CN104745883A - Nickel-based alloy and application thereof - Google Patents
Nickel-based alloy and application thereof Download PDFInfo
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- CN104745883A CN104745883A CN201310737777.1A CN201310737777A CN104745883A CN 104745883 A CN104745883 A CN 104745883A CN 201310737777 A CN201310737777 A CN 201310737777A CN 104745883 A CN104745883 A CN 104745883A
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Abstract
The invention provides a nickel-based alloy, which comprises the following components by weight: 21-26% of chromium, 3.0-5.5% of tungsten, 6.0-8.0% of molybdenum, 1.3-1.7% of aluminum, 0.4-0.7% of manganese, and 3.0-4.5% of iron, and the base material is nickel. The nickel-based alloy has good corrosion resisting performance in supercritical water oxidation environment, and has excellent corrosion resisting capability in the supercritical water oxidation environment containing sulfate radical ions.
Description
Technical field
The present invention relates in general to corrosion resistant material field, more specifically, relates to a kind of nickel-base alloy and application thereof.
Background technology
Growing along with national economy, in the continuous increase of city size and China's industrial production, pharmacy industry and dyeing industry enterprise is on the increase, the problem of municipal effluent, sludge treatment seems more and more outstanding, and a large amount of acid that industrial production produces, alkaline pollutant also get more and more.
When the temperature and pressure postcritical value (374.3 DEG C of water, 22.05MPa) time, water in system is just referred to as the water of " overcritical ", usually by temperature more than 374 DEG C, and pressure is higher than 22.05Mpa(such as 23Mpa) water surrounding be called supercritical water environment.At present, the material that can be applicable to supercritical water oxidation apparatus mostly is nickel-base alloy, wherein most often corrosion-resistant Hastelloy C alloys-276 and nickel-base alloy Inconel625.Wherein, the component of C-276 is: chromium: 15.0% ~ 16.5%, iron: 4.0% ~ 7.0%, molybdenum: 15.0% ~ 17.0%, tungsten: 3.0% ~ 4.5%, vanadium: 0.1% ~ 0.3%, carbon: < 0.01%, manganese: < 1.0%, silicon: < 0.08%, cobalt: < 2.5%, phosphorus: < 0.015%, sulphur: < 0.01%, all the other are base material nickel.But the corrosion resistance nature of C-276 and Inconel625 of the prior art under supercritical water environment not fully up to expectations.After the super critical point reaching water, the content of sulfate radical will be subject to the solubleness of oxygen and the impact of pressure, and the corrosion of alloy is generally chemical oxidation of gold, and the oxide film easily destroying alloy forms general corrosion.When temperature reaches more than the super critical point of water, sulfate ion has stronger destructiveness to the oxide film of the chromium in nickel-base alloy in 380 DEG C ~ 550 DEG C intervals, especially in pharmacy waste water, coal gasification waste water the like waste, sulfate radical and/or sulfide (can sulfate radical be converted into after process) content very high, therefore to the requirement also corresponding raising of material, in prior art, the shortcoming of material corrosion resistance difference constrains the development at supercritical water oxidation environment sewerage disposing device.
Summary of the invention
For the shortcoming of material of the prior art poor corrosion resistance in supercritical water oxidation environment, the invention provides a kind of nickel-base alloy, comprising:
Chromium, 21%(weight) ~ 26%(weight);
Tungsten, 3.0%(weight) ~ 5.5%(weight);
Molybdenum, 6.0%(weight) ~ 8.0%(weight);
Aluminium, 1.3%(weight) ~ 1.7%(weight);
Manganese, 0.4%(weight) ~ 0.7%(weight);
Iron, 3.0%(weight) ~ 4.5%(weight);
Base material is nickel.
According to some embodiments, the content of chromium is 21.5%(weight) ~ 25.4%(weight).
According to some embodiments, the content of tungsten is 3.2%(weight) ~ 5.1%(weight).
According to some embodiments, the content of molybdenum is 6.3%(weight) ~ 7.6%(weight).
According to some embodiments, the content of iron is 3.2%(weight) ~ 4.3%(weight).
According to some embodiments, nickel-base alloy also comprises 0.8%(weight) ~ 1.1%(weight) tantalum.
According to some embodiments, nickel-base alloy also comprises carbon and/or silicon, and wherein, the content of carbon is less than or equal to 0.05%(weight), the content of silicon is less than or equal to 0.2%(weight).
Another aspect of the present invention comprises the application of above-mentioned nickel-base alloy in corrosive environment.
According to some embodiments, corrosive environment is supercritical water oxidation environment.
According to some embodiments, the pH value of supercritical water oxidation environment is between 4 to 7.
