A method for preventing corrosion in polar ice base material by mixing steel fibers

Abstract

The application discloses a kind of polar ice base material inner mixing steel fiber corrosion prevention method, belong to steel fiber corrosion prevention technology field for ice base material, by oil removal, pickling, washing to steel fiber, then immerse in water, phosphoric acid, nitric acid, nickel nitrate, sodium molybdate, nickel carbonate and manganese carbonate composition film-forming solution, place in hydrothermal kettle and carry out surface oxidation treatment, prepare polar ice base material for corrosion-resistant steel fiber.The beneficial effects of the application are: using hydrothermal method, by chemical deposition on the surface of steel fiber a layer of wear-resistant, corrosion-resistant manganese-nickel-based crystal film, improve the corrosion resistance of steel fiber, at the same time, the surface roughness of the conversion film formed on the surface of the steel fiber is large, thereby improving the bonding strength of the steel fiber and the matrix, and improving the mechanical properties of the material.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of steel fiber corrosion prevention, and particularly relates to a method for preventing corrosion of steel fibers mixed in polar ice base materials. BACKGROUND

[0002] The total area of the north and south poles is more than 35 million square kilometers. At present, China has established its own polar research stations in the north and south poles. The exploration and evaluation report points out that the north and south poles have rich resources such as energy, minerals and biology. For example, the north pole has 13% of the world's unproven oil reserves, 30% of the world's undeveloped natural gas reserves and 9% of the world's coal resources. The polar region contains minerals such as gold, copper, iron, lead, platinum, nickel and zinc. In addition, due to its special geographical pattern, the polar region has very important strategic significance in the military field. Therefore, the development and utilization of the polar region are increasingly valued by countries.

[0003] The polar environment is an extreme environment with low temperature, high seawater salinity, strong wind, high sea waves, storm and snow, floating ice and polar night. It is obviously different from the traditional marine corrosion environment, and therefore puts forward more stringent requirements for the corrosion of polar materials. The super high performance ice base material is a new type of composite material with super high mechanical properties, high toughness, super high durability and excellent pouring and forming performance. The steel fiber mixed in the ice base material accounts for a large proportion as a structural material, can fully play the characteristics of each component material and the performance transmission between them, improve the mechanical properties of the ice base material, has the advantages of good toughness, strong fatigue resistance, wear resistance, and can effectively limit crack opening and crack propagation in any direction. The application of steel fiber ice base material has obvious advantages, fully plays the advantages of steel fiber matrix reinforcement, and the reliable bonding between steel fiber and ice base material is the basic condition for their common work. However, the corrosion of steel fiber is the most prominent problem affecting the durability of components in actual engineering application. The main factors affecting material corrosion in the polar region include the following four points: first, the wind speed is high, and the particles in the wind can damage the surface of the material; second, the high solar radiation leads to the aging of organic materials; third, the soluble salt in the snow and ice on the surface of the material; fourth, the temperature in summer is higher than the melting point of ice and snow, which leads to the covering of the surface of the material by the soluble salt film. Research shows that the corrosion of steel materials is relatively slight in the areas with high altitude and close to the south pole, which is 0.03 um / a. In the areas with low altitude, the corrosion is relatively serious and fluctuates greatly, which is 3.35-36.4 um / a. In the areas with slightly lower latitude in the north pole, the corrosion is relatively serious, and the highest corrosion rate can reach 222 um / a. Therefore, the corrosion of materials in the polar environment is obvious. In order to prevent the durability problem of the structure, the steel fiber can be subjected to corrosion prevention process, so that the steel fiber material can still bear the stress of the component and support the overall safety and stability of the structure in the corrosion environment.

[0004] The existing steel fiber surface corrosion prevention treatment mostly adopts the method of copper plating, and the process has the defects of easy sediment, thin plating film, uneven film, poor durability and the like, and it is difficult to meet the demand of large-scale engineering application, based on this, the application provides an anti-corrosion steel fiber for ice-based material, a manganese-nickel-based crystal film with wear resistance and corrosion resistance is chemically deposited on the surface of the steel fiber by using the hydrothermal method, the corrosion resistance of the steel fiber is improved, the surface roughness of the conversion film formed on the surface of the steel fiber is large, and then the bonding strength of the steel fiber and the matrix is improved, and the mechanical properties of the material are improved. SUMMARY

[0005] In view of the defects of the prior art, the application aims to provide a polar ice-based material internally mixed with steel fiber corrosion prevention method, which is used to solve the defects of the existing corrosion prevention treatment, such as easy sediment, thin plating film, uneven film, poor durability and the like, and difficult to meet the demand of large-scale engineering application.

