CN111118385A - Anti-corrosion alloy sucker rod and manufacturing method thereof - Google Patents

Anti-corrosion alloy sucker rod and manufacturing method thereof Download PDF

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Publication number
CN111118385A
CN111118385A CN201811280567.3A CN201811280567A CN111118385A CN 111118385 A CN111118385 A CN 111118385A CN 201811280567 A CN201811280567 A CN 201811280567A CN 111118385 A CN111118385 A CN 111118385A
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China
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temperature
corrosion
sucker rod
chromium
parts
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CN201811280567.3A
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Chinese (zh)
Inventor
钱钦
智勤功
姜东�
周娜
周宏斌
王峰
杜玮暄
朱泽军
肖萍
孙衍东
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China Petroleum and Chemical Corp
Sinopec Research Institute of Petroleum Engineering Shengli Co
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China Petroleum and Chemical Corp
Sinopec Research Institute of Petroleum Engineering Shengli Co
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Priority to CN201811280567.3A priority Critical patent/CN111118385A/en
Publication of CN111118385A publication Critical patent/CN111118385A/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH DRILLING; MINING
    • E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B17/00—Drilling rods or pipes; Flexible drill strings; Kellies; Drill collars; Sucker rods; Cables; Casings; Tubings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention relates to an anti-corrosion alloy sucker rod and a manufacturing method thereof, wherein the anti-corrosion alloy sucker rod comprises a rod body and a joint, the rod body sequentially comprises a steel substrate, a TiCrN hard film, a TiCrSiN anti-corrosion film and a polyether-ether-ketone anti-corrosion layer from inside to outside, and the steel substrate has stronger anti-corrosion property; the TiCrN hard film has higher hardness, higher working stability and oxidation resistance; the TiCrSiN anticorrosive film has excellent abrasive grain wear resistance, corrosion resistance and oxidation resistance; the corrosion resistance of the polyether-ether-ketone anticorrosive layer is similar to that of nickel steel, so that the rod body has excellent corrosion resistance and high strength and long service life.

Description

Anti-corrosion alloy sucker rod and manufacturing method thereof
Technical Field
The invention relates to the technical field of sucker rods for oil exploration, in particular to an anti-corrosion alloy sucker rod and a manufacturing method thereof.
Background
At present, the sucker rod is an important component of sucker rod pumping equipment, and transmits the power of the pumping unit to a downhole oil well pump. In the oil extraction process, the sucker rod string bears the action of asymmetric cyclic load, the working medium is well fluid, most of the well fluid contains corrosive medium, so that the main failure modes of the sucker rod are fatigue fracture and corrosion fatigue fracture, and the fatigue strength and the service life of the sucker rod determine and influence the maximum pump depth and the displacement of the whole set of oil pumping equipment.
The Chinese patent with the publication number of CN102839333B in the prior patent discloses a steel, a sucker rod comprising the same and application of the steel, wherein the steel comprises the following raw material components: carbon, silicon, manganese, phosphorus, sulfur, chromium, nickel, molybdenum, copper, aluminum, titanium, vanadium, niobium, tungsten, cobalt, antimony, and iron; another chinese patent with publication number CN103233172B discloses an ultrahigh strength and high toughness steel for sucker rods and a production process thereof, wherein the steel comprises the following chemical components by mass percent: 0.32 to 0.38%, Si: 0.17 to 0.37%, Mn: 1.6-1.8%, Cr: 1.1-1.3%, Mo: 0.2-0.3%, V: 0.2-0.3%, Al: 0.015-0.035%, P is less than or equal to 0.020%, S: less than or equal to 0.010 percent, less than or equal to 0.002 percent of [ O ], less than or equal to 0.0002 percent of [ H ], and the balance of Fe. The invention has reasonable component design and advanced process, and has higher strength and toughness compared with the steel for the high-strength sucker rod supplied in the current market.
