CN109022926B - High-temperature-resistant corrosion-resistant thermal spraying wire and preparation method thereof - Google Patents
High-temperature-resistant corrosion-resistant thermal spraying wire and preparation method thereof Download PDFInfo
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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
- C22C19/03—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
- C22C19/052—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 40%
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- 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
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/023—Alloys based on nickel
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- 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
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/06—Alloys based on chromium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- 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
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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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
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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
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
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- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
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Abstract
The invention belongs to the field of thermal spraying materials, and particularly relates to a high-temperature-resistant corrosion-resistant spraying material and a preparation method thereof, wherein the thermal spraying wire comprises the following components in percentage by mass: cr: 45-49%, Ti: 2-3%, C: 0.05-0.3%, active elements: 0.1-5%, and the balance of Ni and impurities, wherein the impurities are: o: 0.02% or less, P: 0.05% or less, S: less than 0.01 percent and meets the mass ratio of Ni/Cr of 0.9-1.1. The high-temperature-resistant steel contains more Cr and Ni elements, can form a stable austenite structure, dissolves more alloy elements in solid solution, further improves the stability of a system, can improve the high-temperature strength by adding C, can improve the processing performance by controlling the mass ratio of Ni to Cr to be 0.9-1.1, and is easy to process into wires; active nitrogen atoms cracked from ammonia gas in the preparation process can form hard nitrides with Ti, Si, B and the like, and the hard nitrides are pinned at a crystal boundary, so that austenite grains are prevented from growing and deforming, the stability of austenite is improved, and the high-temperature corrosion resistance and the wear resistance are further improved.
Description
Technical Field
The invention belongs to the field of thermal spraying materials, and particularly relates to a high-temperature-resistant corrosion-resistant thermal spraying wire and a preparation method thereof.
Background
The four boiler tubes (water wall tube, superheater tube, reheater tube and economizer tube) cover all the heated surfaces of the boiler, the interior of the four boiler tubes is subjected to the action of working medium pressure and some chemical components, the exterior of the four boiler tubes is subjected to the environmental influence of high temperature, erosion and abrasion, and the four boiler tubes are harmonized between water and fire, so that the problems of failure and leakage are easily caused. The leakage accidents of the four pipes are more, which not only poses serious threat to the stable operation of the unit, affects the completion of the power generation index and reduces the economic benefit, but also directly affects the normal dispatching of the power grid.
Fly ash abrasion and mechanical abrasion of a heating surface of a pulverized coal boiler are main reasons influencing long-term safe operation of the boiler, and pipe leakage is caused by strength reduction due to the fact that a pipe wall becomes thin due to long-time hand abrasion. In addition, alkali metals in the ash are biochemical at high temperature, and react with SO in the flue gas3Generating compound sulfate which is condensed on the pipe wall to destroy the oxide film on the surface of the pipe wall, namely generating high-temperature corrosion. Therefore, it is very important to improve the wear resistance, high temperature corrosion resistance and sulfate corrosion resistance of the surfaces of the four tubes of the boiler.
Disclosure of Invention
The invention discloses a high-temperature-resistant and corrosion-resistant thermal spraying wire and a preparation method thereof, aiming at solving the problem that four pipes of a boiler leak due to abrasion and corrosion.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-temperature-resistant corrosion-resistant thermal spraying wire comprises the following components in percentage by mass: cr: 45-49%, Ti: 2-3%, C: 0.05-0.3%, active elements: 0.1-5%, and the balance of Ni and impurities, wherein the impurities are: o: 0.02% or less, P: 0.05% or less, S: less than 0.01 percent and meets the mass ratio of Ni/Cr of 0.9-1.1. The system contains more Cr and Ni elements, can form a stable austenite structure, and can dissolve more alloy elements, and the addition of C can improve the high-temperature strength. Experiments prove that the Ni/Cr mass ratio is controlled to be between 0.9 and 1.1, the processing performance can be improved, and the wire is easy to process.
