CN110983113A - Cobalt-based high-temperature alloy wire and preparation method thereof - Google Patents
Cobalt-based high-temperature alloy wire and preparation method thereof Download PDFInfo
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- CN110983113A CN110983113A CN201911414430.7A CN201911414430A CN110983113A CN 110983113 A CN110983113 A CN 110983113A CN 201911414430 A CN201911414430 A CN 201911414430A CN 110983113 A CN110983113 A CN 110983113A
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- 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
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
- B21C37/047—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire of fine wires
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- 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
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
Abstract
The invention provides a cobalt-based high-temperature alloy wire which comprises the following chemical components in percentage by mass: 0.06 to 0.12 percent of C, less than or equal to 0.3 percent of Si, 1.1 to 1.8 percent of Mn1, less than or equal to 0.015 percent of P, less than or equal to 0.015 percent of S, 19.2 to 20 percent of Cr19, 9.5 to 10.5 percent of Ni0, 14.2 to 15.5 percent of W, less than or equal to 2.8 percent of Fe, less than or equal to 0.4 percent of other impurities, and the balance of Co. The addition of 19.2-20% of Cr has excellent corrosion resistance, and does not promote the generation of epsilon-Co and sigma phases due to the excessively high Cr content, so that a two-phase region appears to reduce the high-temperature strength. The cobalt-base alloy contains a large amount of Co, 14.2-15.5% of W, 19.2-20% of Cr and other elements as a matrix, so that the stacking fault energy can be reduced, and the high-temperature strength of the alloy is improved. The content of W is controlled to be 19.2-20%, and the conditions of prominent work hardening, difficult cold working and poor stability of the alloy caused by excessive content of W are ensured not to occur. The Ni content of 9.5-10.5% is helpful for improving the structural stability of the alloy and reducing the precipitation of Co7W6 phase. 1.1-1.8% of Mn is added to effectively improve the oxidation resistance of the Ni-Cr alloy.
Description
Technical Field
The invention relates to preparation of alloy materials, in particular to a cobalt-based high-temperature alloy wire and a preparation method thereof.
Background
With the development of industrial technology. High temperature materials with higher temperature fatigue, creep, thermal stability and oxidation resistance are required to meet the design requirements of advanced equipment (mainly for aerospace applications), and therefore development of various high temperature alloy materials has never been stopped for more than half a century. High temperature alloys are also called hot strength alloys, superalloys. Materials can be divided into three categories according to the matrix structure: iron-based, nickel-based, and chromium-based. Cobalt-based alloys are those which contain cobalt as a major component, a significant amount of nickel, chromium, tungsten, and a small amount of alloying elements such as molybdenum, niobium, tantalum, titanium, lanthanum, and occasionally iron. According to different components in the alloy, the alloy can be made into welding wires, powder is used for processes such as hard surface overlaying, thermal spraying, spray welding and the like, and can also be made into casting and forging pieces and powder metallurgy pieces. The impurity content in the existing cobalt-based alloy can not be effectively controlled, and the corrosion resistance, high-temperature oxidation resistance and the like of the cobalt-based alloy can not be well improved by controlling the content of each component during smelting.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a cobalt-based high-temperature alloy wire and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a cobalt-based high-temperature alloy wire comprises the following chemical components in percentage by mass: 0.06 to 0.12 percent of C, less than or equal to 0.3 percent of Si, 1.1 to 1.8 percent of MnP, less than or equal to 0.015 percent of P, less than or equal to 0.015 percent of S, 19.2 to 20 percent of Cr19, 9.5 to 10.5 percent of Ni0, 14.2 to 15.5 percent of W, 1.6 to 2.8 percent of Fe1, less than or equal to 0.4 percent of other impurities, and the balance of Co.
Preferably, the composition comprises the following chemical components in percentage by mass: 0.07 percent of C, less than or equal to 0.3 percent of Si, 1.2 percent of MnP, less than or equal to 0.015 percent of P, less than or equal to 0.015 percent of S, 20 percent of Cr, 10.5 percent of Ni10, 14.6 percent of W, 2.0 percent of Fe2, less than or equal to 0.4 percent of other impurities, and the balance of Co.
