CN112342487B - Microbial corrosion resistant treatment method for pipeline steel surface - Google Patents
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- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
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- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
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- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/14—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying for coating elongate material
- C23C4/16—Wires; Tubes
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/004—Dispersions; Precipitations
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
Abstract
The invention discloses a microbial corrosion resistant treatment method for the surface of pipeline steel, which comprises the following steps: firstly, uniformly mixing chromium powder, titanium powder and nickel powder to obtain alloyed powder; secondly, spraying alloying powder on the surface of the treated pipeline steel by supersonic flame spraying; and thirdly, scanning and strengthening the surface of the pipeline steel sprayed with the alloying powder by adopting a continuous laser, and then polishing according to the finish requirement of the surface of the pipeline steel. The invention utilizes the laser alloying surface treatment technology to lead the alloying element and the matrix component to generate the physical and chemical metallurgical reaction in the molten pool, and a layer of surface alloying structure with different components, structures and properties from the base material is prepared on the surface of the pipeline steel after the molten pool is solidified.
Description
Technical Field
The invention belongs to the technical field of laser surface alloying, and particularly relates to a microbial corrosion resistant treatment method for a pipeline steel surface.
Background
With the rapid development of the petroleum and energy industry in China in recent years, the mileage of a buried pipeline is longer and longer by 8 kilometers, the buried pipeline accounts for 2.5 percent of the total amount of the whole world, and 70 percent of petroleum and 99 percent of natural gas in China are transported by pipelines. The corrosion problem caused by the contact of the long-distance pipeline with the soil accounts for the largest proportion of the total corrosion amount due to the fact that most of the long-distance pipeline is buried under the soil, so that the leakage of a pipeline through hole and serious cracking accidents can be caused, and the corrosion problem of the long-distance pipeline is researched, namely the corrosion problem of the long-distance pipeline in contact with the soil is researched. In recent years, with the increasing of the conveying pressure of buried pipelines and the increasing of the quantity of high-sulfur, high-acid and high-salt crude oil, higher requirements are put on pipeline steel. At present, high-pressure, large-pipe-diameter and high-steel-grade pipeline steel is a necessary trend in the development of petroleum and natural gas transmission pipelines, so that the problem of corrosion failure becomes an important problem which cannot be avoided in the development, development and application processes of the high-steel-grade pipeline steel. Microbial corrosion refers to the destructive action of metal caused by the corrosion process directly or indirectly promoted by the life activities of microorganisms. The microbial corrosion has a wide range of harm, and the microbial corrosion has serious influence not only on underground buildings, but also on equipment in the fields of machinery, chemical engineering, nuclear energy, petroleum, aviation, electric power and the like. The annual economic losses due to microbial corrosion are in the billions of dollars. The microorganisms causing corrosion generally include, in addition to bacteria and fungi, algae, protozoa, and the like, and in most cases, corrosion is caused by the interaction of various bacteria. Microbial corrosion can cause pitting corrosion, crevice corrosion, selective dealloying corrosion, hydrogen embrittlement, corrosion under a deposition layer and the like of materials to be widely existed in steel, copper, aluminum and alloys thereof. The microbial corrosion can reduce the service life of equipment, and industrial water and circulating cooling water systems, underground water delivery pipelines, oil pipelines and the like are seriously influenced by the microbial corrosion. Extensive pipeline corrosion investigations have shown that, because the backfill surrounding the pipeline provides an environment that is more conducive to microbial growth than does the unmoved soil, the nutrients and cathodic polarization provided by the pipeline coating promote microbial accumulation on the pipeline surface, resulting in microbial corrosion under the release coating on most pipe exterior surfaces. Therefore, the problem of microbial corrosion failure becomes an inevitable important problem in the process of pipeline steel development, development and application.
At present, the microbial corrosion control method for pipeline steel mainly comprises the following steps: (1) physical methods such as sterilization using ultraviolet irradiation or external scraping of the biofilm; (2) chemical methods, such as the use of bactericides; (3) protective coatings, such as antibacterial coatings coated on the surfaces of metal materials, and anti-adhesion super-smooth or super-hydrophobic coatings coated on the surfaces of the metal materials, so that the surfaces of the metal materials are not easy to be adhered by microorganisms; (4) biological control method, namely preventing the microbial corrosion through the relations of competition and antagonism among microorganisms.
