CN117305659B - Corrosion-resistant alloy and preparation method and application thereof - Google Patents
Corrosion-resistant alloy and preparation method and application thereof Download PDFInfo
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- CN117305659B CN117305659B CN202311229923.XA CN202311229923A CN117305659B CN 117305659 B CN117305659 B CN 117305659B CN 202311229923 A CN202311229923 A CN 202311229923A CN 117305659 B CN117305659 B CN 117305659B
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- 239000000956 alloy Substances 0.000 title claims abstract description 78
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 75
- 238000005260 corrosion Methods 0.000 title claims abstract description 55
- 230000007797 corrosion Effects 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 8
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 238000001513 hot isostatic pressing Methods 0.000 claims description 30
- 238000000498 ball milling Methods 0.000 claims description 27
- 238000005245 sintering Methods 0.000 claims description 17
- 238000007789 sealing Methods 0.000 claims description 11
- 239000011812 mixed powder Substances 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000009694 cold isostatic pressing Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 8
- GVEHJMMRQRRJPM-UHFFFAOYSA-N chromium(2+);methanidylidynechromium Chemical compound [Cr+2].[Cr]#[C-].[Cr]#[C-] GVEHJMMRQRRJPM-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910003470 tongbaite Inorganic materials 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 238000004372 laser cladding Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- 238000005054 agglomeration Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 239000013535 sea water Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0433—Nickel- or cobalt-based alloys
- C22C1/0441—Alloys based on intermetallic compounds of the type rare earth - Co, Ni
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- 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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F15—FLUID-PRESSURE ACTUATORS; HYDRAULICS OR PNEUMATICS IN GENERAL
- F15B—SYSTEMS ACTING BY MEANS OF FLUIDS IN GENERAL; FLUID-PRESSURE ACTUATORS, e.g. SERVOMOTORS; DETAILS OF FLUID-PRESSURE SYSTEMS, NOT OTHERWISE PROVIDED FOR
- F15B15/00—Fluid-actuated devices for displacing a member from one position to another; Gearing associated therewith
- F15B15/08—Characterised by the construction of the motor unit
- F15B15/14—Characterised by the construction of the motor unit of the straight-cylinder type
- F15B15/1423—Component parts; Constructional details
- F15B15/1428—Cylinders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/042—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling using a particular milling fluid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F15—FLUID-PRESSURE ACTUATORS; HYDRAULICS OR PNEUMATICS IN GENERAL
- F15B—SYSTEMS ACTING BY MEANS OF FLUIDS IN GENERAL; FLUID-PRESSURE ACTUATORS, e.g. SERVOMOTORS; DETAILS OF FLUID-PRESSURE SYSTEMS, NOT OTHERWISE PROVIDED FOR
- F15B2201/00—Accumulators
- F15B2201/40—Constructional details of accumulators not otherwise provided for
- F15B2201/405—Housings
- F15B2201/4053—Housings characterised by the material
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Engineering & Computer Science (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides a corrosion-resistant alloy, a preparation method and application thereof, and belongs to the technical field of alloy preparation, wherein the alloy comprises the following raw materials in percentage by mass: 7 to 11 percent of B, 23 to 28 percent of Mo, 5 to 10 percent of Cr, 0.5 to 0.9 percent of C, 1 to 4 percent of Nb, 1 to 3 percent of Ti, 0.4 to 0.8 percent of Pr, 0.1 to 0.5 percent of Y, 1 to 4 percent of Mn and the balance of Ni. The alloy prepared by the invention has the characteristics of high hardness, high wear resistance, good corrosion resistance and excellent comprehensive performance, and is particularly suitable for manufacturing ship equipment. The alloy is used for manufacturing the hydraulic cylinder for the ship, so that the hydraulic cylinder has excellent mechanical properties, is used under ocean conditions, has excellent corrosion resistance and wear resistance, prolongs the service time of the hydraulic cylinder, and reduces the replacement cost.
Description
Technical Field
The invention belongs to the technical field of alloy materials, and particularly relates to a corrosion-resistant alloy, a preparation method and application thereof.