According to some embodiments, in supercritical water oxidation environment, comprise the sulfate ion of concentration between 0.135g/L to 0.406g/L.
According to some embodiments, the temperature of supercritical water oxidation environment is in the scope of 380 DEG C to 550 DEG C.
Nickel-base alloy of the present invention has good corrosion resistance nature in supercritical water oxidation environment, in the supercritical water oxidation environment containing sulfate ion, especially show excellent corrosion resistance.
Embodiment
Be clearly and completely described to the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain, all belongs to the scope of protection of the invention.
In an embodiment of the present invention, a kind of very important effect of chromium in superalloy austenitic matrix forms chromium sesquioxide type oxide film, and this oxide film makes high-temperature alloy part have good oxidation-resistance and hot corrosion resistance.Therefore nickel-base alloy of the present invention adds content and controls in 21%(weight) to 26%(weight) scope in chromium to improve the erosion resistance of nickel-base alloy nickel in Oxidant, wherein Oxidant comprises oxidizing acid, oxidative acidic salt, oxidisability basic salt etc.For improving the processing characteristics of nickel-base alloy of the present invention, the content of chromium preferably can be controlled in 21.5%(weight) to 25.8%(weight) scope in.In different environments, the critical chromium content improving nickel-based nickel Chrome metal powder erosion resistance is different, but the content of chromium selected in the present invention all can effectively make nickel-base alloy of the present invention in corrosive environment, have good corrosion resistant effect.In addition, the chromium in superalloy austenitic matrix causes lattice distortion, the intensity of austenite sosoloid is improved, plays the effect of solution strengthening.Chromium can also reduce sosoloid stacking fault energy, and creep rupture strength is significantly improved.
Tungsten atom radius is larger, the effect of solution strengthening is mainly played in nickel-base alloy of the present invention, therefore, in nickel-base alloy of the present invention, the content of tungsten is controlled in tungsten 3.0%(weight) to 5.5%(weight) scope, preferably control in 3.2%(weight) to 5.1%(weight) scope in, thus the lattice distortion caused in superalloy matrix is obviously expanded, forms longer long range stress field, produce tissue dislocation motion simultaneously, and yield strength is significantly improved.In nickel-base alloy of the present invention, tungsten obviously reduces the stacking fault energy of austenitic matrix, effectively can improve the creep property of superalloy.
In nickel-base alloy of the present invention, the addition of molybdenum controls in 6.0%(weight) to 8.0%(weight) scope in, preferably control in 6.3%(weight) to 7.9%(weight) scope in.Within the scope of this addition, molybdenum can improve nickel-base alloy of the present invention in acid condition effectively, especially containing the erosion resistance in the corrosive environment of sulfate radical, and maintains good stable phase.
Aluminium forms the essentially consist element that nickel aluminium strengthens phase in superalloy, therefore in nickel-base alloy of the present invention, add content control in 1.3%(weight) to 1.7%(weight) scope in aluminium, thus make the aluminum portions in alloy enter γ sosoloid, play solution strengthening effect, another part carries out precipitation strength.In addition, aluminium is significantly increased the effect of alloy high-temp antioxidant property, and in corrosive environment, aluminium forms fine and close aluminium sesquioxide oxide film, and intercepts the diffusion of Sauerstoffatom, to carry heavy alloyed anti-oxidant and hot corrosion resistance.
Manganese both hard have be rich in toughness, make alloy be easy to processing, therefore in the present invention by the content control of manganese in 0.4%(weight) ~ 0.7%(weight) and scope in.
Interpolation iron appropriate in the present invention can improve the solubleness of carbon in nickel, and then improves the susceptibility of alloy to intergranular corrosion, improves its anti-permeability performance.Therefore in nickel-base alloy of the present invention, the content of iron is controlled in 3.0%(weight) ~ 4.5%(weight) scope in, preferably, control in 3.1%(weight) ~ 4.3%(weight) scope in.In addition, the use of iron also can fall low-alloyed cost.
Nickel, as matrix element, can dissolve more alloying element and carry out alloying, and still keep the stability of austenite phase.Therefore using the base material of nickel as nickel-base alloy of the present invention, and its content is used for the formula of trim nickel-base alloy, makes alloy total amount be 100%.Nickel is face-centred cubic structure and does not have ppolymorphism to change, and almost all the matrix of superalloy is all the austenite with face-centred cubic structure, because austenite has higher hot strength than body-centred cubic ferrite.The reason that austenitic hot strength is higher is that its atomic diffusion ability is less, and namely self-diffuse activation energy is higher.Simultaneously nickel has higher chemical stability, the etch of not moisture-sensitive gas, water and some salts solution under normal temperature.