However, the existing sucker rod should solve the problem of corrosion prevention at the same time. The oil pumping rod is always in corrosive liquid of hydrogen sulfide, carbon dioxide, dissolved oxygen and conductive drilling fluid in the process of oil exploitation, and in the later stage of oil field development, hydrochloric acid solution is required to be injected into a stratum for fracture acidizing to improve the oil production, so that the corrosion environment of high temperature, wet hydrogen sulfide and chloride ions of the oil pumping rod is intensified, and the oil pumping rod forms a consumable material, so that the problems of corrosion prevention and service life prolonging of the oil pumping rod are solved.
Disclosure of Invention
The invention aims to provide an anti-corrosion alloy sucker rod which has excellent anti-corrosion performance.
The above object of the present invention is achieved by the following technical solutions:
an anti-corrosion alloy sucker rod comprises a rod body and a joint, wherein the rod body sequentially comprises a steel base body, a TiCrN hard film, a TiCrSiN anti-corrosion film and a polyether-ether-ketone anti-corrosion layer from inside to outside.
By adopting the technical scheme, the corrosion resistance of the steel substrate is stronger; cr and Ti in the TiCrN hard film can form an interstitial solid solution, strong lattice distortion is caused after a part of Cr is replaced by Ti, dislocation motion is effectively blocked, and meanwhile, the addition of Cr element also improves the high-temperature oxidation resistance of the TiCrN hard film because Cr atoms preferentially react with O at high temperature to generate Cr2O3，Cr2O3The TiCrN hard film is a substance with a compact structure, has strong chemical stability, slows down the diffusion rate of O to the inside of the TiCrN film, and has higher hardness, higher working stability and oxidation resistance; the TiCrSiN anticorrosive film is formed by introducing Si element into TiCrN, and the addition of Si can refine grains, so that more grain boundaries can be obtained to prolong the oxygen diffusion path, and the wear resistance, corrosion resistance and oxidation resistance of the sucker rod are obviously improved; PEEK belongs to one kind of plastics anticorrosive coating, and PEEK has excellent corrosion resistance, can dissolve or destroy it only concentrated sulfuric acid, and its corrosion resistance is similar with the nickel steel, to sum up, the body of rod of this application has excellent anticorrosive, high strength property, and life is longer.
The invention is further configured that the steel substrate comprises the following components in parts by weight: 0.01-0.03% of carbon element, 0.5-1.0% of manganese element, less than or equal to 0.012% of phosphorus element, less than or equal to 0.005% of sulfur element, 14.0-14.5% of chromium element, 9.0-11.0% of nickel element, 2.0-2.5% of molybdenum element, 0.8-1.0% of rhenium element, 0.4-0.6% of zinc element, 0.05-0.08% of potassium element, 0.1-0.2% of nitrogen element, 0.03-0.05% of boron element and the balance of iron element; wherein, the chromium element and the molybdenum element are processed into nano-scale by cage type silsesquioxane hot rolling.
The invention is further configured to: the steel base body comprises the following components in parts by weight: 0.015-0.020% of carbon element, 0.6-0.8% of manganese element, less than or equal to 0.009% of phosphorus element, less than or equal to 0.005% of sulfur element, 14.0-14.3% of chromium element, 10.0-10.5% of nickel element, 2.15-2.35% of molybdenum element, 0.80-0.90% of rhenium element, 0.5-0.55% of zinc element, 0.05-0.07% of potassium element, 0.13-0.15% of nitrogen element, 0.035-0.045% of boron element and the balance of iron element; wherein, the chromium element and the molybdenum element are processed into nano-scale by cage type silsesquioxane hot rolling.
By adopting the technical scheme, in the formula of the steel substrate, the chromium element has higher content and is difficult to permeate into other components, the chromium element is subjected to early pretreatment by adopting cage-type silsesquioxane to prepare nanoscale liquid metal, so that the uniform diffusion of metal chromium in steel is facilitated, and the segregation in the microstructure of the finished steel product is reduced; in the formula of the steel base body, rhenium element and potassium element are added, which is helpful for the reduction of oxide in rhenium, so that pure metal rhenium is doped in other components, thereby improving the strength of the steel, and preparing the sucker rod with excellent corrosion resistance, high strength and high impact resistance.
