CN115786752A - Method for improving corrosion resistance of cupronickel alloy pipe - Google Patents
Method for improving corrosion resistance of cupronickel alloy pipe Download PDFInfo
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- CN115786752A CN115786752A CN202211483322.7A CN202211483322A CN115786752A CN 115786752 A CN115786752 A CN 115786752A CN 202211483322 A CN202211483322 A CN 202211483322A CN 115786752 A CN115786752 A CN 115786752A
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- cupronickel alloy
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- 239000000956 alloy Substances 0.000 title claims abstract description 63
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 61
- 229910000570 Cupronickel Inorganic materials 0.000 title claims abstract description 49
- 230000007797 corrosion Effects 0.000 title claims abstract description 47
- 238000005260 corrosion Methods 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000005266 casting Methods 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003610 charcoal Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 229910052582 BN Inorganic materials 0.000 claims abstract description 20
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000011777 magnesium Substances 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 13
- 239000004519 grease Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 10
- 230000001050 lubricating effect Effects 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 13
- 230000006698 induction Effects 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 13
- 239000011572 manganese Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- 238000003723 Smelting Methods 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000005096 rolling process Methods 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 7
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 6
- 239000012964 benzotriazole Substances 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 239000002356 single layer Substances 0.000 claims description 6
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 238000010309 melting process Methods 0.000 claims 1
- 229940051841 polyoxyethylene ether Drugs 0.000 claims 1
- 229920000056 polyoxyethylene ether Polymers 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- 238000005507 spraying Methods 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- -1 halogen ions Chemical class 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 206010027146 Melanoderma Diseases 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910017827 Cu—Fe Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Abstract
The invention discloses a method for improving corrosion resistance of a cupronickel alloy pipe, belonging to the technical field of metal product processing technology. The invention describes the process steps of cast ingot casting and carbon film residue treatment on the surface of a cupronickel alloy pipe in the preparation process of the cupronickel alloy pipe in detail. The cast ingot casting process comprises the following steps: coating boron nitride on a casting system, feeding, heating, preserving heat, adding nickel, adding a charcoal covering agent, preserving heat, cooling, adding magnesium and the charcoal covering agent, preserving heat and casting; the process for treating the carbon film residue on the surface of the pipe comprises the following steps: the method comprises the steps of cleaning lubricating grease on the surface of the pipe, spraying a surfactant, and rubbing and cleaning blackish brown spots by using rubber balls after annealing. The carbon content of the cupronickel alloy cast ingot prepared by the method is controlled to be below 0.05wt.%, the qualified rate of the finished pipe is improved, the surface of the prepared pipe is bright, and the probability of occurrence of late service pitting of the pipe is greatly reduced.
Description
Technical Field
The invention belongs to the technical field of metal product processing technology, and particularly relates to a method for improving corrosion resistance of a cupronickel alloy pipe.
Background
The cupronickel alloy takes Ni as a main additive element, wherein the Ni content is 10wt.% and 30wt.% B10 and B30 alloys, and the better corrosion resistance is widely applied to the fields of large naval vessels, ocean drilling platforms, seawater condensation pipelines and the like due to the lower cost. Corrosion of cupronickel tubing in marine environments is dominated by uniform corrosion, pitting corrosion being one of the main failure modes. The occurrence of pitting corrosion generally requires that conditions in three aspects of material, medium and electrochemistry be met. Pitting corrosion is likely to occur at sensitive sites such as grain boundaries, inclusions, dislocations, anisotropic structures, etc., because the surface structure and structural non-uniformity of the metal material weakens some portions of the surface passivation film, thereby becoming a site where pitting corrosion is likely to nucleate. Stainless steel is easy to be in the presence of Cl ions containing halogen ions - 、Br - 、I - In solution of (1) to cause pitting corrosion, copper alloy pair