Preferably, the active element is one or more of Fe, Mn, Si, Zr, V, Mo and B.
Preferably, the thermal spraying wire comprises the following components in percentage by mass: cr: 45-49%, Ti: 2-3%, C: 0.05-0.3%, Fe: 0.1-0.5%, Mn: 0.5-1%, Si: 0.5-1%, and the balance of Ni and impurities, wherein the impurities are: o: 0.02% or less, P: 0.05% or less, S: less than 0.01 percent and meets the mass ratio of Ni/Cr of 0.9-1.1. On one hand, Si has smaller atomic radius and can diffuse to an oxidation area to participate in reaction, so that the compactness of an oxide is increased, the corrosion resistance is further improved, and the corrosion of sulfuric acid and sulfate can be obviously resisted; on the other hand, the silicon carbide can react with carbon in a matrix alloy material to be sprayed to generate silicon carbide, and the silicon carbide is a superhard substance, has lubricity and wear resistance, is an atomic crystal, resists oxidation at high temperature, can resist cold and hot impact, and is also beneficial to improving the high-temperature corrosion resistance.
Preferably, the thermal spraying wire comprises the following components in percentage by mass: cr: 45-49%, Ti: 2-3%, C: 0.05 to 0.3%, Si: 0.5-1%, Zr: 1-2%, and the balance of Ni and impurities, wherein the impurities are: o: 0.02% or less, P: 0.05% or less, S: less than 0.01 percent and meets the mass ratio of Ni/Cr of 0.9-1.1. Ti and Zr are strong carbide forming elements, and can react with carbon in the base material to form carbide in preference to Cr, so that Cr generated by the reaction of Cr and carbon in the system is reduced23C6And excessive consumption, which not only can reduce the Cr content2O3The content is reduced to loosen an oxide film, so that the high-temperature corrosion resistance is influenced, and the condition that the intergranular corrosion resistance is reduced due to local chromium depletion can be avoided as much as possible. Further, Zr does not oxidize and nitrify as easily as Ti, and thus, the addition of Zr can secure fixation of carbon to reduce negative effects of carbon, compared to the addition of Ti alone.
Preferably, the thermal spraying wire comprises the following components in percentage by mass: cr: 45-49%, Ti: 2-3%, C: 0.05 to 0.3%, Zr: 1-2%, V: 0.1-0.5%, B: 1-2%, and the balance of Ni and impurities, wherein the impurities are: o: 0.02% or less, P: 0.05% or less, S: less than 0.01 percent and meets the mass ratio of Ni/Cr of 0.9-1.1. V is also a strong carbide former for fixing carbon.
Preferably, the thermal spraying wire comprises the following components in percentage by mass: cr: 45-49%, Ti: 2-3%, C: 0.05 to 0.3%, Zr: 1-2%, Mo: 0.1-0.5%, and the balance of Ni and impurities, wherein the impurities are: o: 0.02% or less, P: 0.05% or less, S: less than 0.01 percent and meets the mass ratio of Ni/Cr of 0.9-1.1. The addition of Mo can improve the corrosion resistance of the coating in an oxidizing medium and a reducing medium.
Preferably, the thermal spraying wire comprises the following components in percentage by mass: cr: 45-49%, Ti: 2-3%, C: 0.05 to 0.3%, Si: 0.1-0.5%, Zr: 1-2%, B: 1-2%, and the balance of Ni and impurities, wherein the impurities are: o: 0.02% or less, P: 0.05% or less, S: less than 0.01 percent and meets the mass ratio of Ni/Cr of 0.9-1.1.
Preferably, the thermal spraying wire comprises the following components in percentage by mass: cr: 45-49%, Ti: 2-3%, C: 0.05 to 0.3%, Si: 0.1-0.8%, Zr: 1-2%, Mo: 0.1-0.5%, B: 0.1-0.5%, and the balance of Ni and impurities, wherein the impurities are: o: 0.02% or less, P: 0.05% or less, S: less than 0.01 percent and meets the mass ratio of Ni/Cr of 0.9-1.1.