The invention is further configured such that the method of preparing the steel substrate comprises the steps of:
(1) pretreatment of chromium element and molybdenum element: melting the cage-type silsesquioxane at a high temperature of 400-450 ℃, and continuously introducing N2Continuously heating to 1050-1150 ℃, adding chromium and molybdenum according to the weight ratio of the polyhedral oligomeric silsesquioxane to the chromium being 1:3, carrying out hot rolling treatment, and stirring at the rotating speed of 180-200 r/min for 1.5-2 h to obtain nanoscale liquid chromium and molybdenum;
(2) in the smelting process of an electric arc furnace, firstly, raising the temperature of the furnace to 760-780 ℃, putting 0.01-0.03% of carbon element, 0.5-1.0% of manganese element, less than or equal to 0.012% of phosphorus element, less than or equal to 0.005% of sulfur element, 9.0-11.0% of nickel element, 0.8-1.0% of rhenium element, 0.4-0.6% of zinc element, 0.05-0.08% of potassium element, 0.1-0.2% of nitrogen element, 0.03-0.05% of boron element and the balance of iron element into the electric arc furnace, then raising the temperature to 1100-1200 ℃, and preserving the temperature for 1-2 hours;
(3) adding the liquid chromium element and the liquid molybdenum element prepared in the step (1) into an electric arc furnace, adjusting the temperature in real time, and keeping the temperature at 1100-1200 ℃;
(4) refining in an LF furnace, wherein the refining temperature is 1550-1650 ℃, fine adjustment of components, heat preservation is carried out for 2-4 h, argon is blown in the whole process for stirring, so that the chemical components meet the component requirements, and then the temperature is reduced to 1250-1300 ℃;
(5) degassing: degassing at 1050-1080 ℃, vacuum degree of 60-65 Pa, and pumping for 2-4 h;
(6) carrying out argon protection die casting at 1280-1300 ℃, keeping the temperature at 950-980 ℃ after solidification, keeping the temperature for 48-72 h, and finally air-cooling to room temperature;
(7) and (3) carrying out heat treatment on the forged steel plate: and (3) putting the steel plate into a heating furnace, heating to 680-690 ℃, preserving heat for 30-45 min, and cooling to room temperature at the speed of 9-10 ℃/s by air cooling.
By adopting the technical scheme, the metal chromium and the metal molybdenum are pretreated, so that the metal chromium and the metal molybdenum are nanocrystallized, the infiltration of other components is facilitated, the steel substrate is prepared by smelting, refining, degassing and other processes, the process is simple, and the efficiency is high.
The invention is further configured that the preparation method of the TiCrN hard film comprises the following steps:
feeding a steel substrate sample into a sputtering chamber, connecting a Ti target into a direct current power supply, connecting a Cr target into a radio frequency power supply, wherein the working environment is inert gas, and the reaction gas is N2The vacuum degree is 5.8-6.2 x 10-4And forming the TiCrN hard film at the working pressure of 0.45-0.55 Pa and the sample temperature of 340-360 ℃.
By adopting the technical scheme, the TiCrN hard film is prepared by adopting a magnetron sputtering mode, the process parameters are set, the film forming is stable, and the efficiency is high.
The invention is further configured to: the preparation method of the TiCrSiN anticorrosive film comprises the following steps: connecting Ti and Si targets to a direct current power supply, connecting Cr targets to a radio frequency power supply, wherein the working environment is inert gas, and the reaction gas is N2The vacuum degree is 6.3-6.5 x 10-4And forming the TiCrSiN anticorrosive film at the working pressure of 0.55-0.65 Pa and the sample temperature of 340-360 ℃.