In some other embodiment of the present invention, also comprise content and control in 0.8%(weight) ~ 1.1%(weight) scope in tantalum.Tantalum can strengthen the high-temperature ductility of alloy in nickel-base alloy of the present invention, and improves the processing characteristics of alloy.
In other embodiments of the present invention, also comprise carbon and silicon.Carbon and silicon can improve alloy strength, but excessive carbon and silicon can destroy material erosion resistance in acid condition.Therefore, in nickel-base alloy of the present invention by the content control of carbon and silicon be: the content of carbon is less than or equal to 0.05%(weight), the content of silicon is less than or equal to 0.2%(weight).
It should be understood by one skilled in the art that, tantalum only for putting forward heavy alloyed high-temperature ductility and corresponding mechanical property, uses the nickel-base alloy without the formula of tantalum can reach corrosion resistant effect in supercritical water environment equally in nickel-base alloy of the present invention; Carbon and the corrosion resistance nature of silicon to nickel-base alloy of the present invention do not help, and therefore, when not comprising carbon and silicon, nickel-base alloy of the present invention can reach corrosion resistant effect equally.Simultaneously, although be not specifically described impurity contained in nickel-base alloy of the present invention, but, it should be understood by one skilled in the art that, inevitably be retained in final alloy by the impurity of trace in the manufacturing processed of alloy, these impurity may comprise oxygen, phosphorus or sulphur etc.
The preparation method of the nickel-base alloy applied under being applicable to supercritical water oxidation condition:
Raw material metal chromium, tungsten, molybdenum, nickel, iron etc. are joined in vacuum induction furnace on request, closes stove evacuation, until vacuum tightness is less than 10Pa.Then, start deposite metal with the power power transmission of 30KW, continue ten minutes, then with the power power transmission of 50KW until change clear.Utilize infrared radiation detection apparatus to detect furnace temperature, power to the liquid steel temperature of adjustment fusing is simultaneously stabilized in 1480 DEG C, enters refining period, keeps furnace temperature 10-15 minute at this temperature.In the refining later stage, vacuum tightness should lower than 1Pa.After refining terminates, have a power failure and stop power delivery, carry out lowering the temperature until freeze conjunctiva, in stove, pass into the argon gas of 0.04MPa pressure.In alloying step, power transmission is become civilized, and joins in melt lentamente by aluminium, send high-power stirring.In a preferred embodiment, tantalum and aluminium are joined in melt simultaneously.Then lower the temperature.Add sweetening agent, induction furnace is found time, then pass into argon gas with the pressure of 0.04MPa, and evenly add manganese.After freezing melt, power transmission temperature adjustment is poured into a mould.
Embodiment
The present invention is further illustrated below by specific embodiment and comparative alloy, in following examples and comparative alloy, the corrosion resistance nature of nickel-base alloy of the present invention is described by the hanging test under varying environment (differing temps, different pH value and different sulfate ion concentrations), and in conjunction with comparative alloy, advantage of the present invention is described.In table 1, examples of alloys 1-7 is the nickel-base alloy of the different components content of same recipe in the present invention, and in table, data are all weight percentage, and " Bal. " uses Ni trim component for representing.
Table 1
| Ni | Cr | W | Mo | Al | Mn | Fe | Ta | C | |
| Embodiment 1 | Bal. | 21.0 | 3.2 | 6.8 | 1.3 | 0.5 | 3.0 | 0.9 | ≤0.05 |
| Embodiment 2 | Bal. | 21.5 | 4.9 | 6.0 | 1.3 | 0.7 | 4.1 | 1.0 | ≤0.05 |
| Embodiment 3 | Bal. | 22.4 | 5.5 | 6.6 | 1.4 | 0.6 | 3.9 | 1.1 | ≤0.05 |
| Embodiment 4 | Bal. | 23.6 | 4.7 | 7.4 | 1.5 | 0.6 | 4.5 | 0.8 | ≤0.05 |
| Embodiment 5 | Bal. | 25.4 | 5.1 | 8.0 | 1.7 | 0.5 | 3.5 | 0 | ≤0.05 |
| Embodiment 6 | Bal. | 25.8 | 3.0 | 6.3 | 1.6 | 0.4 | 3.2 | 0.9 | ≤0.05 |
| Embodiment 7 | Bal. | 26.0 | 3.5 | 7.6 | 1.5 | 0.6 | 4.3 | 0 | ≤0.05 |
Comparative alloy 1
Corrosion-resistant Hastelloy C alloys-276, its component of weight percent comprises:
Chromium: 15.0% ~ 16.5%
Iron: 4.0% ~ 7.0%
Molybdenum: 15.0% ~ 17.0%
Tungsten: 3.0% ~ 4.5%
Vanadium: 0.1% ~ 0.3%
Carbon: < 0.01%
Manganese: < 1.0%
Silicon: < 0.08%
Cobalt: < 2.5%
Phosphorus: < 0.015%
Sulphur: < 0.01%
All the other are base material nickel.