Is particularly sensitive. If deposits and loose porous deposits in the copper alloy pipe are attached to the pipe wall, the concentration difference of metal ions or oxygen between the bottom of the deposits and the solution body is caused, so that a corrosion galvanic cell is formed, and the local corrosion of the pipe wall is caused. Containing S in flowing cooling water 2- The original protective film of the copper pipe can be damaged, and the copper pipe can be subjected to pitting corrosion. Pitting corrosion needs to occur above the pitting potential. The factors affecting pitting corrosion may be divided into environmental factors and metallurgical factors. The type, concentration, temperature, PH, and flow rate of the corrosive medium in the environment all contribute to corrosion. The common methods for preventing the occurrence of the pitting corrosion mainly comprise the methods of improving medium conditions, selecting alloy materials resistant to the pitting corrosion, passivating the surface of materials, performing cathodic protection on the materials and the like. The even corrosion performance of B10 cupronickel alloy pipes with small and medium diameters produced in China can be improvedSo as to reach the level equivalent to the foreign pipes with the same specification, but the domestic pipes are easy to have pitting phenomenon in the service process to cause corrosion failure. Carbon is a main impurity element in the cupronickel alloy pipe, and the content of the carbon has important influence on the quality of the cupronickel alloy cast ingot and the forming performance of the pipe. When the carbon content of the cupronickel alloy cast ingot exceeds the standard, the cupronickel alloy cast ingot is easy to have defects such as holes, and the like, and cracks are easy to appear in the later-stage pipe rolling process, so that the yield of the pipe is reduced. When the carbon content in the cupronickel alloy exceeds the dissolution limit, the cupronickel alloy is precipitated in the crystal in the form of graphite strips along the crystal boundary or in the form of clusters. Graphite precipitated along grain boundaries can cause the alloy to become cold brittle and reduce corrosion resistance. Meanwhile, carbon-based lubricating grease remains on the inner surface and the outer surface if the pipe is not cleaned in place after the processes of extrusion, rolling, drawing and the like are carried out on the pipe, in the subsequent seawater corrosion process, because the potential of a region covered by the grease is a positive potential and the potential of a region uncovered by the grease is a negative potential, corrosion batteries are formed due to the difference of electrode potentials, corrosion products are accumulated on the opening of a corrosion pit to form a bulge to seal the corrosion pit, and the inside of the corrosion pit is partially blocked, so that pitting and perforation of the pipe are caused.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for reducing the pitting tendency of the cupronickel alloy pipe and further improving the corrosion resistance.
The invention is realized by the following technical scheme.
A B10 cupronickel alloy material comprises the following components in percentage by mass: 9.5 to 10.5 percent of nickel, 1.2 to 2.0 percent of iron, 0.4 to 1.2 percent of manganese and the balance of copper.
A method for improving the corrosion resistance of a cupronickel alloy pipe comprises the following steps:
(1) Coating double-layer boron nitride on the inner wall of a graphite stopper rod, a cone body and a pouring pipe of a pouring system, which are in contact with pouring liquid, and coating single-layer boron nitride on the outer wall of the pouring system; the thickness of each layer of boron nitride is 5-10 μm;
(2) Preheating an induction smelting furnace to 950-1000 ℃, drying raw materials, firstly placing weighed copper blocks, copper-iron intermediate alloy and pure manganese into a magnesia crucible, placing the crucible into the center of a high-frequency induction coil in the induction smelting furnace, heating to 1200-1350 ℃, preserving heat for 5-20 minutes, adding metallic nickel after the metal is completely melted, adding a charcoal covering agent, preserving heat for 2-10 minutes, then quickly fishing out charcoal slag, cooling to 1050-1080 ℃, adding magnesium and charcoal into a melt as the covering agent, wherein the adding amount of magnesium is 0.02-0.03 wt% of the mass of the melt, fishing out the covering agent after preserving heat for 5-15 minutes, and finally casting and molding in a casting system treated in the step (1) to obtain an ingot;
(3) Extruding, rolling and drawing the obtained cast ingot to prepare a cupronickel alloy pipe;
(4) The surface of the cupronickel alloy pipe is attached with lubricating grease after the production, the lubricating grease on the surface of the pipe is firstly erased before the pipe is annealed, then the surface active agent is used for spraying and cleaning the inner surface and the outer surface of the pipe and then annealing is carried out, the inner surface and the outer surface of the pipe are inspected after the pipe is annealed, and when black spots such as black brown spots, patches or black patches with stripe-shaped appearance exist on the surface, a local black spot is erased by adopting a rubber ball friction mode.
In the invention, the raw materials in the step (2) comprise a copper block, pure nickel, a Cu-Fe intermediate alloy and pure manganese, and the specifications of the used main raw materials are as follows: copper block, T2 copper, purity ≥ 99.9wt.%; pure nickel, purity ≥ 99.9wt.%; cu-Fe intermediate alloy, cu-40Fe intermediate alloy, purity is more than or equal to 99.9wt.%; pure manganese with purity of more than or equal to 99.9wt.%.
In the invention, the clay casting mold is adopted in the step (2) of casting molding.
In the present invention, the surfactant component in the step (4) comprises: 20-25 by volume: 30 to 40:10 to 20:10 to 20: 150-180 parts of potassium pyrophosphate, benzotriazole, alkylphenol polyoxyethylene, anhydrous sodium metasilicate and alcohol. The alcohol concentration was 95%.