Background
Ships are susceptible to corrosion in marine environments, mainly due to water, salt and climatic conditions. Seawater contains abundant salt and microorganisms, and chloride ions, dissolved oxygen, sulfides and other substances can accelerate the corrosion process of metals. The humidity, temperature and climate change in the marine environment all cause a certain corrosion effect on the ship. For example, high humidity and humid climates can increase the corrosion rate of metals. There are contaminants in the ocean, such as petroleum, chemicals and industrial waste water, which can have corrosive effects on ship metals and coatings. Collisions and friction with other objects may occur during sailing and berthing of the vessel, which impacts and wear also lead to metal corrosion.
Hydraulic cylinders are a frequently used device on board a ship. The exposed use environment causes the surface of the piston rod of the hydraulic cylinder to be subjected to abnormal corrosion and abrasion of seawater or salt mist and moisture, and a series of protection measures are required to be taken. In marine environments, special alloy materials are often used in order to improve the corrosion resistance, wear resistance and other properties of the materials. The existing alloy material can realize better comprehensive performance, but still further improves the material strength, especially the corrosion resistance, and still can not meet the requirements of ship operation.
Disclosure of Invention
The invention aims at providing a corrosion-resistant alloy and a preparation method thereof, and the prepared alloy has high hardness, high wear resistance, good corrosion resistance and excellent comprehensive performance, and is particularly suitable for preparing hydraulic cylinders used on ships.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a corrosion-resistant alloy, which comprises the following raw materials in percentage by mass: 7 to 11 percent of B, 23 to 28 percent of Mo, 5 to 10 percent of Cr, 0.5 to 0.9 percent of C, 1 to 4 percent of Nb, 1 to 3 percent of Ti, 0.4 to 0.8 percent of Pr, 0.1 to 0.5 percent of Y, 1 to 4 percent of Mn and the balance of Ni.
Further, the total content of Pr and Y accounts for less than or equal to 1.0 percent of the mass of the raw materials.
The rare earth mixture Pr and Y is added in the alloy to form a layer of rare earth conversion film on the surface of intermetallic compound in the alloy, so that the flow of corrosive electrons is blocked, and the intergranular corrosion resistance and stress corrosion resistance of the alloy are improved. With the change of the addition amount of the rare earth Pr and the Y elements, the morphology and the structure of the alloy structure are changed, and when the addition amount of Pr is 0.4-0.8% and 0.1-0.5% respectively in the system of the invention, the phase in the alloy in the cast structure is in a fine punctiform state, thereby effectively playing a role in refining the micro-alloy, improving the corrosion resistance and the wear resistance of the alloy and simultaneously improving the mechanical property of the alloy. When the total content of Pr and Y added singly or mixed is more than 1.0%, coarse massive phases can be seen in the tissue. According to the invention, the corrosion resistance of the alloy can be improved by adding V and Ti, and the acid and alkali medium erosion resistance of the alloy is improved. The addition of Mn can improve the wettability of the liquid phase to the hard phase during sintering, thereby refining the grains and improving the bending strength of the hard alloy. The Mo content has a great influence on the microstructure of the alloy, and when the Mo addition amount is 40-45%, the wear resistance of the alloy is best.
Further, the preparation method comprises the following steps:
(1) Weighing the raw materials of all the components according to a proportion;
(2) Carrying out wet ball milling on raw materials of the alloy to obtain mixed powder, and carrying out vacuum drying at 65-75 ℃ for 10-15 h;
(3) Delivering the dried mixed powder into a pressing die for pressing and forming treatment to obtain a pressed blank;
(4) Sintering the pressed compact in a non-oxygen atmosphere to obtain a sintered compact;
(5) And carrying out hot isostatic pressing treatment on the sintered blank to obtain the corrosion-resistant alloy profile.
Further, the wet ball milling conditions are as follows: the ball milling medium is absolute ethyl alcohol, 85-90 g absolute ethyl alcohol is added into every 100g raw material, the ball-material ratio is 5-7:1, the ball milling rotating speed is 300-350 rpm, and the ball milling time is 15-20 h.
