixture.

[0057] Example 2

[0058] Put 200 kg of water-reducing mother liquor into the stirred kettle, then put in 1600 kg of water, while stirring, put in 0.8 kg of air entraining agent sodium dodecyl benzene sulfonate, 0.3 kg of defoaming agent polyether modified silicone oil, 5 kg of disodium phosphate, 1.0 kg of polyurethane associated thickener, 1.0 kg of modified betaine, 0.5 kg of seaweed glue, then put in 6.0 kg of nano titanium dioxide sol, finally put in 0.5 kg of nano barium sulfate powder two hours before the admixture test, and keep stirring to form a suspension, to obtain a radiation-proof concrete admixture.

[0059] Example 3

[0060] Put 200 kg of water-reducing mother liquor into the stirred kettle, then put in 1600 kg of water, while stirring, put in 0.8 kg of air entraining agent sodium dodecyl benzene sulfonate, 0.3 kg of defoaming agent polyether modified silicone oil, 5 kg of disodium phosphate, 1.0 kg of polyurethane associated thickener, 1.0 kg of modified betaine, 0.5 kg of seaweed glue, then put in 8.0 kg of nano titanium dioxide sol, finally put in 0.5 kg of nano barium sulfate powder two hours before the admixture test, and keep stirring to form a suspension, to obtain a radiation-proof concrete admixture.

[0061] Comparative Example 1

[0062] Comparative Example 1 differs from Example 1 in that the admixture components do not contain seaweed glue, and the other steps are the same as Example 1.

[0063] Comparative Example 2

[0064] Comparative Example 2 differs from Example 1 in that the admixture components do not contain polyurethane associated thickener and modified betaine, and the other steps are the same as Example 1.

[0065] Comparative Example 3

[0066] Comparative Example 3 differs from Example 1 in that the admixture component does not contain nanoscale titanium dioxide sol, and other steps are the same as Example 1.

[0067] Comparative Example 4

[0068] Comparative Example 4 differs from Example 1 in that the admixture component does not contain nanoscale barium sulfate, and other steps are the same as Example 1.

[0069] The preparation steps of the water-reducing mother liquor used in the examples and comparative examples are as follows:

[0070] The starting dropwise addition temperature of the reaction is 15°C by weight fraction, 250 parts of polyethylene glycol macromonomer, 8 parts of acrylamide, 1 part of hydrogen peroxide are mixed to obtain a first mixed solution;

[0071] A liquid and B liquid are added dropwise to the first mixed solution, and after the dropwise addition is completed, the reaction is kept for 1-3h to obtain a second mixed solution; A liquid includes 30 parts of acrylic acid, water, and B liquid includes 0.3 parts of ascorbic acid, 1 part of mercaptoacetic acid, water;

[0072] The time for adding A liquid and B liquid is 50 min.

[0073] The pH of the second mixed solution is adjusted to 5-6 to obtain the water-reducing mother liquor.

[0074] The preparation steps of the nanoscale TiO2 sol used in the examples and comparative examples are as follows:

[0075] 100ml of n-tetrabutyl titanate and 350ml of anhydrous ethanol, 40ml of acetylacetone are mixed to obtain an n-tetrabutyl titanate mixed solution;

[0076] 300ml of anhydrous ethanol and 100ml of distilled water are mixed to prepare a dropwise addition liquid;

[0077] Under magnetic stirring, dilute hydrochloric acid is added dropwise to adjust the n-tetrabutyl titanate mixed solution to pH=2.5, and the dropwise addition liquid is slowly added to the n-tetrabutyl titanate mixed solution. After the dropwise addition is completed, a light yellow solution is obtained.

[0078] The solution is moved into a three-necked flask and stirred in a 40°C warm water bath, and after 1 hour, a white sol is obtained. After natural cooling, a transparent nanoscale TiO2 sol is prepared by ultrasonic debonding.

[0079] The radiation-proof concrete admixtures prepared in Examples 1-3 and Comparative Examples 1-4 were applied to concrete, and the slump and spread of the concrete were tested according to the provisions of GB / T50080. The concrete was tested for radiation-proof performance according to GB18871. The mechanical properties of the concrete were tested according to GB50080-2002. A nuclear radiation detector was used to measure gamma rays, and a neutron source was used to measure neutron rays. The concrete mix proportions are shown in Table 1.

[0080] Table 1: Concrete mix proportions / m 3

[0081] Strength class Cement / kg Machine sand / kg Macadam (10-20 mm) / kg Water / kg C30 380 980 1080 165

[0082] Table 2: Linear attenuation coefficients (cm -1 ) of the radiation-proof concrete of Examples 1-3 and Comparative Examples 1-4.

[0083] Table 2: Linear attenuation coefficients (cm -1 ) of the radiation-proof concrete of Examples 1-3 and Comparative Examples 1-4.

[0084]

[0085] As can be seen from the data in Table 2, the linear attenuation coefficients of the radiation-proof concrete of Example 1 for gamma rays and neutron rays are significantly higher than those of Comparative Examples 1-2, and the linear attenuation coefficients of the radiation-proof concrete of Examples 2-3 for gamma rays and neutron rays are significantly higher than those of Comparative Examples 1-4. This indicates that the radiation-proof performance of the concrete is greatly improved by adding the novel radiation-proof admixture of the present application.