[0006] To achieve the above object, the application adopts the following technical scheme: a polar ice-based material internally mixed with steel fiber corrosion prevention method, the steel fiber is subjected to oil removal, pickling, washing, then immersed in a film forming solution composed of water, phosphoric acid, nitric acid, nickel nitrate, sodium molybdate, nickel carbonate and manganese carbonate, and subjected to surface oxidation treatment in a hydrothermal kettle to obtain the polar ice-based material anti-corrosion steel fiber.

[0007] The film forming solution comprises the following components in weight fraction: 150-200 parts of phosphoric acid, 35-45 parts of nitric acid, 5-10 parts of nickel nitrate, 10-20 parts of sodium molybdate, 1-5 parts of nickel carbonate, 50-70 parts of manganese carbonate and 350-450 parts of water.

[0008] The phosphoric acid used is analytical pure, a medium-strength inorganic acid, with a concentration of more than 85%;

[0009] The nitric acid used is a strong inorganic acid, commercially available with a concentration of about 68%;

[0010] The nickel nitrate used is analytical pure, a green crystalline powder, with a purity of 99.5%;

[0011] The sodium molybdate used is analytical pure, a white crystalline body, with a purity of 99%;

[0012] The nickel carbonate used is analytical pure, a light green powder, with a purity of 99.9%;

[0013] The manganese carbonate used is analytical pure, a white powder, with a purity of 99.5%.

[0014] The film forming solution comprises the following components: 150 parts of phosphoric acid, 35 parts of nitric acid, 5 parts of nickel nitrate, 10 parts of sodium molybdate, 1 part of nickel carbonate, 50 parts of manganese carbonate and 350 parts of water.

[0015] The film forming solution comprises the following components: phosphoric acid 200 parts, nitric acid 45 parts, nickel nitrate 10 parts, sodium molybdate 20 parts, nickel carbonate 5 parts, manganese carbonate 70 parts, and water 450 parts.

[0016] The film forming solution comprises the following components: phosphoric acid 180 parts, nitric acid 40 parts, nickel nitrate 8 parts, sodium molybdate 15 parts, nickel carbonate 3 parts, manganese carbonate 60 parts, and water 400 parts.

[0017] The film forming solution comprises the following components: phosphoric acid 200 parts, nitric acid 42 parts, nickel nitrate 9 parts, sodium molybdate 18 parts, nickel carbonate 4 parts, manganese carbonate 60 parts, and water 420 parts.

[0018] The polar ice base material internally mixed with steel fibers based on the above-mentioned corrosion prevention method comprises the following steps:

[0019] Step one: weigh the components of the film forming solution, first mix water, phosphoric acid and nitric acid and stir uniformly to obtain a mixed solution, and wait for the reaction temperature to decrease to room temperature before operating the next step;

[0020] Step two: add nickel nitrate, sodium molybdate and nickel carbonate to the mixed solution obtained in step one and stir for 15-20 minutes to fully dissolve them;

[0021] Step three: on the basis of step two, add manganese carbonate and stir for about 5 minutes until the solution reaction is clear;

[0022] Step four: remove the oil from the steel fibers, remove the rust on the surface using a 10% hydrochloric acid aqueous solution and then rinse twice with water, then place the steel fibers in a hydrothermal reaction kettle, pour the clear solution obtained in step three into the steel fibers;

[0023] Step five: place the hydrothermal reaction kettle in a 110°C oven and react for 20-30 minutes, then take it out, and the polar ice base material internally mixed with corrosion-resistant steel fibers can be taken out after the hydrothermal reaction kettle is naturally cooled.