Laser surface alloying, also known as laser chemical heat treatment, is a new surface alloy layer using the original base material as the base body, which is formed by heating and melting the surface layer of the base body and the added elements by high-energy laser beams, and rapidly solidifying the mixture. Laser surface alloying has many unique advantages: (1) non-contact local treatment can be carried out, and irregular part machining is easy to realize; (2) the regional heating has high energy utilization rate; (3) the range of an alloy system is wide, and multiple alloy matching is convenient to realize; (4) can accurately control each process parameter and realize the depth control of the alloying layer; (4) the heat affected zone is small, and the deformation of the workpiece is small.
With the continuous development and improvement of the laser surface alloying technology and the expansion of the application field, the microbial corrosion resistance superiority of the laser surface alloying structure is more and more widely applied to the protection of the pipeline steel, the laser surface alloying structure can effectively control the microbial corrosion problem of the pipeline steel in the using process, and the method is an economic and reliable surface treatment method received by people and effectively solves the problem of the microbial corrosion protection of the pipeline steel.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for treating the microbial corrosion resistance of the surface of pipeline steel aiming at the defects of the prior art. The method utilizes a laser alloying surface treatment technology to enable alloying elements and matrix components to generate physical and chemical metallurgical reaction in a molten pool, and a layer of surface alloying structure with different components, structures and properties from a base material is prepared on the surface of the pipeline steel after the molten pool is solidified.
In order to solve the technical problems, the invention adopts the technical scheme that: a method for treating microbial corrosion resistance of the surface of pipeline steel is characterized by comprising the following steps:
step one, uniformly mixing chromium powder, titanium powder and nickel powder to obtain alloyed powder; the mass percentage of the chromium powder in the alloying powder is 30-40%, the mass percentage of the titanium powder is 30-40%, and the balance is nickel powder;
step two, carrying out surface rust removal, descaling and oil removal cleaning treatment on the surface of the pipeline steel; then spraying the alloying powder in the first step on the surface of the treated pipeline steel by adopting supersonic flame spraying;
and step three, scanning and strengthening the surface of the pipeline steel sprayed with the alloying powder in the step two by using a continuous laser, and then polishing according to the finish requirement of the surface of the pipeline steel.
The microbial corrosion resistance treatment method for the surface of the pipeline steel is characterized in that in the first step, the mass percentage of chromium in the chromium powder is more than 99.9%, and the average particle size is less than 20 mu m; the titanium powder contains more than 99.9 percent of titanium by mass and has an average particle size of less than 20 mu m; the nickel powder contains more than 99.9 percent of nickel by mass and has an average particle size of less than 20 mu m.
The method for the microbial corrosion resistance treatment of the surface of the pipeline steel is characterized by further comprising the step two of drying the alloyed powder at the temperature of 80-120 ℃ for 40-60 min before supersonic flame spraying.
The method for treating the microbial corrosion resistance of the surface of the pipeline steel is characterized in that the process conditions of the supersonic flame spraying in the step two are as follows: the oxygen flow of the combustion improver is 80L/min-120L/min, the gas propane flow is 80L/min-120L/min, the nitrogen flow of the powder feeding gas is 60L/min-80L/min, the moving speed of the spray gun is 40 mm/s-80 mm/s, the spraying distance is 200 mm-400 mm, and the spraying thickness is 800 μm-1000 μm.
The method for treating the microbial corrosion resistance of the surface of the pipeline steel is characterized in that the scanning strengthening process parameters in the step three are as follows: the laser power P is 4000W-8000W, the scanning speed V is 200 mm/min-400 mm/min, the diameter of a light spot is 2 mm-4 mm, nitrogen is continuously introduced as protective gas in the scanning process, the gas pressure is 1.0 MPa-2.0 MPa, the gas flow is 10L/min-20L/min, the scanning mode is single-path linear scanning, and the lap joint between two adjacent single paths is 50%.
Compared with the prior art, the invention has the following advantages:
1. the invention utilizes the laser alloying surface treatment technology to lead the alloying element and the matrix component to generate the physical and chemical metallurgical reaction in the molten pool, and a layer of surface alloying structure with different components, structures and properties from the base material is prepared on the surface of the pipeline steel after the molten pool is solidified.