By adopting the technical scheme, the TiCrSiN anticorrosive film is prepared by adopting a magnetron sputtering mode, the process parameters are set, the film forming is stable, and the efficiency is high.
The invention further provides a preparation method of the polyether-ether-ketone anticorrosive layer, which comprises the following steps: and spraying a polyether-ether-ketone preservative on the surface of the TiCrSiN anticorrosive film, wherein the polyether-ether-ketone preservative comprises the following components in parts by weight: 20-30 parts of polyether ether ketone resin, 10-15 parts of thermosetting phenolic resin, 10-15 parts of methyl phenyl silicone resin, 10-20 parts of PTFE wax powder, 5-10 parts of cage type silsesquioxane, 1-3 parts of silane coupling agent, 1-2 parts of defoaming agent and 0.5-1 part of curing agent.
By adopting the technical scheme, the PEEK has excellent corrosion resistance, only concentrated sulfuric acid can dissolve or damage the PEEK, and the corrosion resistance of the PEEK is similar to that of nickel steel; the thermosetting phenolic resin is used as an anticorrosive material in the form of coating, glass fiber reinforced plastic and daub, has important application in the field of corrosion prevention, and the methylphenyl silicon resin is a cross-linked semi-inorganic high polymer which takes silicon-oxygen-silicon as a main chain and has an organic group connected to a silicon atom, has outstanding weather resistance, can be used as a heat-resistant and weather-resistant anticorrosive coating, a metal protective coating and a building engineering waterproof and moistureproof coating, and is beneficial to improving the bonding property with coated steel; the blend of the polyether-ether-ketone resin, the thermosetting phenolic resin and the methyl phenyl silicone resin is used as a matrix to ensure that the matrix has better corrosion resistance and weather resistance, PTFE wax powder, nano graphite and cage type silsesquioxane are continuously added, and the nano graphite and the cage type silsesquioxane act together to ensure that the prepared surface coating has excellent corrosion resistance, rust resistance and better weather resistance.
The invention also discloses a manufacturing method of the anti-corrosion alloy sucker rod, which comprises the following steps:
(1) forming a steel base body;
(2) magnetron sputtering a TiCrN hard film on a steel substrate;
(3) magnetron sputtering a TiCrSiN anticorrosive film on the TiCrN hard film;
(4) and a polyetheretherketone anticorrosive layer is sprayed on the TiCrSiN anticorrosive film.
By adopting the technical scheme and the steps, the anti-corrosion and high-strength sucker rod can be manufactured, the method is simple, and the forming efficiency is high.
In conclusion, the beneficial technical effects of the invention are as follows:
(1) the cage-type silsesquioxane has a nano-scale cubic three-dimensional structure cavity, has good chemical inertia and thermodynamic stability due to large Si-O bond energy, and can be applied to pretreatment of metal elements;
(2) in the formula of the steel substrate, the chromium element has high content and is difficult to permeate into other components, the chromium element is pretreated in the early stage by adopting cage type silsesquioxane to prepare nanoscale liquid metal, which is beneficial to uniform diffusion of metal chromium in steel and reduces segregation in the microstructure of finished steel products;
(3) in the formula, rhenium element and potassium element are added, which is helpful for the reduction of oxide in rhenium, so that pure metal rhenium is doped in other components, thereby improving the strength of the steel substrate;
(4) the initial smelting temperature is 760-780 ℃, the temperature is raised to 1100-1200 ℃, after all components in the system are melted, liquid metal elements are added into the molten system, and the temperature is maintained at 1100-1200 ℃, so that all metal components can be uniformly dispersed, the smelting temperature is low, and the energy consumption in production is reduced;
(5) in the refining process, the refining temperature is 1550-1650 ℃, after refining for a period of time, the temperature is reduced to 1250-1300 ℃, so that the thermal compensation in a molten phase and the later degassing process are facilitated, and the dispersion performance of each component in the steel is further improved;
(6) the TiCrN has a face-centered cubic crystal structure, Cr atoms are introduced into the TiN to replace partial Ti atoms in the TiN to form TiCrN solid solution, and the thermal expansion coefficient is close to that of sucker rod steel, so that the adhesion force with the sucker rod is firm;
(7) si element is introduced into the TiCrN, the formed TiCrSiN film has a nano composite structure, and the addition of Si can refine grains, so that more grain boundaries can be obtained to prolong the diffusion path of oxygen, and the wear resistance, corrosion resistance and oxidation resistance of the sucker rod are obviously improved; meanwhile, the friction factor is small;
(8) the PEEK has excellent corrosion resistance, only concentrated sulfuric acid can dissolve or damage the PEEK, the corrosion resistance of the PEEK is similar to that of nickel steel, and a PEEK anticorrosive layer is sprayed on the PEEK anticorrosive layer, so that the anticorrosive performance of the sucker rod is further improved.