A method of making a cobalt-based superalloy wire as in any of the preceding claims, comprising: comprises that
Step 1, preparing materials, cleaning surface oxide skin and ensuring brightness and no impurities;
step 2, vacuum smelting, namely feeding according to the sequence of returned feed-C-Ni-Cr-Co-W-Co-Fe, adding W into the middle part of the induction coil, covering the W with Co, and melting in high vacuum; alloying the molten steel by using a rocking furnace, wherein the melting temperature is 1330-1410 ℃, the refining temperature is 1560 ℃, the tapping temperature is 1520 ℃, and 35kg of electrode rods are cast;
step 3, electroslag remelting, wherein the slag system proportion is CaF 2: AL2O 3: CaO: MgO = 60: 20: 10: 10, electric power system: 45-50V, current: 2200 and 2800A, 5 minutes later feeding, 36kg of electroslag steel ingot, and slow cooling by hot sand;
step 4, forging, wherein the forging heating temperature is 1160-1180 ℃, the forging starting temperature is more than or equal to 1140 ℃, the finish forging temperature is more than or equal to 920 ℃, and the forging specification is as follows: 42 × 42 square rods, and slow cooling hot sand;
step 5, hot rolling, namely, the heating temperature of the square bar hot rolling is 1180 ℃, the heat preservation is carried out for 25 minutes, the initial rolling temperature is more than or equal to 1100 ℃, the final rolling temperature is more than or equal to 900 ℃, and the wire rod with the hot rolling specification phi 10 is air-cooled;
step 6, carrying out heat treatment on the wire rod, heating the electric furnace to 700 ℃, and charging to a set temperature: 1175-1230 ℃, preserving the temperature for 45 minutes, and then cooling by water;
step 7, cold drawing, namely, drawing at a low speed, removing crack defects by solid solution pickling surface polishing after drawing once, and then drawing;
and 8, checking and packaging.
Preferably, the vacuum melting in the step 2 is carried out, the melting vacuum degree is less than or equal to 5.0Pa, and the vacuum degree in the refining period is less than or equal to 1.0 Pa.
Preferably, when the rocking furnace is used for alloying the molten steel in the step 2, the rocking furnace is stirred back and forth for 2 to 3 times, and the refining time is more than 25 minutes.
Preferably, the forging heating temperature in step 4 is set to 1170 ℃.
Preferably, in the drawing process in the step 7, the deformation amount of each pass is controlled to be 15% -45%, and the final deformation amount is controlled to be 40%, namely 0.07 is drawn by using 0.16, and 0.1 is drawn by using 0.24.
Compared with the prior art, the invention has the beneficial effects that:
adding 19.2-20% Cr to form Cr on the surface2O3The film layer has excellent corrosion resistance, and does not promote the generation of epsilon-Co and sigma phases due to the overhigh Cr content to generate a two-phase region so as to reduce the high-temperature strength. In addition, a large amount of Co, 14.2-15.5% of W, 19.2-20% of Cr and other elements which are used as a matrix in the cobalt-based alloy can reduce the stacking fault energy, form a large amount of stacking faults and twin crystals in the alloy, hinder the movement of dislocation and improve the high-temperature strength of the alloy; and the content of W is controlled to be 19.2-20%, so that the conditions of prominent work hardening, difficult cold working and poor stability of the alloy caused by excessive W content are avoided. Meanwhile, the cobalt-based alloy contains 9.5-10.5% of Ni, which is beneficial to improving the structural stability of the alloy and reducing Co7W6And separating out the phases. 1.1-1.8% of Mn is added to effectively improve the oxidation resistance of the Ni-Cr alloy to form MnCr2O4The spinel has a barrier effect on oxygen, and can reduce the oxygen partial pressure of a spinel/chromium oxide interface, further reduce the oxidation speed of the alloy and improve the oxidation resistance of the cobalt-based alloy.
In the preparation process, the feeding is covered by Co according to the sequence of the returned feeding of-C-Ni-Cr-Co-W-Co-Fe, and the Co is melted by high vacuum pumping, so that a better smelting effect can be obtained.