2. The invention takes titanium, chromium and nickel as the added elements of the laser surface alloying structure. Alloying elements of titanium, chromium and nickel and iron in the matrix generate a FeTiCrNi quaternary eutectic compound in the laser alloying process, and the quaternary eutectic compound has excellent microbial corrosion resistance and is used as a corrosion-resistant phase of the laser surface alloying structure, so that the microbial corrosion resistance of the laser surface alloying structure is greatly improved.
3. The invention takes titanium as an additive element of the laser surface alloying structure. Nitrogen as a nitrogen source is injected into the metal melting pool in the laser alloying process to perform nitridation reaction with titanium which is an element forming nitride ceramics so as to form titanium nitride ceramic particles. The ceramic particles are dispersed in the alloying layer, play a role in resisting microbial corrosion in a microbial corrosion environment, and further improve the microbial corrosion resistance of the laser surface alloying structure.
4. In the laser beam scanning process, the lap joint between two adjacent single tracks is 50%, so that the hardening layer is influenced by the lap joint tempering effect, a matrix structure generates a tempered sorbite structure, and the tempered sorbite structure is a tempered structure of martensite and is a mixture of ferrite and granular carbide. The ferrite of the tempered sorbite structure has basically no carbon supersaturation, and the carbide is also stable carbide and is a balanced structure at normal temperature. Therefore, the tempered sorbite structure has higher corrosion resistance.
The matrix tissue of the laser surface alloying tissue is a tempered sorbite, the FeTiCrNi quaternary eutectic compound is used as a compound microbial corrosion resistant phase, and the titanium nitride ceramic particles are used as a ceramic microbial corrosion resistant phase, so that the laser surface alloying tissue has excellent microbial corrosion resistant performance, can effectively improve the microbial corrosion resistant phase performance of pipeline steel, and has an effective microbial corrosion resistant protection effect on the pipeline steel.
5. Compared with the traditional alloying powder coating prepared by vapor deposition, bonding, electroplating and other processes, the alloying powder coating prepared by the method has the advantages of high bonding strength with a matrix, difficult shedding of the alloying powder coating in the laser alloying process and the like.
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and embodiments.
Drawings
FIG. 1 is a metallographic photograph of a laser surface alloyed structure prepared in example 1 of the present invention.
Detailed Description
Example 1
The laser alloying surface strengthening treatment method for the pipeline steel is characterized by comprising the following steps of:
step one, uniformly mixing chromium powder (the mass percentage of chromium is more than 99.9 percent, and the average particle size is less than 20 mu m), titanium powder (the mass percentage of titanium is more than 99.9 percent, and the average particle size is less than 20 mu m) and nickel powder (the mass percentage of nickel is more than 99.9 percent, and the average particle size is less than 20 mu m) to obtain alloyed powder; the mass percentage of the chromium powder in the alloying powder is 40%, the mass percentage of the titanium powder is 30%, and the balance is nickel powder;
step two, carrying out surface rust removal, descaling and oil removal cleaning treatment on the surface of the pipeline steel (X80); drying the alloying powder in the step one for 40min at the temperature of 80 ℃, and then spraying the dried alloying powder on the surface of the treated pipeline steel by adopting supersonic flame; the process conditions of the supersonic flame spraying are as follows: the oxygen flow of the combustion improver is 80L/min, the propane flow of the fuel gas is 80L/min, the nitrogen flow of the powder feeding gas is 60L/min, the moving speed of the spray gun is 40mm/s, the spraying distance is 200mm, and the spraying thickness is 800 mu m;
thirdly, scanning and strengthening the surface of the pipeline steel sprayed with the alloying powder in the second step by adopting a continuous laser, and then polishing according to the finish requirement of the surface of the pipeline steel to obtain a laser surface alloying structure on the surface of the pipeline steel; the process parameters of the scanning reinforcement are as follows: the laser power P is 4000W, the scanning speed V is 200mm/min, the diameter of a light spot is 2mm, nitrogen is continuously introduced as protective gas in the scanning process, the gas pressure is 1.0MPa, the gas flow is 10L/min, the scanning mode is single-channel linear scanning, and the lap joint between two adjacent single channels is 50%.