[0024] The beneficial effects of the present application are:

[0025] 1. By using the hydrothermal method to react in a closed reaction kettle, the interface reaction between the solution and the steel fibers is more rapid due to the certain temperature and pressure of the hydrothermal reaction kettle, the crystal is more easily crystallized into a film, and the film and the matrix are more firmly combined under a certain pressure, which is more efficient and the film is more compact than the traditional film forming method;

[0026] 2. The prepared steel fiber has high film forming efficiency and large film thickness on the surface. Due to the presence of nickel, molybdenum and manganese elements, the formed surface crystal film has rough, wear-resistant and corrosion-resistant characteristics compared with traditional copper plating and other measures. The crystal film blocks the contact between the steel fiber substrate and the external medium, hinders the chemical and electrochemical reactions of the metal, and thus can effectively prevent the corrosion of the steel fiber material. At the same time, due to the roughness of the crystal film to a certain extent, the adhesion between the steel fiber and the ice-based material can be increased, and thus the mechanical properties and structural stability of the ice-based material can be improved. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 Figure 6 is a 600-fold scanning electron microscope micrograph of the surface of the steel fiber after hydrothermal plating in Example 3 of the present application;

[0028] Figure 2 Figure 7 is a 5000-fold scanning electron microscope micrograph of the surface of the steel fiber after hydrothermal plating in Example 3 of the present application;

[0029] Figure 3 Figure 8 is a 200-fold optical microscope micrograph of the compact film on the surface of the steel fiber after corrosion for 30 days after hydrothermal plating in Example 3 of the present application;

[0030] Figure 4 Figure 9 is a 500-fold optical microscope micrograph of the compact film on the surface of the steel fiber after corrosion for 30 days after hydrothermal plating in Example 3 of the present application. DETAILED DESCRIPTION

[0031] The specific embodiments of the present application are described below to facilitate understanding of the present application by those skilled in the art, but it should be clear that the present application is not limited to the scope of the specific embodiments. For those skilled in the art, it is obvious that various changes are within the spirit and scope of the present application as defined in the appended claims, and all inventions utilizing the concept of the present application are within the scope of protection.

[0032] The following examples are provided in conjunction with the content of the present application, but the present application is not limited to the following examples: Example 1

[0033] A method for preventing corrosion of steel fibers in polar ice-based materials, the film forming solution of the steel fiber comprises the following components by weight fraction: 150 parts of phosphoric acid, 35 parts of nitric acid, 5 parts of nickel nitrate, 10 parts of sodium molybdate, 1 part of nickel carbonate, 50 parts of manganese carbonate, and 350 parts of water;

[0034] The above method for preventing corrosion of steel fibers in polar ice-based materials comprises the following steps:

[0035] Step one: take the weight of each component of the film-forming solution, first mix water, phosphoric acid and nitric acid and stir until uniform to obtain a mixed solution, and wait for the reaction temperature to decrease to room temperature before operating the next step;

[0036] Step two: add nickel nitrate, sodium molybdate and nickel carbonate to the mixed solution obtained in step one and stir for 15-20 minutes to fully dissolve them;

[0037] Step three: on the basis of step two, add manganese carbonate and stir for about 5 minutes until the solution reaction is clear;

[0038] Step four: remove oil from the steel fibers, remove rust on their surface using a 10% hydrochloric acid solution and then rinse twice with clean water, then place the steel fibers in a hydrothermal reaction kettle, pour the clear solution obtained in step three into the kettle and submerge the steel fibers;

[0039] Step five: place the hydrothermal reaction kettle in a 110°C oven and react for 20-30 minutes, then take it out, let the hydrothermal reaction kettle cool naturally, and then take out the polar ice base material with corrosion-resistant steel fibers. Example 2:

[0040] A method for preventing corrosion of a polar ice base material by mixing steel fibers inside, the film-forming solution of the steel fibers includes the following components by weight: phosphoric acid 200 parts, nitric acid 45 parts, nickel nitrate 10 parts, sodium molybdate 20 parts, nickel carbonate 5 parts, manganese carbonate 70 parts, and water 450 parts;

[0041] The above method for preventing corrosion of a polar ice base material by mixing steel fibers inside includes the following steps:

[0042] Step one: take the weight of each component of the film-forming solution, first mix water, phosphoric acid and nitric acid and stir until uniform to obtain a mixed solution, and wait for the reaction temperature to decrease to room temperature before operating the next step;