Detailed Description
The present invention is described in further detail below with reference to the accompanying drawings.
The first embodiment is as follows:
an anti-corrosion alloy sucker rod is prepared by the following steps:
(1) forming a steel base body;
(a) preparing materials: 0.015% of carbon element, 0.6% of manganese element, 0.009% of phosphorus element, 0.005% of sulfur element, 14.0% of chromium element, 10.0% of nickel element, 2.15% of molybdenum element, 0.80% of rhenium element, 0.4% of zinc element, 0.05% of potassium element, 0.13% of nitrogen element, 0.035% of boron element and the balance of iron element;
(b) pretreatment of chromium element and molybdenum element: melting the cage-type silsesquioxane at a high temperature of 400-450 ℃, and continuously introducing N2Continuously heating to 1050-1150 ℃, adding chromium and molybdenum according to the weight ratio of the polyhedral oligomeric silsesquioxane to the chromium being 1:3, carrying out hot rolling treatment, and stirring at the rotating speed of 180-200 r/min for 1.5-2 h to obtain nanoscale liquid chromium and molybdenum;
(c) in the smelting process of an electric arc furnace, firstly, heating the furnace to 760-780 ℃, putting carbon element, manganese element, phosphorus element, sulfur element, nickel element, rhenium element, zinc element, potassium element, nitrogen element, boron element and the balance of iron element into the electric arc furnace, then heating to 1100-1200 ℃, and preserving heat for 1-2 hours;
(d) adding the liquid chromium element and the liquid molybdenum element prepared in the step (1) into an electric arc furnace, adjusting the temperature in real time, and keeping the temperature at 1100-1200 ℃;
(e) refining in an LF furnace, wherein the refining temperature is 1550-1650 ℃, fine adjustment of components, heat preservation is carried out for 2-4 h, argon is blown in the whole process for stirring, so that the chemical components meet the component requirements, and then the temperature is reduced to 1250-1300 ℃;
(f) degassing: degassing at 1050-1080 ℃, vacuum degree of 60-65 Pa, and pumping for 2-4 h;
(g) carrying out argon protection die casting at 1280-1300 ℃, keeping the temperature at 950-980 ℃ after solidification, keeping the temperature for 48-72 h, and finally air-cooling to room temperature;
(h) carrying out heat treatment on the forged steel substrate: and (3) putting the steel substrate into a heating furnace, heating to 680-690 ℃, preserving heat for 30-45 min, and cooling to room temperature at the speed of 9-10 ℃/s by air cooling.
(2) Magnetron sputtering a TiCrN hard film on a steel substrate;
feeding a steel substrate sample into a sputtering chamber, connecting a Ti target into a direct current power supply, connecting a Cr target into a radio frequency power supply, wherein the working environment is inert gas, and the reaction gas is N2The vacuum degree is 5.8-6.2 x 10-4And forming the TiCrN hard film at the working pressure of 0.45-0.55 Pa and the sample temperature of 340-360 ℃.