The invention selects the wet ball milling to be more uniform than the dry ball milling to obtain the particles, the wear resistance of the alloy is better, and the research and development process shows that the addition of the binder in the system of the invention can reduce the corrosion resistance stability and durability of the alloy final product if the dry ball milling is used. The invention can reduce the particle agglomeration, improve the alloy density and make the corrosion resistance of the alloy final product longer by adjusting the conditions of wet ball milling to make the average grain size of the alloy smaller.
Further, the press forming treatment is cold isostatic pressing treatment, the pressure is 150-250 MPa, and the pressure maintaining time is 10-40 min.
Further, the conditions of the sintering treatment are: the sintering temperature is 1500-1600 ℃, the heating rate is 4-8 ℃/min, and the sintering time is 1-2 h.
Further, the step of hot isostatic pressing treatment is as follows:
the first step, the hot isostatic pressing temperature is 1200-1300 ℃, the hot isostatic pressing pressure is 110-120 MPa, and the heat preservation and pressure maintaining time is 1-2 h;
secondly, the hot isostatic pressing temperature is 1350-1450 ℃, the hot isostatic pressing pressure is 130-140 MPa, and the heat preservation and pressure maintaining time is 1-2 h;
thirdly, the hot isostatic pressing temperature is 1500-1600 ℃, the hot isostatic pressing pressure is 150-160 MPa, and the heat preservation and pressure maintaining time is 2-5 h.
The alloy subjected to gradient hot isostatic pressing has smaller particle size, obviously reduced porosity and improved mechanical property. The inventors have also unexpectedly found that the alloy prepared under this condition has excellent resistance to marine microbial corrosion.
Further, the non-oxygen atmosphere is a nitrogen, hydrogen or argon atmosphere.
The second aspect of the invention provides the use of the corrosion resistant alloy.
Further, the use of said alloy in the preparation of equipment on board a ship.
Further, the alloy is used for preparing a hydraulic cylinder for ships, the hydraulic cylinder comprises an earring and a piston rod, one end of the earring is connected with one end of the piston rod, the other end of the piston rod is provided with a piston, a cylinder barrel is arranged outside the piston rod, and a sealing element A is arranged between the piston and the cylinder barrel; a guide sleeve is arranged between the cylinder barrel and one end of the piston rod, which is close to the earrings, and a sealing element B is arranged between the guide sleeve and the piston rod.
The alloy of the present invention is used for manufacturing hydraulic cylinders for ships, and needs stronger hardness, bending resistance, wear resistance and corrosion resistance, and the alloy of the present invention imparts excellent mechanical properties thereto. The hydraulic cylinder is mainly used under the conditions of ocean and the like, and the alloy has excellent corrosion resistance and wear resistance, so that the service time of the hydraulic cylinder is prolonged, and the replacement cost is reduced.
Hydraulic cylinders often operate under harsh environmental conditions and may be exposed to corrosive media such as moisture, water, chemicals, and the like. The piston rod of the hydraulic cylinder is in close contact with the sealing element during movement, and if the surface of the piston rod is corroded, the abrasion of the sealing element is increased, so that the performance and the service life of the hydraulic cylinder are affected. The piston rod is a key component for bearing the pushing force or the pulling force of the hydraulic cylinder, and if the piston rod is corroded, the problems of strength reduction, fatigue cracking or deformation and the like of the piston rod can be caused, so that the service life of the hydraulic cylinder is reduced. Corrosion can lead to a smaller diameter of the cylinder rod, which can affect sealing performance and motion smoothness. Corrosion prevention can improve the reliability of the system and ensure the normal operation of the hydraulic system. In this case, laser cladding can also be performed on the surface of the piston rod, so that the performance of the piston rod is further improved.