[0043] Step two: add nickel nitrate, sodium molybdate and nickel carbonate to the mixed solution obtained in step one and stir for 15-20 minutes to fully dissolve them;

[0044] Step three: on the basis of step two, add manganese carbonate and stir for about 5 minutes until the solution reaction is clear;

[0045] Step four: remove oil from the steel fibers, remove rust on their surface using a 10% hydrochloric acid solution and then rinse twice with clean water, then place the steel fibers in a hydrothermal reaction kettle, pour the clear solution obtained in step three into the kettle and submerge the steel fibers;

[0046] Step five: place the hydrothermal reaction kettle in a 110°C oven and react for 20-30 minutes, then take it out, let the hydrothermal reaction kettle cool naturally, and then take out the polar ice base material with corrosion-resistant steel fibers. Example 3:

[0047] A kind of polar ice base material in steel fiber anticorrosion method of mixing, steel fiber film-forming solution is calculated according to weight fraction, including the following components: phosphoric acid 180 parts, nitric acid 40 parts, nickel nitrate 8 parts, sodium molybdate 15 parts, nickel carbonate 3 parts, manganese carbonate 60 parts, water 400 parts;

[0048] The above-mentioned polar ice base material in steel fiber anticorrosion method of mixing includes the following steps:

[0049] Step one: weigh the weight of each component of film-forming solution, first mix water, phosphoric acid and nitric acid uniformly to obtain a mixed solution, and wait for the reaction temperature to decrease to room temperature before operating the next step;

[0050] Step two: add nickel nitrate, sodium molybdate and nickel carbonate to the mixed solution obtained in step one and stir for 15-20 minutes to fully dissolve them;

[0051] Step three: on the basis of step two, add manganese carbonate and stir for about 5 minutes until the solution reaction is clear;

[0052] Step four: remove oil from steel fiber, remove rust on its surface using 10% hydrochloric acid solution and then rinse with water twice, then place the steel fiber in a hydrothermal reactor, pour the clear solution obtained in step three and submerge the steel fiber;

[0053] Step five: place the hydrothermal reactor in a 110°C oven and react for 20-30 minutes, then take it out, and the polar ice base material can be taken out after the hydrothermal reactor is naturally cooled. Example 4:

[0054] A kind of polar ice base material in steel fiber anticorrosion method of mixing, steel fiber film-forming solution is calculated according to weight fraction, including the following components: phosphoric acid 200 parts, nitric acid 42 parts, nickel nitrate 9 parts, sodium molybdate 18 parts, nickel carbonate 4 parts, manganese carbonate 60 parts, water 420 parts;

[0055] The above-mentioned polar ice base material in steel fiber anticorrosion method of mixing includes the following steps:

[0056] Step one: weigh the weight of each component of film-forming solution, first mix water, phosphoric acid and nitric acid uniformly to obtain a mixed solution, and wait for the reaction temperature to decrease to room temperature before operating the next step;

[0057] Step two: add nickel nitrate, sodium molybdate and nickel carbonate to the mixed solution obtained in step one and stir for 15-20 minutes to fully dissolve them;

[0058] Step three: on the basis of step two, add manganese carbonate and stir for about 5 minutes until the solution reaction is clear;

[0059] Step 4: Degrease the steel fibers. Remove the rust on the surface with a 10% hydrochloric acid solution and rinse twice with clean water. Then place the steel fibers in a hydrothermal reactor and pour in the clear solution obtained in Step 3 until it covers the steel fibers.

[0060] Step 5: Place the hydrothermal reactor in an oven at 110℃ for 20-30 minutes and then remove it. After the hydrothermal reactor has cooled naturally, the anti-corrosion steel fiber for the polar ice-based material can be removed.

[0061] The surface crystalline films formed in the implementation cases have similar microstructures, with the test results of Example 3 being used as a reference. Figures 1-4 :

[0062] Depend on Figure 1 The surface of the steel fiber after hydrothermal coating was examined under a scanning electron microscope at 600x magnification. Figure 2 After hydrothermal coating, the surface of the steel fiber was examined under a scanning electron microscope at 5000x magnification. The results showed that the crystalline film formed on the surface of the steel fiber was dense and crystalline.