The alloy contains less harmful impurities and less internal defects, and can effectively reduce the precipitation and segregation of harmful carbides. Controlling the smelting temperature and time, wherein the forging heating temperature is 1160-1180 ℃, the heat treatment temperature of the wire rod is 1175-1230 ℃, and the peak value of the tensile strength can be ensured under the conditions of 14.2-15.5% of W and 19.2-20% of Cr. Vacuum melting and high-temperature refining are adopted to remove and reduce harmful impurities, and the purity and plasticity of the alloy are improved. The traditional single-joint metallurgy is changed into double-joint metallurgy of smelting and electroslag remelting, so that impurities in the alloy are obviously reduced, the purity of the alloy is further improved, and the mechanical property is greatly improved.
Detailed Description
In order to further understand the objects, structures, features and functions of the present invention, the following embodiments are described in detail.
Example 1:
the embodiment provides a cobalt-based high-temperature alloy wire which comprises the following chemical components in percentage by mass: 0.06% of C, less than or equal to 0.3% of Si, 1.1% of Mn1, 0.015% of P, 0.015% of S, 19.2% of Cr19.2%, 9.5% of Ni9, 14.2% of W, 1.6% of Fe1.6%, 0.4% of other impurities and the balance of Co.
Example 2:
the embodiment provides a cobalt-based superalloy wire, which comprises the following chemical components in percentage by mass: 0.07% of C, 0.2% of Si, 1.2% of Mn1, 0.01% of P, 0.01% of S, 20% of Cr, 10.5% of Ni, 14.6% of W, 0.0% of Fe2, 0.3% of other impurities and the balance of Co.
Example 3
The embodiment provides a cobalt-based high-temperature alloy wire which comprises the following chemical components in percentage by mass: 0.10% of C, 0.2% of Si, 1.5% of Mn1, 0.015% of P, 0.015% of S, 19.6% of Cr19, 10.5% of Ni10, 15.5% of W, 0.8% of Fe2.8%, 0.3% of other impurities and the balance of Co.
Adding 19.2-20% Cr to form Cr on the surface2O3The film layer has excellent corrosion resistance, and does not promote the generation of epsilon-Co and sigma phases due to the overhigh Cr content to generate a two-phase region so as to reduce the high-temperature strength. In addition, a large amount of Co, 14.2-15.5% of W, 19.2-20% of Cr and other elements which are used as a matrix in the cobalt-based alloy can reduce the stacking fault energy, form a large amount of stacking faults and twin crystals in the alloy, hinder the movement of dislocation and improve the high-temperature strength of the alloy; and the content of W is controlled to be 19.2-20%, so that the conditions of prominent work hardening, difficult cold working and poor stability of the alloy caused by excessive W content are avoided.
Meanwhile, the cobalt-based alloy contains 9.5-10.5% of Ni, which is beneficial to improving the structural stability of the alloy and reducing Co7W6Separating out a phase; as the Ni content increases, the average size of γ' increases, but when the Ni content increasesWhen the alloy is further increased, Ni atoms may form some impurity phases with other atoms, and the formation of a gamma 'strengthening phase is inhibited, so that the volume fraction of gamma' is reduced, and the yield strength and the plastic deformation capability of the alloy are reduced.
1.1-1.8% of Mn is added to effectively improve the oxidation resistance of the Ni-Cr alloy to form MnCr2O4The spinel has a barrier effect on oxygen, and can reduce the oxygen partial pressure of a spinel/chromium oxide interface, further reduce the oxidation speed of the alloy and improve the oxidation resistance of the cobalt-based alloy.