(3) Magnetron sputtering a TiCrSiN anticorrosive film on the TiCrN hard film;
connecting Ti and Si targets to a direct current power supply, connecting Cr targets to a radio frequency power supply, wherein the working environment is inert gas, and the reaction gas is N2The vacuum degree is 6.3-6.5 x 10-4And forming the TiCrSiN anticorrosive film at the working pressure of 0.55-0.65 Pa and the sample temperature of 340-360 ℃.
(4) Spraying a polyether-ether-ketone anticorrosive layer on the TiCrSiN anticorrosive film;
the polyether-ether-ketone anticorrosive layer is formed by spraying a polyether-ether-ketone preservative, and the polyether-ether-ketone preservative comprises the following components in parts by weight: 20-30 parts of polyether ether ketone resin, 10-15 parts of thermosetting phenolic resin, 10-15 parts of methyl phenyl silicone resin, 10-20 parts of PTFE wax powder, 5-10 parts of cage type silsesquioxane, 1-3 parts of silane coupling agent, 1-2 parts of defoaming agent and 0.5-1 part of curing agent.
Example two:
an anti-corrosion alloy sucker rod is different from the first embodiment in the formula of a steel substrate. Wherein, the carbon element is 0.015 percent, the manganese element is 0.6 percent, the chromium element is 14.2 percent, the nickel element is 9.5 percent, the molybdenum element is 2.2 percent, the rhenium element is 0.85 percent, the zinc element is 0.45 percent, the potassium element is 0.06 percent, the nitrogen element is 0.12 percent, the boron element is 0.03 percent, and the rest is the iron element.
Example three:
an anti-corrosion alloy sucker rod is different from the first embodiment in the formula of a steel substrate. Wherein, carbon element 0.02%, manganese element 0.8%, phosphorus element 0.04%, sulfur element 0.002%, chromium element 14.3%, nickel element 10.0%, molybdenum element 2.3%, rhenium element 0.9%, zinc element 0.5%, potassium element 0.07%, nitrogen element 0.15%, boron element 0.04%, and the rest is iron element.
Example four:
an anti-corrosion alloy sucker rod is different from the first embodiment in the formula of a steel substrate. The alloy comprises 0.025% of carbon element, 0.9% of manganese element, 0.008% of phosphorus element, 0.004% of sulfur element, 14.4% of chromium element, 10.5% of nickel element, 2.4% of molybdenum element, 0.95% of rhenium element, 0.55% of zinc element, 0.08% of potassium element, 0.18% of nitrogen element, 0.04% of boron element and the balance of iron element.
Example five:
an anti-corrosion alloy sucker rod is different from the first embodiment in the formula of a steel substrate. Wherein, carbon element 0.03%, manganese element 1.0%, phosphorus element 0.0010%, sulfur element 0.004%, chromium element 14.5%, nickel element 11.0%, molybdenum element 2.5%, rhenium element 1.0%, zinc element 0.6%, potassium element 0.08%, nitrogen element 0.2%, boron element 0.05%, and the balance of iron element.
Comparative example: the prior patent, the publication number of which is CN102839333B, is used as a comparative example.
The detection method comprises the following steps:
(1) carrying out a salt spray corrosion experiment according to GB/T2423, observing initial corrosion of a sample, and evaluating the corrosion resistance for 120 hours;
(2) performing an anti-corrosion test by using an autoclave, adjusting the pressure of the autoclave to be 20MPa, the temperature to be 300 ℃, and the duration to be 24h, and observing the surface corrosion condition of the material by using a high power microscope;
(3) electrochemical corrosion experimental study is carried out according to the GB/T17998-2009 stainless steel point of pitting corrosion standard.
The results of the salt spray corrosion resistance measurements are shown in the following table:
Figure BDA0001847957750000071
as can be seen from the table above, the average corrosion rate of each sucker rod is extremely low, and the sucker rod has excellent salt spray corrosion resistance and can adapt to a strong corrosion environment.