Further, taking chromium carbide powder as a cladding raw material, and forming a cladding layer on the surface of a piston rod by adopting a laser cladding method, wherein the chromium carbide powder is gray, the chromium carbide is in an orthorhombic crystal structure, and the chemical components of the chromium carbide powder comprise the following weight percent: total carbon is 13.2 plus or minus 0.2 percent, free carbon is less than or equal to 0.3 percent, impurity content O is less than or equal to 1 percent, N is less than or equal to 0.1 percent, fe is less than or equal to 0.1 percent, ca is less than or equal to 0.02 percent, si is less than or equal to 0.05 percent, na is less than or equal to 0.01 percent, al is less than or equal to 0.02 percent, and average granularity FSSS is less than or equal to 1.0 mu m. Purchased from south huashi technologies, inc.
Further, the scanning speed of the laser beam relative to the surface of the piston rod is 8-10 m/min; the laser power of the laser beam of the laser cladding is 2-4 kW.
According to the invention, the chromium carbide cladding material is added on the surface of the piston rod by utilizing laser cladding, and the filling material is melted by utilizing the laser beam with high energy density, so that the cladding layer and the piston rod are metallurgically bonded, the alloy bonding property of the chromium carbide and the piston rod is better, the comprehensive performance of the piston rod can be further obviously improved, the service life of the piston rod is prolonged, and the corrosion resistance and the wear resistance are further improved.
Compared with the prior art, the invention has the advantages that:
1. the invention aims at providing a corrosion-resistant alloy and a preparation method thereof, and the prepared alloy has high hardness, high wear resistance, good corrosion resistance and excellent comprehensive performance, and is particularly suitable for manufacturing hydraulic cylinders of ships.
2. The rare earth mixture Pr and Y is added to form a layer of rare earth conversion film on the surface of an intermetallic compound in the alloy, so that the flow of corrosive electrons is blocked, and the intergranular corrosion resistance and stress corrosion resistance are improved.
3. The corrosion resistance of the alloy can be improved by adding V and Ti, and the acid and alkali medium erosion resistance of the alloy is improved. The addition of Mn can improve the wettability of the liquid phase to the hard phase during sintering, thereby refining the grains and improving the bending strength of the hard alloy. The Mo content has a great influence on the microstructure of the alloy, and when the Mo addition amount is 23-28%, the wear resistance of the alloy is best.
4. The invention adopts wet ball milling to obtain uniform particles and has better wear resistance than dry ball milling. The wet ball milling condition of the invention makes the average grain size of the alloy smaller, can reduce the particle agglomeration, improves the alloy density, and makes the corrosion resistance of the alloy final product longer.
5. The alloy subjected to gradient hot isostatic pressing has smaller particle size, obviously reduced porosity and improved mechanical property, and the inventor also unexpectedly discovers that the alloy has excellent marine microorganism corrosion resistance.
6. The alloy provided by the invention is used for manufacturing hydraulic cylinders for ships, has stronger bending resistance, and has excellent mechanical properties. The hydraulic cylinder is mainly used under the conditions of ocean and the like, and the alloy has excellent corrosion resistance and wear resistance, so that the service time of the hydraulic cylinder is prolonged, and the replacement cost is reduced.
Drawings
FIG. 1 is a schematic structural view of a marine hydraulic cylinder of the present invention;
fig. 2 is a schematic cross-sectional structure of the hydraulic cylinder for a ship according to the present invention.
In the figure, 1, earrings, 2, sealing elements B,3, a guide sleeve, 4, a piston rod, 5, a cylinder barrel, 6, sealing elements A,7 and a piston.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a corrosion-resistant alloy, which comprises the following raw materials in percentage by mass: b9%, mo25%, cr7%, C0.7%, nb3%, ti2%, pr0.6%, Y0.4% and Mn3%, the balance being Ni.
The preparation method of the corrosion-resistant alloy comprises the following steps:
(1) Weighing the raw materials of all the components according to a proportion;
(2) Carrying out wet ball milling on raw materials of the alloy to obtain mixed powder, and carrying out vacuum drying at 70 ℃ for 12 hours; the wet ball milling conditions are as follows: the ball milling medium is absolute ethyl alcohol, 87g of absolute ethyl alcohol is added into every 100g of raw materials, the ball-material ratio is 6:1, the ball milling rotating speed is 320rpm, and the ball milling time is 18 hours.