A method of producing a cobalt-based superalloy wire according to any of claims 1 to 2, wherein: comprises that
Step 1, preparing materials, cleaning surface oxide skin and ensuring brightness and no impurities;
step 2, vacuum smelting, namely feeding according to the sequence of returned feed-C-Ni-Cr-Co-W-Co-Fe, adding W into the middle part of the induction coil, covering the W with Co, and melting in high vacuum; alloying the molten steel by using a rocking furnace, wherein the melting temperature is 1330-1410 ℃, the refining temperature is 1560 ℃, the tapping temperature is 1520 ℃, and 35kg of electrode rods are cast;
step 3, electroslag remelting, wherein the slag system proportion is CaF 2: AL2O 3: CaO: MgO = 60: 20: 10: 10, electric power system: 45-50V, current: 2200 and 2800A, 5 minutes later feeding, 36kg of electroslag steel ingot, and slow cooling by hot sand;
step 4, forging, wherein the forging heating temperature is 1160-1180 ℃, the forging starting temperature is more than or equal to 1140 ℃, the finish forging temperature is more than or equal to 920 ℃, and the forging specification is as follows: 42 × 42 square rods, and slow cooling hot sand;
step 5, hot rolling, namely, the heating temperature of the square bar hot rolling is 1180 ℃, the heat preservation is carried out for 25 minutes, the initial rolling temperature is more than or equal to 1100 ℃, the final rolling temperature is more than or equal to 900 ℃, and the wire rod with the hot rolling specification phi 10 is air-cooled;
step 6, carrying out heat treatment on the wire rod, heating the electric furnace to 700 ℃, and charging to a set temperature: 1175-1230 ℃, preserving the temperature for 45 minutes, and then cooling by water;
step 7, cold drawing, namely, drawing at a low speed, removing crack defects by solid solution pickling surface polishing after drawing once, and then drawing;
and 8, checking and packaging.
Preferably, the vacuum melting in the step 2 is carried out, the melting vacuum degree is less than or equal to 5.0Pa, and the vacuum degree in the refining period is less than or equal to 1.0 Pa.
Preferably, when the rocking furnace is used for alloying the molten steel in the step 2, the rocking furnace is stirred back and forth for 2 to 3 times, and the refining time is more than 25 minutes.
Preferably, the forging heating temperature in step 4 is set to 1170 ℃.
Preferably, in the drawing process in the step 7, the deformation amount of each pass is controlled to be 15% -45%, and the final deformation amount is controlled to be 40%, namely 0.07 is drawn by using 0.16, and 0.1 is drawn by using 0.24.
Controlling the smelting temperature and time, wherein the forging heating temperature is 1160-1180 ℃, the heat treatment temperature of the wire rod is 1175-1230 ℃, and the peak value of the tensile strength can be ensured under the conditions of 14.2-15.5% of W and 19.2-20% of Cr.
Vacuum melting and high-temperature refining are adopted to remove and reduce harmful impurities, and the purity and plasticity of the alloy are improved. The traditional single-joint metallurgy is changed into double-joint metallurgy of smelting and electroslag remelting, so that impurities in the alloy are obviously reduced, the purity of the alloy is further improved, and the mechanical property is greatly improved.
The test performance of the cobalt-based high-temperature alloy wire material is as follows:
from the above, 19.2-20% of Cr is added to generate Cr on the surface2O3The film layer has excellent corrosion resistance, and does not promote the generation of epsilon-Co and sigma phases due to the overhigh Cr content to generate a two-phase region so as to reduce the high-temperature strength. In addition, a large amount of Co, 14.2-15.5% of W, 19.2-20% of Cr and other elements which are used as a matrix in the cobalt-based alloy can reduce the stacking fault energy, form a large amount of stacking faults and twin crystals in the alloy, hinder the movement of dislocation and improve the high-temperature strength of the alloy; and the conditions of outstanding alloy work hardening condition, difficult cold working and poor stability caused by excessive W content are avoided. Meanwhile, the cobalt-based alloy contains 9.5-10.5% of Ni, which is beneficial to improving the structural stability of the alloy and reducing Co7W6And separating out the phases.
In the preparation process, the feeding is covered by Co according to the sequence of the returned feeding-C-Ni-Cr-Co-W-Co-Fe, high vacuum melting is performed, better smelting effect can be obtained, electroslag remelting is performed by adopting a reasonable slag system proportion, and the estimated high-temperature alloy wire with stronger performances in various aspects such as thermal stability, high-temperature oxidation resistance, wear resistance and the like is obtained after forging, hot rolling, wire rod heat treatment and cold drawing at a set temperature.