Comparative alloy 2
Nickel-base alloy Inconel625, its component of weight percent comprises:
Chromium: 20% ~ 23%
Molybdenum: 8% ~ 10%
Niobium: 3.15% ~ 4.15%
Iron: < 5%
Aluminium: < 0.4%
Titanium: < 0.4%
Carbon: < 0.1%
Manganese: < 0.5%
Silicon: < 0.5%
Copper: < 0.5%
Phosphorus: < 0.015%
Sulphur: < 0.015%
All the other are base material nickel.
Respectively the nickel-base alloy (ESM-V) in embodiment 1-7 and comparative alloy 1,2 are tested as follows
Experiment 1
At 450 DEG C, 23MPa, and under pH is respectively the condition of 4,5,7, use the coupon test containing 3% hydrogen peroxide (for providing oxygen) and respectively the nickel-base alloy (ESM-V) in embodiment 1,2 and 3 is carried out 500 hours, wherein, the sodium sulfate (that is, sulfate ion concentration is 0.270g/L) that concentration is 0.4g/L is dissolved with in hydrogen peroxide.Place Inconel-625 and C-276 print simultaneously and be used for contrast.Experimental result is as shown in table 2, and in table 2, data are the material annual erosion rate (mm/yr) of carrying out gained after hanging test, and erosion rate absolute value lower explanation corrosion resistance nature is better.
Table 2
Experimental result shows, in supercritical water oxidation environment, has good anticorrosion effect with alloy phase of the prior art than nickel-base alloy ESM-V of the present invention.Nickel-base alloy ESM-V of the present invention shows excellent corrosion resistance nature in acid supercritical water oxidation environment.In the supercritical water oxidation environment of pH value between 4 to 7, the annual erosion rate of nickel-base alloy of the present invention is all lower than the annual erosion rate of prior art interalloy.
Experiment 2
At 450 DEG C, 23MPa, and pH is under the condition of 5, use the coupon test containing 3% hydrogen peroxide (for providing oxygen) and respectively the nickel-base alloy (ESM-V) in embodiment 2,4 and 5 is carried out 500 hours, wherein, be dissolved with respectively in hydrogen peroxide concentration be 0.2g/L(namely, sulfate ion concentration is 0.135g/L), 0.4g/L(namely, sulfate ion concentration is 0.270g/L) and 0.6g/L(namely, sulfate ion concentration is 0.406g/L) sodium sulfate.Place Inconel-625 and C-276 print simultaneously and be used for contrast.Experimental result is as shown in table 3, and in table 3, data are the material annual erosion rate (mm/yr) of carrying out gained after hanging test, and erosion rate absolute value lower explanation corrosion resistance nature is better.
Table 3
Experimental result shows, in supercritical water oxidation environment, than nickel-base alloy ESM-V of the present invention, there is good anticorrosion effect with alloy phase of the prior art, simultaneously, nickel-base alloy ESM-V of the present invention shows the performance of excellent resistance to sulfate ion corrosion, at sulfate ion concentration in the supercritical water oxidation environment of 0.135g/L to 0.406g/L, the annual erosion rate of nickel-base alloy of the present invention is all lower than the annual erosion rate of prior art interalloy.
Experiment 3
At 23MPa, and pH is under the condition of 5, use the coupon test containing 3% hydrogen peroxide (for providing oxygen) and respectively the nickel-base alloy (ESM-V) in embodiment 2,6,7 is carried out 500 hours, wherein, be dissolved with respectively in hydrogen peroxide concentration be 0.4g/L(namely, sulfate ion concentration is 0.270g/L) sodium sulfate.In this experiment, test temperature is respectively 380 DEG C, 450 DEG C and 550 DEG C.Place Inconel-625 and C-276 print simultaneously and be used for contrast.Experimental result is as shown in table 4, and in table 4, data are the material annual erosion rate (mm/yr) of carrying out gained after hanging test, and erosion rate absolute value lower explanation corrosion resistance nature is better.
Table 4
Experimental result shows, in supercritical water oxidation environment, have good anticorrosion effect with alloy phase of the prior art than nickel-base alloy ESM-V of the present invention, meanwhile, nickel-base alloy ESM-V of the present invention shows the performance of excellent resistance to sulfate ion corrosion.In the supercritical water oxidation environment of 380 DEG C to 550 DEG C, the annual erosion rate of nickel-base alloy of the present invention is all lower than the annual erosion rate of prior art interalloy.