(3) Delivering the dried mixed powder into a pressing die for pressing and forming treatment to obtain a pressed blank; the press forming treatment is cold isostatic pressing treatment, the pressure is 200MPa, and the dwell time is 25min.
(4) Sintering the pressed compact in argon atmosphere to obtain a sintered compact; the sintering treatment conditions are as follows: the sintering temperature is 1550 ℃, the heating rate is 6 ℃/min, and the sintering time is 1.5h.
(5) Performing hot isostatic pressing treatment on the sintered blank, wherein the hot isostatic pressing treatment comprises the following steps of: the first step, the hot isostatic pressing temperature is 1250 ℃, the hot isostatic pressing pressure is 115MPa, and the heat preservation and pressure maintaining time is 1.5h; secondly, the hot isostatic pressing temperature is 1400 ℃, the hot isostatic pressing pressure is 135MPa, and the heat preservation and pressure maintaining time is 1.5h; thirdly, the hot isostatic pressing temperature is 1550 ℃, the hot isostatic pressing pressure is 155MPa, and the heat preservation and pressure maintaining time is 3.5 hours; and obtaining the corrosion-resistant alloy profile.
As shown in fig. 1-2, the marine hydraulic cylinder prepared by using the alloy of the embodiment comprises an earring 1 and a piston rod 4, wherein one end of the earring 1 is connected with one end of the piston rod 4, the other end of the piston rod 4 is provided with a piston 7, a cylinder 5 is arranged outside the piston rod 4, and a sealing element A6 is arranged between the piston 7 and the cylinder 5; a guide sleeve 3 is arranged between the cylinder 5 and one end of the piston rod 4, which is close to the earring 1, and a sealing element B2 is arranged between the guide sleeve 3 and the piston rod 4.
Example 2
The differences between this embodiment and embodiment 1 are: a corrosion resistant alloy comprising the following raw materials in mass percent: b8%, mo26%, cr5%, C0.9%, nb1%, ti3%, pr0.4%, Y0.4% and Mn4%, the balance being Ni.
Example 3
The differences between this embodiment and embodiment 1 are: a corrosion resistant alloy comprising the following raw materials in mass percent: b7%, mo27%, cr5%, C0.8%, nb4%, ti2%, pr0.7%, Y0.3% and Mn4%, the balance being Ni.
Comparative example 1
The difference between this comparative example and example 1 is: a corrosion resistant alloy comprising the following raw materials in mass percent: b7%, mo35%, cr4%, C0.4%, nb0.5%, ti2.3%, pr0.8%, Y0.5% and Mn4%, the balance being Ni.
Comparative example 2
The difference between this comparative example and example 1 is: the wet ball milling conditions are as follows: the ball milling medium is absolute ethyl alcohol, 70g absolute ethyl alcohol is added into every 100g raw material, the ball-material ratio is 8:1, the ball milling rotating speed is 300rpm, and the ball milling time is 24 hours. The press forming treatment is cold isostatic pressing treatment, the pressure is 200MPa, and the dwell time is 30min. The sintering temperature is 1700 ℃, the heating rate is 10 ℃/min, and the sintering time is 1h.
Comparative example 3
The difference between this comparative example and example 1 is: the hot isostatic pressing treatment comprises the following steps: the hot isostatic pressing temperature is 1400 ℃, the hot isostatic pressing pressure is 150MPa, and the heat preservation and pressure maintaining time is 6h.
Performance testing
The properties of the example and comparative alloys were measured, with the U.S. Inconel600 alloy as a control. The method comprises the following steps: hardness was measured using a normal rockwell hardness tester; the flexural strength of the alloys of the examples and comparative examples was determined by the three-point bending method with reference to test standard GB/T6569-1986; adopting a microcomputer to control a plane thrust abrasion tester, and dry-grinding for 120min at normal temperature under the experimental force of 100N and the rotating speed of 200r/min to determine the abrasion loss; soaking in 10% hydrochloric acid solution for 10h respectively, and measuring the corrosion rate by using a corrosion rate measuring instrument; co-culturing with pseudomonas aeruginosa for 24 hours, and determining corrosion potential according to electrochemical electrokinetic potential polarization curve. The results are shown in Table 1.