Fig. 1 is a metallographic photograph of the laser surface alloyed structure prepared in this example, and it can be seen from fig. 1 that the bonding condition of the pipeline steel substrate and the laser surface alloyed structure is good, the structure is uniform, the laser surface alloyed structure is compact, and no obvious aggregated pores or macrocracks exist.
The laser surface alloying structure prepared by the embodiment has excellent microbial corrosion resistance, is used for the microbial corrosion resistance working environment of the long-distance pipeline steel, can meet the requirement of the working environment of the long-distance pipeline steel, effectively solves the problem of microbial corrosion resistance of the long-distance pipeline steel, and has good application prospect in the field of long-distance pipeline protection.
Example 2
The laser alloying surface strengthening treatment method for the pipeline steel is characterized by comprising the following steps of:
step one, uniformly mixing chromium powder (the mass percentage of chromium is more than 99.9 percent, and the average particle size is less than 20 mu m), titanium powder (the mass percentage of titanium is more than 99.9 percent, and the average particle size is less than 20 mu m) and nickel powder (the mass percentage of nickel is more than 99.9 percent, and the average particle size is less than 20 mu m) to obtain alloyed powder; the mass percentage of the chromium powder in the alloying powder is 30%, the mass percentage of the titanium powder is 40%, and the balance is nickel powder;
step two, carrying out surface rust removal, descaling and oil removal cleaning treatment on the surface of the pipeline steel (X70); drying the alloying powder in the step one for 50min at the temperature of 100 ℃, and then spraying the dried alloying powder on the surface of the treated pipeline steel by adopting supersonic flame spraying; the process conditions of the supersonic flame spraying are as follows: the oxygen flow of the combustion improver is 100L/min, the propane flow of the fuel gas is 100L/min, the nitrogen flow of the powder feeding gas is 70L/min, the moving speed of the spray gun is 60mm/s, the spraying distance is 300mm, and the spraying thickness is 900 micrometers;
thirdly, scanning and strengthening the surface of the pipeline steel sprayed with the alloying powder in the second step by adopting a continuous laser, and then polishing according to the finish requirement of the surface of the pipeline steel to obtain a laser surface alloying structure on the surface of the pipeline steel; the process parameters of the scanning reinforcement are as follows: the laser power P is 6000W, the scanning speed V is 300mm/min, the diameter of a light spot is 3mm, nitrogen is continuously introduced as protective gas in the scanning process, the gas pressure is 1.5MPa, the gas flow is 15L/min, the scanning mode is single-channel linear scanning, and the lap joint between two adjacent single channels is 50%.
The laser surface alloying structure prepared by the embodiment has excellent microbial corrosion resistance, is used for the microbial corrosion resistance working environment of the long-distance pipeline steel, can meet the requirement of the working environment of the long-distance pipeline steel, effectively solves the problem of microbial corrosion resistance of the long-distance pipeline steel, and has good application prospect in the field of long-distance pipeline protection.
Example 3
The laser alloying surface strengthening treatment method for the pipeline steel is characterized by comprising the following steps of:
step one, uniformly mixing chromium powder (the mass percentage of chromium is more than 99.9 percent, and the average particle size is less than 20 mu m), titanium powder (the mass percentage of titanium is more than 99.9 percent, and the average particle size is less than 20 mu m) and nickel powder (the mass percentage of nickel is more than 99.9 percent, and the average particle size is less than 20 mu m) to obtain alloyed powder; the mass percentage of the chromium powder, the mass percentage of the titanium powder and the balance of the nickel powder in the alloying powder are respectively 35 percent and 35 percent;
step two, carrying out surface rust removal, descaling and oil removal cleaning treatment on the surface of the pipeline steel (X100); drying the alloying powder in the step one for 60min at 120 ℃, and then spraying the dried alloying powder on the surface of the treated pipeline steel by adopting supersonic flame spraying; the process conditions of the supersonic flame spraying are as follows: the oxygen flow of the combustion improver is 120L/min, the propane flow of the fuel gas is 120L/min, the nitrogen flow of the powder feeding gas is 80L/min, the moving speed of the spray gun is 80mm/s, the spraying distance is 400mm, and the spraying thickness is 1000 mu m;
thirdly, scanning and strengthening the surface of the pipeline steel sprayed with the alloying powder in the second step by adopting a continuous laser, and then polishing according to the finish requirement of the surface of the pipeline steel to obtain a laser surface alloying structure on the surface of the pipeline steel; the process parameters of the scanning reinforcement are as follows: the laser power P is 8000W, the scanning speed V is 400mm/min, the spot diameter is 4mm, nitrogen is continuously introduced as protective gas in the scanning process, the gas pressure is 2.0MPa, the gas flow is 20L/min, the scanning mode is single-channel linear scanning, and the lap joint between two adjacent single channels is 50%.