The carbon content of the cupronickel alloy cast ingot prepared by the method can reach below 0.05wt.%, and the probability of occurrence of cast ingot hole defects is greatly reduced. The surface of the cupronickel alloy pipe processed by the method is bright, and the probability of the occurrence of pitting in later service of the pipe is greatly reduced.
Compared with the prior art, the invention has the beneficial technical effects that: according to the invention, the yield of the cupronickel alloy pipe is improved and the time for generating the pitting corrosion of the cupronickel alloy pipe is reduced by improving the preparation process of the cupronickel alloy ingot and eliminating the combination of the residual carbon films on the surface of the cupronickel alloy pipe.
Detailed Description
The invention provides a method for improving corrosion resistance of a cupronickel alloy pipe, and particularly relates to process steps of ingot casting and carbon film residue treatment on the surface of the pipe in the preparation process of the cupronickel alloy pipe. The ingot casting process comprises the following steps: coating boron nitride on a casting system, feeding, heating, preserving heat, adding nickel, adding a charcoal covering agent, preserving heat, cooling, adding magnesium and the charcoal covering agent, preserving heat and casting; the process for treating the carbon film residue on the surface of the pipe comprises the following steps: the method comprises the steps of cleaning lubricating grease on the surface of a pipe, spraying a surfactant, and rubbing and cleaning black brown spots by using rubber balls after annealing.
The present invention will be described in detail with reference to the following embodiments.
Example 1
A method for improving corrosion resistance of a cupronickel alloy pipe comprises the following steps:
(1) Coating double-layer boron nitride on the inner wall of a graphite stopper rod, a cone and a pouring tube of a pouring system, which can be in contact with pouring liquid, and coating single-layer boron nitride on the outer wall of the graphite stopper rod, the cone and the pouring tube; the thickness of each layer of boron nitride was 5 μm.
(2) Preparing materials: taking a pure copper block, pure nickel, a Cu-40Fe intermediate alloy and pure manganese according to the mass ratio, and drying;
(3) Smelting: preheating an induction smelting furnace to 1000 ℃, putting weighed pure copper blocks, cu-40Fe intermediate alloy and pure manganese into a magnesia crucible, putting the crucible into the center of a high-frequency induction coil, heating to 1350 ℃, preserving heat for 5 minutes, adding metal nickel after the metal is completely melted, adding a charcoal covering agent, preserving heat for 2 minutes, then quickly taking out charcoal slag, cooling to 1080 ℃, adding magnesium and charcoal into a melt as the covering agent, wherein the adding amount of magnesium is 0.02 wt% of the mass of the melt, taking out the covering agent after preserving heat for 5 minutes, finally casting and molding in a casting system, and adopting a volume of 3000cm 3 Casting the clay to obtain an ingot;
(4) Extruding, rolling and drawing the obtained cast ingot to prepare a cupronickel alloy pipe; before the pipe annealing, lubricating grease is manually erased, and then spraying cleaning of the inner surface and the outer surface of the pipe is carried out by using a surfactant, wherein the surfactant comprises the following components: according to the volume ratio of 20:30:10:10:150 parts of potassium pyrophosphate, benzotriazole, alkylphenol polyoxyethylene, anhydrous sodium metasilicate and alcohol, wherein the alcohol concentration is 95%, the inner and outer surface states of the pipe are inspected after the pipe is annealed, black brown spots, black spots in the shape of stripes or stripes and the like exist on the surface, and the local black spots are removed by adopting a rubber ball friction erasing mode.
Example 2
A method for improving the corrosion resistance of a cupronickel alloy pipe comprises the following steps:
(1) Coating double-layer boron nitride on the inner wall of a graphite stopper rod, a cone and a pouring tube of a pouring system, which can be in contact with pouring liquid, and coating single-layer boron nitride on the outer wall of the graphite stopper rod, the cone and the pouring tube; the thickness of each layer of boron nitride was 8 μm.