A preparation method of a high-temperature-resistant corrosion-resistant thermal spraying wire material comprises the following specific steps:
(1) weighing raw material components in proportion in a mixed atmosphere of ammonia gas and argon gas, smelting according to the sequence of Ni, Cr, Ti, active elements and the rest components, preserving heat for 1-5h, and then casting into an alloy ingot;
(2) heating the alloy ingot to 1100-1200 ℃, and forging into a blank of 50 x 50 mm;
(3) carrying out first annealing treatment on the blank at 900-1000 ℃ under the protection of argon;
(4) the blank is swaged into a wire with the diameter of 1.6-2mm on a swaging machine at 1100-1250 ℃;
(5) removing oxide skin and rusty materials on the surface of the wire material by acid washing;
(6) and (3) carrying out secondary dehydrogenation annealing treatment on the wire material at 1100 ℃ under the protection of argon.
Experiments prove that the smelting and feeding sequence in the step (1) is strictly followed to be beneficial to forming uniform and stable alloy components, so that the high-temperature corrosion resistance is improved. The secondary annealing of step (6) helps to eliminate work hardening and residual internal stress and stabilize the dimensions.
Preferably, the volume ratio of the ammonia gas to the argon gas in the mixed atmosphere of the ammonia gas and the argon gas in the step (1) is 1: 4-8.
The wire prepared by the invention contains a large amount of Cr and Ni, an austenite structure can be formed after the wire is thermally sprayed into a coating, active nitrogen atoms generated by high-temperature pyrolysis of ammonia gas can react with Ti, Si, B and the like to form nitrides, and the nitrides are very hard and can be pinned at an austenite grain boundary, so that the growth and deformation of austenite grains are prevented, the stability of austenite is improved, and the high-temperature corrosion resistance of the thermally sprayed coating is further improved. However, in order to prevent excessive nitride formation and consume Ti, Si, B and other simple substances, the volume ratio of ammonia to argon in the mixed atmosphere of nitrogen and argon is 1:4-8, so that a small part of nitride is formed, and most of the simple substances are reserved.
The invention has the following beneficial effects: (1) the high-temperature-resistant corrosion-resistant thermal spraying wire (QDYC45) contains more Cr and Ni elements, can form a stable austenite structure, dissolves more alloy elements in a solid manner, further improves the stability of a system, can improve the high-temperature strength by adding C, controls the mass ratio of Ni to Cr to be 0.9-1.1, can improve the processing performance, and is easy to process into wires;
(2) on one hand, the added Si has smaller atomic radius and can diffuse to an oxidation area to participate in reaction, so that the compactness of an oxide is increased, the corrosion resistance is further improved, and the corrosion of sulfuric acid and sulfate can be remarkably resisted; on the other hand, the silicon carbide can react with carbon in a matrix alloy material to be sprayed to generate silicon carbide, and the silicon carbide is a superhard substance, has lubricity and wear resistance, is an atomic crystal, resists oxidation at high temperature, can resist cold and hot impact and is also beneficial to improving the high-temperature corrosion resistance;
(3) in the invention, Zr is a strong carbide forming element and can react with carbon in the base material to form carbide in preference to Cr, so that Cr generated by the reaction of Cr and carbon in the system is reduced23C6And excessive consumption, which not only can reduce the Cr content2O3The content is reduced to loosen an oxide film, so that the high-temperature corrosion resistance is influenced, and the condition that the intergranular corrosion resistance is reduced due to local chromium depletion can be avoided as much as possible. In addition, Zr does not resemble Ti is as easily oxidized and nitrided, so the addition of Zr can ensure the fixation of carbon to reduce the negative effects of carbon compared to the addition of Ti alone;
(4) the addition of Mo in the invention can improve the corrosion resistance of the coating in an oxidizing medium and a reducing medium;
(5) the wire prepared by the invention contains a large amount of Cr and Ni, an austenite structure can be formed after the wire is thermally sprayed into a coating, nitrogen can form nitrides with Ti, Si, B and the like, the nitrides are very hard, and the nitrides can be pinned at an austenite grain boundary, so that the growth and deformation of austenite grains are prevented, the stability of austenite is improved, the high-temperature corrosion resistance of the thermal spraying coating is improved, and the wear resistance of the coating can be improved;
(6) the invention does not contain rare earth elements and has low cost.