[0063] Depend on Figure 3 After hydrothermal coating and surface etching of steel fibers for 30 days, the morphology of the dense film under an optical microscope at 200x magnification is as follows: Figure 4 After 30 days of hydrothermal coating, the morphology of the dense film on the steel fiber surface was observed under an optical microscope at 500x magnification. The results showed that the steel fiber surface remained tight, dense, and uniform after 30 days of corrosion. The surface was still a black, rough crystalline morphology without any corrosion holes or rust spots.

[0064] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

[0065] The parts of this invention not described in detail are prior art.

Claims

1. A method for preventing corrosion in polar ice base material by mixing steel fibers into the ice base material, characterized by: The polar ice base material corrosion resistant steel fiber is prepared by oil removal, pickling, water washing, then immersing in a film forming solution composed of water, phosphoric acid, nitric acid, nickel nitrate, sodium molybdate, nickel carbonate and manganese carbonate, and then placing in a hydrothermal kettle for surface oxidation treatment; The film forming solution comprises the following components in parts by weight: phosphoric acid 150-200 parts, nitric acid 35-45 parts, nickel nitrate 5-10 parts, sodium molybdate 10-20 parts, nickel carbonate 1-5 parts, manganese carbonate 50-70 parts, and water 350-450 parts; The phosphoric acid used in the film forming solution is analytical pure, a medium-strength inorganic acid, and has a concentration of 85% or above; The nitric acid used is a strong inorganic acid, and has a concentration of 68%; The nickel nitrate used is analytical pure, a green crystalline powder, and has a purity of 99.5%; The sodium molybdate used is analytical pure, a white crystalline substance, and has a purity of 99%; The nickel carbonate used is analytical pure, a light green powder, and has a purity of 99.9%; The manganese carbonate used is analytical pure, a white powder, and has a purity of 99.5%; The polar ice base material corrosion resistant method comprises the following steps: Step one: weigh the components of the film forming solution, mix water, phosphoric acid and nitric acid to obtain a mixed solution, and wait for the reaction temperature to decrease to room temperature before proceeding to the next step; Step two: add nickel nitrate, sodium molybdate and nickel carbonate to the mixed solution obtained in step one, stir for 15-20 minutes to ensure complete dissolution; Step three: add manganese carbonate to the solution obtained in step two, stir for 5 minutes, and then use the solution; Step four: remove the oil on the steel fiber, remove the rust on the surface of the steel fiber using a 10% hydrochloric acid solution, and then rinse the steel fiber with water twice, then place the steel fiber in a hydrothermal reaction kettle, pour the clear solution obtained in step three into the kettle, and immerse the steel fiber in the solution; Step five: place the hydrothermal reaction kettle in an oven at 110°C for 20-30 minutes, then take it out, and then take out the polar ice base material corrosion resistant steel fiber after the hydrothermal reaction kettle cools down naturally.

2. The method according to claim 1, characterized in that: The film forming solution comprises the following components: phosphoric acid 150 parts, nitric acid 35 parts, nickel nitrate 5 parts, sodium molybdate 10 parts, nickel carbonate 1 part, manganese carbonate 50 parts, and water 350 parts.

3. The method for corrosion protection of polar ice-based materials by incorporating steel fibers according to claim 1, characterized in that: The film forming solution comprises the following components: phosphoric acid 200 parts, nitric acid 45 parts, nickel nitrate 10 parts, sodium molybdate 20 parts, nickel carbonate 5 parts, manganese carbonate 70 parts, and water 450 parts.

4. The method for corrosion protection of polar ice-based materials by incorporating steel fibers according to claim 1, characterized in that: The film forming solution comprises the following components: phosphoric acid 180 parts, nitric acid 40 parts, nickel nitrate 8 parts, sodium molybdate 15 parts, nickel carbonate 3 parts, manganese carbonate 60 parts, and water 400 parts.

5. The method for corrosion protection of polar ice-based materials by incorporating steel fibers according to claim 1, characterized in that: The film forming solution comprises the following components: phosphoric acid 200 parts, nitric acid 42 parts, nickel nitrate 9 parts, sodium molybdate 18 parts, nickel carbonate 4 parts, manganese carbonate 60 parts, and water 420 parts.

Images