(2) Preparing materials: taking a pure copper block, pure nickel, a Cu-40Fe intermediate alloy and pure manganese according to the mass ratio, and drying;
(3) Smelting: preheating an induction smelting furnace to 980 ℃, placing weighed pure copper blocks, cu-40Fe intermediate alloy and pure manganese into a magnesia crucible, placing the crucible into the center of a high-frequency induction coil, heating to 1300 ℃, preserving heat for 10 minutes, adding metal nickel after the metal is completely melted, adding a charcoal covering agent, preserving heat for 5 minutes, then quickly fishing out charcoal slag, cooling to 1070 ℃, adding magnesium and charcoal as the covering agent into a melt, wherein the adding amount of magnesium is 0.025 wt% of the mass of the melt, fishing out the covering agent after the heat is preserved for 8 minutes, finally casting and molding in a casting system, and adopting the volume of 3000cm 3 Casting the clay to obtain an ingot;
(4) Extruding, rolling and drawing the obtained cast ingot to prepare a cupronickel alloy pipe; before the annealing of the pipe, lubricating grease is manually erased, and then the spraying cleaning of the inner surface and the outer surface of the pipe is carried out by using a surfactant, wherein the surfactant comprises the following components: according to the volume ratio of 20:32:13:12:160 of potassium pyrophosphate, benzotriazole, alkylphenol polyoxyethylene, anhydrous sodium metasilicate and alcohol, wherein the alcohol concentration is 95%, the inner surface state and the outer surface state of the pipe are checked after the pipe is annealed, and when black spots such as blackish brown spots, patches or stripe-shaped appearance exist on the surface, a local black spot is removed by adopting a rubber ball friction erasing mode.
Example 3
A method for improving the corrosion resistance of a cupronickel alloy pipe comprises the following steps:
(1) Coating double-layer boron nitride on the inner wall of a graphite stopper rod, a cone and a pouring tube of a pouring system, which can be in contact with pouring liquid, and coating single-layer boron nitride on the outer wall of the graphite stopper rod, the cone and the pouring tube; the thickness of each layer of boron nitride was 8 μm.
(2) Preparing materials: taking a pure copper block, pure nickel, a Cu-40Fe intermediate alloy and pure manganese according to the mass ratio, and drying;
(3) Smelting: preheating an induction smelting furnace to 960 ℃, placing weighed pure copper blocks, cu-40Fe intermediate alloy and pure manganese into a magnesia crucible, placing the crucible into the center of a high-frequency induction coil, heating to 1250 ℃, preserving heat for 15 minutes, adding metal nickel after the metal is completely melted, adding a charcoal covering agent, preserving heat for 7 minutes, then quickly fishing out charcoal slag, cooling to 1060 ℃, then adding magnesium and charcoal which are used as covering agents into a melt, wherein the adding amount of magnesium is 0.028 wt% of the mass of the melt, fishing out the covering agent after preserving heat for 12 minutes, finally casting and molding in a casting system, and adopting a volume of 3000cm 3 Casting the clay to obtain an ingot;
(4) Extruding, rolling and drawing the obtained cast ingot to prepare a cupronickel alloy pipe; before the annealing of the pipe, lubricating grease is manually erased, and then the spraying cleaning of the inner surface and the outer surface of the pipe is carried out by using a surfactant, wherein the surfactant comprises the following components: according to the volume ratio of 22:35:14:15:170 of potassium pyrophosphate, benzotriazole, alkylphenol polyoxyethylene, anhydrous sodium metasilicate and alcohol, wherein the concentration of the alcohol is 95 percent, the inner surface state and the outer surface state of the pipe are checked after the pipe is annealed, and when black spots such as blackish brown spots, patches or stripe-shaped appearance exist on the surface, a local black spot is removed by adopting a rubber ball friction erasing mode.
Example 4
A method for improving corrosion resistance of a cupronickel alloy pipe comprises the following steps:
(1) Coating double-layer boron nitride on the inner wall of a graphite stopper rod, a cone and a pouring tube of a pouring system, which can be in contact with pouring liquid, and coating single-layer boron nitride on the outer wall of the graphite stopper rod, the cone and the pouring tube; the thickness of each layer of boron nitride was 10 μm.
(2) Preparing materials: taking a pure copper block, pure nickel, a Cu-40Fe intermediate alloy and pure manganese according to the mass ratio, and drying;
(3) Smelting: preheating an induction smelting furnace to 950 ℃, placing weighed pure copper blocks, cu-40Fe intermediate alloy and pure manganese into a magnesia crucible, placing the crucible into the center of a high-frequency induction coil, heating to 1200 ℃, preserving heat for 20 minutes, adding metal nickel after the metal is completely melted, adding a charcoal covering agent, preserving heat for 10 minutes, then quickly fishing out charcoal slag, cooling to 1050 ℃, adding magnesium and charcoal as the covering agent into a melt, wherein the adding amount of magnesium is 0.03 wt% of the mass of the melt, fishing out the covering agent after preserving heat for 15 minutes, finally casting and molding in a casting system, and adopting a volume of 3000cm 3 Casting the clay to obtain an ingot;
(4) Extruding, rolling and drawing the obtained cast ingot to prepare a cupronickel alloy pipe; before the pipe annealing, lubricating grease is manually erased, and then spraying cleaning of the inner surface and the outer surface of the pipe is carried out by using a surfactant, wherein the surfactant comprises the following components: according to the volume ratio of 25:40:20:20:180 parts of potassium pyrophosphate, benzotriazole, alkylphenol polyoxyethylene, anhydrous sodium metasilicate and alcohol, wherein the alcohol concentration is 95%, the inner and outer surface states of the pipe are checked after the pipe is annealed, and when black spots such as blackish brown spots, patches or black spots with stripe-shaped appearance exist on the surface, a local black spot is removed by adopting a rubber ball friction erasing mode.