The results of the autoclave corrosion resistance test are shown in the following table:
sample (I) Surface topography
Example one Surface particle uniformity
Example two Surface particle uniformity
EXAMPLE III Surface particle uniformity
Example four Surface particle uniformity
EXAMPLE five Surface particle uniformity
Comparative example Surface particle unevenness
As can be seen from the above table, after the sucker rod of the embodiment is subjected to corrosion resistance detection of the high-pressure kettle, the surface particles are uniform, the specification and the size are uniform, and the sucker rod has excellent temperature resistance and pressure corrosion resistance; and the particles on the surface of the sample of the comparative example are arranged in a staggered way, and the difference is large and irregular.
The results of the electrochemical corrosion experiment are as follows:
Figure BDA0001847957750000072
Figure BDA0001847957750000081
as can be seen from the table above, the pitting potential of each sucker rod in the embodiment is greater than 1, so that the excellent performance that the steel is basically not easy to corrode is ensured, and compared with the comparative example, the prepared steel can be used in an anti-corrosion environment.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.

Claims (8)

1. The utility model provides an anticorrosion alloy sucker rod, includes the body of rod and connects, its characterized in that: the rod body sequentially comprises a steel base body, a TiCrN hard film, a TiCrSiN anticorrosive film and a polyether-ether-ketone anticorrosive layer from inside to outside.
2. The anti-corrosion alloy sucker rod of claim 1, wherein the steel substrate comprises the following components in parts by weight: 0.01-0.03% of carbon element, 0.5-1.0% of manganese element, less than or equal to 0.012% of phosphorus element, less than or equal to 0.005% of sulfur element, 14.0-14.5% of chromium element, 9.0-11.0% of nickel element, 2.0-2.5% of molybdenum element, 0.8-1.0% of rhenium element, 0.4-0.6% of zinc element, 0.05-0.08% of potassium element, 0.1-0.2% of nitrogen element, 0.03-0.05% of boron element and the balance of iron element; wherein, the chromium element and the molybdenum element are processed into nano-scale by cage type silsesquioxane hot rolling.
3. The anti-corrosion alloy sucker rod of claim 1, wherein the steel substrate comprises the following components in parts by weight: 0.015-0.020% of carbon element, 0.6-0.8% of manganese element, less than or equal to 0.009% of phosphorus element, less than or equal to 0.005% of sulfur element, 14.0-14.3% of chromium element, 10.0-10.5% of nickel element, 2.15-2.35% of molybdenum element, 0.80-0.9% of rhenium element, 0.5-0.55% of zinc element, 0.05-0.07% of potassium element, 0.13-0.15% of nitrogen element, 0.035-0.045% of boron element and the balance of iron element; wherein, the chromium element and the molybdenum element are processed into nano-scale by cage type silsesquioxane hot rolling.