Detailed Description
The present invention will now be described in further detail with reference to examples.
Example 1
A high-temperature-resistant corrosion-resistant thermal spraying wire comprises the following components in percentage by mass: cr: 45%, Ti: 3%, C: 0.25%, Fe: 0.38%, Mn: 0.8%, Si: 1%, and the balance of Ni and impurities, wherein the impurities are: o: 0.02% or less, P: 0.05% or less, S: less than 0.01 percent.
The preparation method of the high-temperature-resistant corrosion-resistant thermal spraying wire material comprises the following specific steps:
(1) weighing raw material components in proportion in a mixed atmosphere of ammonia gas and argon gas, smelting according to the sequence of Ni, Cr, Ti, active elements and the rest components, preserving heat for 1-5h, and then casting into an alloy ingot;
(2) heating the alloy ingot to 1100-1200 ℃, and forging into a blank of 50 x 50 mm;
(3) carrying out first annealing treatment on the blank at 900-1000 ℃ under the protection of argon;
(4) the blank is swaged into a wire with the diameter of 1.6-2mm on a swaging machine at 1100-1250 ℃;
(5) removing oxide skin and rusty materials on the surface of the wire material by acid washing;
(6) and (3) carrying out secondary dehydrogenation annealing treatment on the wire material at 1100 ℃ under the protection of argon.
Wherein the volume ratio of the ammonia gas to the argon gas in the step (1) is 1: 4.
The components and their amounts in parts by weight of examples 1-6 are detailed in Table 1.
TABLE 1
The above Ni/Cr mass ratio is a calculation result when the maximum value is taken at O, P, S.
The components and their amounts in parts by weight of comparative examples 1-11 are detailed in Table 2.
TABLE 2
The above Ni/Cr mass ratio is a calculation result when the maximum value is taken at O, P, S.
Comparative example 14 is substantially the same as example 2 except that in step (1), Ti, active elements, Ni, Cr and the rest of the components were melted in this order.
Comparative example 15 is substantially the same as example 2 except that in step (1), Ti, Ni, an active element, Cr and the rest are melted in this order.
Comparative example 16 is substantially the same as example 2 except that all components are melted simultaneously in step (1).
Comparative example 17, substantially the same as example 2 except that step (6) was not performed in the wire production process.
Table 3 shows the mechanical properties of the thermal spray wires prepared in examples 1 to 6 and comparative examples 1 to 17.
TABLE 3
The thermal spray wires prepared in examples 1 to 6 and comparative examples 1 to 13 were used to prepare coatings on the surfaces of 304 stainless steel, which is commonly used for four tubes of boilers, and Table 4 shows the properties of the prepared coatings.