Detecting components of the cast ingot: ingredients were dosed and the ingredients of the examples tested according to table 1.
Table 1 ingredient standard and ingot measured ingredients (wt.%) of
Testing the surface treatment of the pipe: samples 1 to 4 are the pipes prepared in examples 1 to 4, and sample 5 is a pipe subjected to surface treatment by a factory process.
Five pipes in 3.5wt.% Cl - +0.05wt.％S 2- The solution of (2) is subjected to accelerated corrosion, and the surface state of the sample is recorded in a mode of timing taking and surface observation.
TABLE 2 comparison of test times
The invention realizes the purpose of controlling the carbon content of the cupronickel cast ingot and the carbon residue film of the pipe by improving the cupronickel cast ingot preparation and pipe surface treatment process. Finally, the forming performance and the corrosion resistance of the cupronickel alloy pipe are improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. It should be noted that those skilled in the art, on the basis of the teachings provided herein, may make other modifications equivalent to those already described, and should be considered within the scope of the present invention.
Claims (8)
1. A method for improving corrosion resistance of a cupronickel alloy pipe is characterized by comprising the following steps:
(1) Coating double-layer boron nitride on the inner wall of a graphite stopper rod, a cone body and a pouring pipe of a pouring system, which are in contact with pouring liquid, and coating single-layer boron nitride on the outer wall of the pouring system;
(2) Preheating an induction smelting furnace to 950-1000 ℃, drying raw materials, firstly placing weighed copper blocks, copper-iron intermediate alloy and pure manganese in the induction smelting furnace, heating to 1200-1350 ℃, preserving heat for 5-20 minutes, adding metallic nickel after the metal is completely melted, adding a charcoal covering agent, preserving heat for 2-10 minutes, cooling to 1050-1080 ℃, adding Mg and the charcoal as the charcoal covering agent into a melt, preserving heat for 5-15 minutes, and finally casting and molding in a casting system treated in the step (1) to obtain a cast ingot;
(3) Extruding, rolling and drawing the obtained cast ingot to prepare a cupronickel alloy pipe;
(4) Before the annealing of the pipe, the lubricating grease on the surface of the pipe is removed, and then the surface of the pipe is subjected to spray cleaning by using a surfactant and then the annealing is performed.
2. The method for improving the corrosion resistance of the cupronickel alloy pipe material according to claim 1, wherein the thickness of each layer of boron nitride in the step (1) is 5-10 μm.
3. The method for improving the corrosion resistance of the cupronickel alloy pipe material according to claim 1 or 2, characterized in that, the specifications of the raw materials in the step (2) are as follows: copper block, T2 copper, purity ≥ 99.9wt.%; pure nickel, purity ≥ 99.9wt.%; cu-40Fe intermediate alloy with purity more than or equal to 99.9wt.%; pure manganese with purity of more than or equal to 99.9wt.%.
4. The method for improving the corrosion resistance of the cupronickel alloy pipe material according to the claim 1 or 2, characterized in that the magnesium is added in the step (2) in the amount of 0.02-0.03 wt.% of the melt quality.
5. The method for improving the corrosion resistance of the cupronickel alloy pipe as recited in claim 1 or 2, wherein the melting crucible used in the melting process in the step (2) is made of magnesia, and a clay mold is used for casting.
6. The method for improving the corrosion resistance of the cupronickel alloy pipe material according to claim 1 or 2, characterized in that, the surfactant component in the step (4) comprises: 20-25 by volume: 30 to 40:10 to 20:10 to 20: 150-180 parts of potassium pyrophosphate, benzotriazole, alkylphenol polyoxyethylene ether, anhydrous sodium metasilicate and alcohol.
7. The method for improving corrosion resistance of cupronickel alloy tubing of claim 6, wherein the alcohol concentration is 95%.
8. The method for improving the corrosion resistance of the cupronickel alloy pipe according to claim 1 or 2, characterized in that the black spots on the surface of the pipe are removed by using rubber balls after the pipe in the step (4) is annealed.
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