[0086] Table 3: Construction performance test results of the radiation-proof concrete of Examples 1-3 and Comparative Examples 1-4

[0087] Table 3: Construction performance of the radiation-proof concrete

[0088]

[0089] As can be seen from Table 3, the strength of the concrete of the examples is significantly higher than that of the concrete of the comparative examples.

[0090] As can be seen from the data in Table 2 of Example 1 and Comparative Example 1, the radiation-proof performance of the concrete decreases without the addition of the nano-sized titanium dioxide sol, indicating that the nano-sized titanium dioxide sol has a radiation-proof effect.

[0091] As can be seen from the data in Table 2 of Example 1 and Comparative Example 2, the radiation-proof performance of the concrete decreases without the addition of the nano-sized barium sulfate, indicating that the nano-sized barium sulfate has a radiation-proof effect.

[0092] It can be seen from the data in Table 3 of Example 1 and Comparative Example 3 that the strength of the concrete is reduced without adding the seaweed glue, which indicates that the seaweed glue can effectively enhance the strength of the concrete.

[0093] It can be seen from the data in Table 3 of Example 1 and Comparative Example 4 that the slump of the concrete is significantly reduced without adding the polyurethane associative thickening agent and modified betaine, which indicates that the polyurethane associative thickening agent and modified betaine can effectively enhance the rheological property of the concrete and improve the segregation state of the concrete.

[0094] It should be noted that the specific parameters or some reagents in the above examples are specific examples or preferred examples under the concept of the present application, but are not limited thereto; those skilled in the art can make adaptive adjustments within the scope of the concept and protection of the present application.

Claims

1. A radiation shielding concrete admixture, characterized by, The preparation raw materials of the anti-radiation concrete admixture include, in terms of weight parts: A water-reducing mother liquor 20.0-40.0 parts; An air entraining agent 0.06-0.15 parts; An antifoaming agent 0.02-0.05 parts; A setting regulator 0.5-0.8 parts; A water-retaining thickening agent 0.2-0.4 parts; An anti-radiation agent 0.5-1.0 parts; and Water; The anti-radiation agent includes nano-TiO2 sol and nano-sized barium sulfate. The preparation steps of the nano-TiO2 sol are as follows: Tetrabutyl titanate and an alcohol solution are mixed to obtain a tetrabutyl titanate mixed solution; under magnetic stirring, dilute hydrochloric acid is added dropwise to adjust the tetrabutyl titanate mixed solution to be acidic, and an ethanol solution is slowly added dropwise into the tetrabutyl titanate mixed solution, and after the dropwise addition is completed, a light yellow solution is obtained; The light yellow solution is moved into a three-necked flask and stirred in a 40°C warm water bath, and after 1 hour, a white sol is obtained, and after natural cooling, the nano-TiO2 sol is prepared by ultrasonic gel breaking; The water-retaining thickening agent includes a polyurethane associated thickening agent, modified betaine and seaweed glue.

2. The radiation shielding concrete admixture according to claim 1, characterized in that, The preparation raw materials of the water-reducing mother liquor include, in terms of weight parts: An unsaturated acid monomer 15-30 parts; A polyethylene glycol macromonomer 200-300 parts; An oxidizing agent 0.5-2 parts; A reducing agent 0.1-0.5 parts; A ferrous sulfate solution 1.0-5.0 parts; Acrylamide 1-10 parts; A chain transfer agent 0.5-1.5 parts; and Water.

3. The radiation shielding concrete admixture of claim 2, wherein The unsaturated acid monomer includes at least one of acrylic acid and methacrylic acid.

4. The radiation shielding concrete admixture of claim 3, wherein The preparation steps of the water-reducing mother liquor are as follows: The polyethylene glycol macromonomer, the acrylamide and the oxidizing agent are mixed to obtain a first mixed solution; A liquid A and a liquid B are added dropwise into the first mixed solution, and after the dropwise addition is completed, the solution is kept warm for 1-3 hours to obtain a second mixed solution; the liquid A includes an unsaturated acid monomer and water, and the liquid B includes a reducing agent, a chain transfer agent and water; The pH of the second mixed solution is adjusted to 5-6 to obtain the water-reducing mother liquor; The structural formula of the water-reducing mother liquor is as follows: ； wherein the ratio of a to b is 1: (3-5), and n is an integer of 68-113.

5. The radiation shielding concrete admixture of claim 2, wherein The oxidizing agent includes at least one of hydrogen peroxide and ammonium persulfate.

6. The radiation shielding concrete admixture of claim 1, wherein The setting regulator includes at least one of trisodium phosphate, disodium hydrogen phosphate, sodium pyrophosphate and alkyl phosphate.

7. A method of producing the radiation shielding concrete admixture according to any one of claims 1 to 6, characterized by, The steps include: The water-reducing mother liquor and water are stirred and mixed, the air entraining agent, the antifoaming agent, the setting regulator and the water-retaining thickening agent are added while stirring, and finally the anti-radiation agent is added to obtain the anti-radiation concrete admixture.

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