Table 1 measurement results
The result shows that the alloy prepared by the invention has good mechanical property and corrosion resistance.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (5)
1. The corrosion-resistant alloy is characterized by comprising the following raw materials in percentage by mass: 7 to 11 percent of B, 23 to 28 percent of Mo, 5 to 10 percent of Cr, 0.5 to 0.9 percent of C, 1 to 4 percent of Nb, 1 to 3 percent of Ti, 0.4 to 0.8 percent of Pr, 0.1 to 0.5 percent of Y, 1 to 4 percent of Mn and the balance of Ni;
the total content of Pr and Y is less than or equal to 1.0 percent of the mass percentage of the raw materials;
the preparation method comprises the following steps:
(1) Weighing the raw materials of all the components according to a proportion;
(2) Carrying out wet ball milling on the raw materials to obtain mixed powder, and carrying out vacuum drying on the mixed powder at 65-75 ℃ for 10-15 h;
(3) Sending the dried mixed powder into a pressing die, and performing pressing forming treatment to obtain a pressed blank;
(4) Sintering the pressed compact in a non-oxygen atmosphere to obtain a sintered compact;
(5) Performing hot isostatic pressing treatment on the sintered blank to obtain corrosion-resistant alloy;
the wet ball milling conditions are as follows: the ball milling medium is absolute ethyl alcohol, 85-90 g absolute ethyl alcohol is added into every 100g raw material, the ball-material ratio is 5-7:1, the ball milling rotating speed is 300-350 rpm, and the ball milling time is 15-20 h;
the pressing forming treatment is cold isostatic pressing forming treatment, the pressure is 150-250 MPa, and the pressure maintaining time is 10-40 min;
the sintering treatment conditions are as follows: sintering temperature is 1500-1600 ℃, heating rate is 4-8 ℃/min, and sintering time is 1-2 h;
the hot isostatic pressing treatment comprises the following steps:
the first step, the hot isostatic pressing temperature is 1200-1300 ℃, the hot isostatic pressing pressure is 110-120 MPa, and the heat preservation and pressure maintaining time is 1-2 h;
secondly, the hot isostatic pressing temperature is 1350-1450 ℃, the hot isostatic pressing pressure is 130-140 MPa, and the heat preservation and pressure maintaining time is 1-2 h;
thirdly, the hot isostatic pressing temperature is 1500-1600 ℃, the hot isostatic pressing pressure is 150-160 MPa, and the heat preservation and pressure maintaining time is 2-5 h.
2. A method of producing a corrosion resistant alloy according to claim 1, wherein the method of producing comprises the steps of:
(1) Weighing the raw materials of all the components according to a proportion;
(2) Carrying out wet ball milling on the raw materials to obtain mixed powder, and carrying out vacuum drying on the mixed powder at 65-75 ℃ for 10-15 h;
(3) Sending the dried mixed powder into a pressing die, and performing pressing forming treatment to obtain a pressed blank;
(4) Sintering the pressed compact in a non-oxygen atmosphere to obtain a sintered compact;
(5) And carrying out hot isostatic pressing treatment on the sintered blank to obtain the corrosion-resistant alloy.
3. The method of producing a corrosion resistant alloy according to claim 2, wherein the non-oxygen atmosphere is a nitrogen, hydrogen or argon atmosphere.
4. Use of the corrosion resistant alloy of claim 1.
5. The use of the corrosion resistant alloy according to claim 4, wherein the alloy is used for preparing a hydraulic cylinder for a ship, the hydraulic cylinder comprises an earring and a piston rod, one end of the earring is connected with one end of the piston rod, the other end of the piston rod is provided with a piston, a cylinder barrel is arranged outside the piston rod, and a sealing element A is arranged between the piston and the cylinder barrel; a guide sleeve is arranged between the cylinder barrel and one end of the piston rod, which is close to the earrings, and a sealing element B is arranged between the guide sleeve and the piston rod.
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