The present invention has been described in relation to the above embodiments, which are only exemplary of the implementation of the present invention. It should be noted that the disclosed embodiments do not limit the scope of the invention. Rather, it is intended that all such modifications and variations be included within the spirit and scope of this invention.
Claims (7)
1. A cobalt-based high-temperature alloy wire comprises the following chemical components in percentage by mass: 0.06 to 0.12 percent of C, less than or equal to 0.3 percent of Si, 1.1 to 1.8 percent of MnP, less than or equal to 0.015 percent of P, less than or equal to 0.015 percent of S, 19.2 to 20 percent of Cr19, 9.5 to 10.5 percent of Ni0, 14.2 to 15.5 percent of W, 1.6 to 2.8 percent of Fe1, less than or equal to 0.4 percent of other impurities, and the balance of Co.
2. The cobalt-based superalloy wire of claim 1, wherein: the paint comprises the following chemical components in percentage by mass: 0.07 percent of C, less than or equal to 0.3 percent of Si, 1.2 percent of MnP, less than or equal to 0.015 percent of P, less than or equal to 0.015 percent of S, 20 percent of Cr, 10.5 percent of Ni10, 14.6 percent of W, 2.0 percent of Fe2, less than or equal to 0.4 percent of other impurities, and the balance of Co.
3. A method of producing a cobalt-based superalloy wire according to any of claims 1 to 2, wherein: comprises that
Step 1, preparing materials, cleaning surface oxide skin and ensuring brightness and no impurities;
step 2, vacuum smelting, namely feeding according to the sequence of returned feed-C-Ni-Cr-Co-W-Co-Fe, adding W into the middle part of the induction coil, covering the W with Co, and melting in high vacuum; alloying the molten steel by using a rocking furnace, wherein the melting temperature is 1330-1410 ℃, the refining temperature is 1560 ℃, the tapping temperature is 1520 ℃, and 35kg of electrode rods are cast;
step 3, electroslag remelting, wherein the slag system proportion is CaF 2: AL2O 3: CaO: MgO = 60: 20: 10: 10, electric power system: 45-50V, current: 2200 and 2800A, 5 minutes later feeding, 36kg of electroslag steel ingot, and slow cooling by hot sand;
step 4, forging, wherein the forging heating temperature is 1160-1180 ℃, the forging starting temperature is more than or equal to 1140 ℃, the finish forging temperature is more than or equal to 920 ℃, and the forging specification is as follows: 42 × 42 square rods, and slow cooling hot sand;
step 5, hot rolling, namely, the heating temperature of the square bar hot rolling is 1180 ℃, the heat preservation is carried out for 25 minutes, the initial rolling temperature is more than or equal to 1100 ℃, the final rolling temperature is more than or equal to 900 ℃, and the wire rod with the hot rolling specification phi 10 is air-cooled;
step 6, carrying out heat treatment on the wire rod, heating the electric furnace to 700 ℃, and charging to a set temperature: 1175-1230 ℃, preserving the temperature for 45 minutes, and then cooling by water;
step 7, cold drawing, namely, drawing at a low speed, removing crack defects by solid solution pickling surface polishing after drawing once, and then drawing;
and 8, checking and packaging.
4. The method for preparing a cobalt-based superalloy wire of claim 3, wherein: and (3) vacuum melting in the step (2), wherein the melting vacuum degree is less than or equal to 5.0Pa, and the vacuum degree in the refining period is less than or equal to 1.0 Pa.
5. The method for preparing a cobalt-based superalloy wire of claim 3, wherein: and 2, when the rocking furnace is used for alloying the molten steel in the step 2, stirring the rocking furnace back and forth for 2-3 times, wherein the refining time is more than 25 minutes.
6. The method for preparing a cobalt-based superalloy wire of claim 3, wherein: the forging heating temperature in step 4 was set to 1170 ℃.
7. The method for preparing a cobalt-based superalloy wire of claim 3, wherein: in the drawing process in the step 7, the deformation of each pass is controlled to be 15-45%, and the final deformation is controlled to be 40%, namely 0.16 drawing is used for drawing 0.07, and 0.24 drawing is used for drawing 0.1 finished products.
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