TABLE 4
Wherein the hot corrosion resistance is the test result after 100 hours at 1000 ℃.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (6)
1. A high temperature and corrosion resistant thermal spraying wire material is characterized in that: the thermal spraying wire comprises the following components in percentage by mass: cr: 45-49%, Ti: 2-3%, C: 0.05-0.3%, active elements: 0.1-5%, and the balance of Ni and impurities, wherein the impurities are: o: 0.02% or less, P: 0.05% or less, S: less than 0.01 percent, and the mass ratio of Ni/Cr is 0.9-1.1;
the active element is one or more of Fe, Mn, Si, Zr, V, Mo and B,
Fe：0.1-0.5％，
Mn：0.5-1％，
Si：0.5-1％，
Zr：1-2％，
V：0.1-0.5％，
Mo：0.1-0.5％，
B：1-2％；
the preparation method of the high-temperature-resistant corrosion-resistant thermal spraying wire material comprises the following specific steps:
(1) weighing raw material components in proportion in a mixed atmosphere of ammonia gas and argon gas, smelting according to the sequence of Ni, Cr, Ti, active elements and the rest components, preserving heat for 1-5h, and then casting into an alloy ingot;
(2) heating the alloy ingot to 1100-1200 ℃, and forging into a blank of 50 x 50 mm;
(3) carrying out first annealing treatment on the blank at 900-1000 ℃ under the protection of argon;
(4) the blank is swaged into a wire with the diameter of 1.6-2mm on a swaging machine at 1100-1250 ℃;
(5) removing oxide skin and rusty materials on the surface of the wire material by acid washing;
(6) and (3) carrying out secondary dehydrogenation annealing treatment on the wire material at 1100 ℃ under the protection of argon.
2. The high temperature and corrosion resistant thermal spray wire of claim 1, wherein: the thermal spraying wire comprises the following components in percentage by mass: cr: 45-49%, Ti: 2-3%, C: 0.05-0.3%, Fe: 0.1-0.5%, Mn: 0.5-1%, Si: 0.5-1%, and the balance of Ni and impurities, wherein the impurities are: o: 0.02% or less, P: 0.05% or less, S: less than 0.01 percent and meets the mass ratio of Ni/Cr of 0.9-1.1.
3. The high temperature and corrosion resistant thermal spray wire of claim 1, wherein: the thermal spraying wire comprises the following components in percentage by mass: cr: 45-49%, Ti: 2-3%, C: 0.05 to 0.3%, Si: 0.5-1%, Zr: 1-2%, and the balance of Ni and impurities, wherein the impurities are: o: 0.02% or less, P: 0.05% or less, S: less than 0.01 percent and meets the mass ratio of Ni/Cr of 0.9-1.1.
4. The high temperature and corrosion resistant thermal spray wire of claim 1, wherein: the thermal spraying wire comprises the following components in percentage by mass: cr: 45-49%, Ti: 2-3%, C: 0.05 to 0.3%, Zr: 1-2%, V: 0.1-0.5%, B: 1-2%, and the balance of Ni and impurities, wherein the impurities are: o: 0.02% or less, P: 0.05% or less, S: less than 0.01 percent and meets the mass ratio of Ni/Cr of 0.9-1.1.
5. The high temperature and corrosion resistant thermal spray wire of claim 1, wherein: the thermal spraying wire comprises the following components in percentage by mass: cr: 45-49%, Ti: 2-3%, C: 0.05 to 0.3%, Zr: 1-2%, Mo: 0.1-0.5%, and the balance of Ni and impurities, wherein the impurities are: o: 0.02% or less, P: 0.05% or less, S: less than 0.01 percent and meets the mass ratio of Ni/Cr of 0.9-1.1.
6. The high temperature and corrosion resistant thermal spray wire of claim 1, wherein: in the step (1), the volume ratio of ammonia gas to argon gas in the mixed atmosphere of ammonia gas and argon gas is 1: 4-8.
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| DE19845348A1 (en) * | 1998-10-02 | 2000-04-06 | Amil Werkstofftechnologie Gmbh | Core-filled wire, for thermal spraying of wear and/or corrosion resistant layers on heat exchanger and firing unit surfaces, contains an atomized nickel-aluminum or nickel-chromium-titanium alloy powder |
| CN1204280C (en) * | 2001-11-06 | 2005-06-01 | 北京有色金属研究总院 | High-chromium nickel-base alloy and produced spraying wire and its application |
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