Above-mentioned experiment has carried out corrosion resistance test to nickel-base alloy of the present invention under different conditions, experimental result shows, all has good corrosion resistance nature in the environment of nickel-base alloy of the present invention (especially in the supercritical water oxidation environment of 380 DEG C to 550 DEG C), sulfate ion containing different concns under supercritical water oxidation condition, in the environment of different pH value and in the arbitrary combination of above-mentioned environment.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (12)
1. a nickel-base alloy, comprising:
Chromium, 21%(weight) ~ 26%(weight);
Tungsten, 3.0%(weight) ~ 5.5%(weight);
Molybdenum, 6.0%(weight) ~ 8.0%(weight);
Aluminium, 1.3%(weight) ~ 1.7%(weight);
Manganese, 0.4%(weight) ~ 0.7%(weight);
Iron, 3.0%(weight) ~ 4.5%(weight);
Base material is nickel.
2. nickel-base alloy according to claim 1, is characterized in that, the content of chromium is 21.5%(weight) ~ 25.4%(weight).
3. nickel-base alloy according to claim 1, is characterized in that, the content of tungsten is 3.2%(weight) ~ 5.1%(weight).
4. according to the nickel-base alloy described in claim 1, it is characterized in that, the content of molybdenum is 6.3%(weight) ~ 7.6%(weight).
5. according to the nickel-base alloy described in claim 1, it is characterized in that, the content of iron is 3.2%(weight) ~ 4.3%(weight).
6. according to the nickel-base alloy described in claim 1, it is characterized in that, described nickel-base alloy also comprises 0.8%(weight) ~ 1.1%(weight) tantalum.
7. nickel-base alloy according to claim 1, is characterized in that, described nickel-base alloy also comprises carbon and/or silicon, and wherein, the content of carbon is less than or equal to 0.05%(weight), the content of silicon is less than or equal to 0.2%(weight).
8. the application of the nickel-base alloy according to any one of claim 1-7 in corrosive environment.
9. the application of nickel-base alloy according to claim 8 in corrosive environment, is characterized in that, described corrosive environment is supercritical water oxidation environment.
10. the application of nickel-base alloy according to claim 9 in corrosive environment, is characterized in that, the pH value of described supercritical water oxidation environment is between 4 to 7.
11. application of nickel-base alloy according to claim 9 in corrosive environment, is characterized in that, comprise the sulfate ion of concentration between 0.135g/L to 0.406g/L in described supercritical water oxidation environment.
12. application of nickel-base alloy according to claim 9 in corrosive environment, is characterized in that, the temperature of described supercritical water oxidation environment is in the scope of 380 DEG C to 550 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20170007133A (en) * | 2015-07-08 | 2017-01-18 | 헤인스 인터내셔널, 인코포레이티드 | METHOD FOR PRODUCING TWO-PHASE Ni-Cr-Mo ALLOYS |
| CN112038101A (en) * | 2020-07-24 | 2020-12-04 | 东莞东阳光科研发有限公司 | Method for etching electrode foil for aluminum electrolytic capacitor and electrode foil |
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| CN101784685A (en) * | 2007-08-31 | 2010-07-21 | 日立金属株式会社 | Low-thermal-expansion ni-based super-heat-resistant alloy for boiler and having excellent high-temperature strength, and boiler component and boiler component production method using the same |
| CN102498225A (en) * | 2009-09-18 | 2012-06-13 | 住友金属工业株式会社 | Ni-based alloy material |
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| CN101784685A (en) * | 2007-08-31 | 2010-07-21 | 日立金属株式会社 | Low-thermal-expansion ni-based super-heat-resistant alloy for boiler and having excellent high-temperature strength, and boiler component and boiler component production method using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20170007133A (en) * | 2015-07-08 | 2017-01-18 | 헤인스 인터내셔널, 인코포레이티드 | METHOD FOR PRODUCING TWO-PHASE Ni-Cr-Mo ALLOYS |
| KR102660878B1 (en) | 2015-07-08 | 2024-04-26 | 헤인스 인터내셔널, 인코포레이티드 | METHOD FOR PRODUCING TWO-PHASE Ni-Cr-Mo ALLOYS |
| CN112038101A (en) * | 2020-07-24 | 2020-12-04 | 东莞东阳光科研发有限公司 | Method for etching electrode foil for aluminum electrolytic capacitor and electrode foil |
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Application publication date: 20150701 |