The laser surface alloying structure prepared by the embodiment has excellent microbial corrosion resistance, is used for the microbial corrosion resistance working environment of the long-distance pipeline steel, can meet the requirement of the working environment of the long-distance pipeline steel, effectively solves the problem of microbial corrosion resistance of the long-distance pipeline steel, and has good application prospect in the field of long-distance pipeline protection.
The average corrosion rates of the line steels of examples 1, 2 and 3 were measured by a weight loss analysis method in the presence or absence of a laser surface alloyed structure, and table 1 shows the average corrosion rates of the line steels of examples 1, 2 and 3 after immersion in sulfate-reducing bacteria and iron-oxidizing bacteria simulated solutions for 10 days, 20 days, 30 days and 40 days, respectively, in the presence or absence of a laser surface alloyed structure.
TABLE 1 microbial Corrosion resistance of line steels with and without laser surface alloyed organization
From the test data in table 1, it can be observed that under the same microbial corrosion condition, the average corrosion rate of the laser alloyed surface subjected to the microbial corrosion resistant treatment is greatly lower than that of the laser alloyed surface not subjected to the microbial corrosion resistant treatment, so that the laser surface alloyed structure can greatly reduce the corrosion rate of the pipeline steel, and effectively improve the microbial corrosion resistance of the pipeline steel.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (4)
1. A method for treating microbial corrosion resistance of the surface of pipeline steel is characterized by comprising the following steps:
step one, uniformly mixing chromium powder, titanium powder and nickel powder to obtain alloyed powder; the mass percentage of the chromium powder in the alloying powder is 30-40%, the mass percentage of the titanium powder is 30-40%, and the balance is nickel powder;
step two, carrying out surface rust removal, descaling and oil removal cleaning treatment on the surface of the pipeline steel; then spraying the alloying powder in the first step on the surface of the treated pipeline steel by adopting supersonic flame spraying;
thirdly, scanning and strengthening the surface of the pipeline steel sprayed with the alloying powder in the second step by using a continuous laser, and then polishing according to the finish requirement of the surface of the pipeline steel; the process parameters of the scanning reinforcement are as follows: the laser power P is 4000W-8000W, the scanning speed V is 200 mm/min-400 mm/min, the diameter of a light spot is 2 mm-4 mm, nitrogen is continuously introduced as protective gas in the scanning process, the gas pressure is 1.0 MPa-2.0 MPa, the gas flow is 10L/min-20L/min, the scanning mode is single-path linear scanning, and the lap joint between two adjacent single paths is 50%.
2. The method for treating microbial corrosion resistance of the surface of pipeline steel according to claim 1, wherein in the first step, the chromium powder contains more than 99.9% of chromium by mass and has an average particle size of less than 20 μm; the titanium powder contains more than 99.9 percent of titanium by mass and has an average particle size of less than 20 mu m; the nickel powder contains more than 99.9 percent of nickel by mass and has an average particle size of less than 20 mu m.
3. The method for treating the microbial corrosion resistance of the surface of the pipeline steel as claimed in claim 1, further comprising drying the alloyed powder at 80-120 ℃ for 40-60 min before the supersonic flame spraying in the second step.
4. The method for treating the microbial corrosion resistance of the surface of the pipeline steel as claimed in claim 1, wherein the process conditions of the supersonic flame spraying in the second step are as follows: the oxygen flow of the combustion improver is 80L/min-120L/min, the gas propane flow is 80L/min-120L/min, the nitrogen flow of the powder feeding gas is 60L/min-80L/min, the moving speed of the spray gun is 40 mm/s-80 mm/s, the spraying distance is 200 mm-400 mm, and the spraying thickness is 800 μm-1000 μm.
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| CN105420657A (en) * | 2008-12-17 | 2016-03-23 | 高标国际有限公司 | Anti-microbial coating and metal product containing same |
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