4. The anti-corrosion alloy sucker rod of claim 2, wherein the preparation method of the steel substrate comprises the following steps:
(1) pretreatment of chromium element and molybdenum element: melting the cage-type silsesquioxane at a high temperature of 400-450 ℃, and continuously introducing N2Continuously heating to 1050-1150 ℃, adding chromium and molybdenum according to the weight ratio of the polyhedral oligomeric silsesquioxane to the chromium being 1:3, carrying out hot rolling treatment, and stirring at the rotating speed of 180-200 r/min for 1.5-2 h to obtain nanoscale liquid chromium and molybdenum;
(2) in the smelting process of an electric arc furnace, firstly, raising the temperature of the furnace to 760-780 ℃, putting 0.01-0.03% of carbon element, 0.5-1.0% of manganese element, less than or equal to 0.012% of phosphorus element, less than or equal to 0.005% of sulfur element, 9.0-11.0% of nickel element, 0.8-1.0% of rhenium element, 0.4-0.6% of zinc element, 0.05-0.08% of potassium element, 0.1-0.2% of nitrogen element, 0.03-0.05% of boron element and the balance of iron element into the electric arc furnace, then raising the temperature to 1100-1200 ℃, and preserving the temperature for 1-2 hours;
(3) adding the liquid chromium element and the liquid molybdenum element prepared in the step (1) into an electric arc furnace, adjusting the temperature in real time, and keeping the temperature at 1100-1200 ℃;
(4) refining in an LF furnace, wherein the refining temperature is 1550-1650 ℃, fine adjustment of components, heat preservation is carried out for 2-4 h, argon is blown in the whole process for stirring, so that the chemical components meet the component requirements, and then the temperature is reduced to 1250-1300 ℃;
(5) degassing: degassing at 1050-1080 ℃, vacuum degree of 60-65 Pa, and pumping for 2-4 h;
(6) carrying out argon protection die casting at 1280-1300 ℃, keeping the temperature at 950-980 ℃ after solidification, keeping the temperature for 48-72 h, and finally air-cooling to room temperature;
(7) and (3) carrying out heat treatment on the forged steel plate: and (3) putting the steel plate into a heating furnace, heating to 680-690 ℃, preserving heat for 30-45 min, and cooling to room temperature at the speed of 9-10 ℃/s by air cooling.
5. The anti-corrosion alloy sucker rod of claim 1 wherein: the preparation method of the TiCrN hard film comprises the following steps:
feeding a steel substrate sample into a sputtering chamber, connecting a Ti target into a direct current power supply, connecting a Cr target into a radio frequency power supply, wherein the working environment is inert gas, and the reaction gas is N2The vacuum degree is 5.8-6.2 x 10-4And forming the TiCrN hard film at the working pressure of 0.45-0.55 Pa and the sample temperature of 340-360 ℃.
6. The anti-corrosion alloy sucker rod of claim 1 wherein: the preparation method of the TiCrSiN anticorrosive film comprises the following steps:
connecting Ti and Si targets to a direct current power supply, connecting Cr targets to a radio frequency power supply, wherein the working environment is inert gas, and the reaction gas is N2The vacuum degree is 6.3-6.5 x 10-4And forming the TiCrSiN anticorrosive film at the working pressure of 0.55-0.65 Pa and the sample temperature of 340-360 ℃.
7. The anti-corrosion alloy sucker rod of claim 1, wherein the preparation method of the PEEK anti-corrosion layer comprises the following steps: and spraying a polyether-ether-ketone preservative on the surface of the TiCrSiN anticorrosive film, wherein the polyether-ether-ketone preservative comprises the following components in parts by weight: 20-30 parts of polyether ether ketone resin, 10-15 parts of thermosetting phenolic resin, 10-15 parts of methyl phenyl silicone resin, 10-20 parts of PTFE wax powder, 5-10 parts of cage type silsesquioxane, 1-3 parts of silane coupling agent, 1-2 parts of defoaming agent and 0.5-1 part of curing agent.
8. The method for manufacturing an anti-corrosion alloy sucker rod according to any one of claims 1 to 7, which is characterized by comprising the following steps:
(1) forming a steel base body;
(2) magnetron sputtering a TiCrN hard film on a steel substrate;
(3) magnetron sputtering a TiCrSiN anticorrosive film on the TiCrN hard film;
(4) and a polyetheretherketone anticorrosive layer is sprayed on the TiCrSiN anticorrosive film.
CN201811280567.3A 2018-10-30 2018-10-30 Anti-corrosion alloy sucker rod and manufacturing method thereof Pending CN111118385A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113403579A (en) * 2021-06-22 2021-09-17 南京工业职业技术大学 Preparation method of toughened CrTiNiSiN nano composite coating

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* Cited by examiner, † Cited by third party
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熊中实等, 中国建材工业出版社 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113403579A (en) * 2021-06-22 2021-09-17 南京工业职业技术大学 Preparation method of toughened CrTiNiSiN nano composite coating

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