CN112030041B - MonelK500A alloy with corrosion resistance in oxygen-containing hydrofluoric acid - Google Patents
MonelK500A alloy with corrosion resistance in oxygen-containing hydrofluoric acid Download PDFInfo
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- CN112030041B CN112030041B CN202010929341.2A CN202010929341A CN112030041B CN 112030041 B CN112030041 B CN 112030041B CN 202010929341 A CN202010929341 A CN 202010929341A CN 112030041 B CN112030041 B CN 112030041B
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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
- C22C19/058—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
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/16—Remelting metals
- C22B9/18—Electroslag remelting
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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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- 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 belongs to the field of improvement of Monel K500, and particularly relates to Monel K500A alloy with corrosion resistance in oxygen-containing hydrofluoric acid. The improved Monel K500A alloy comprises the following chemical components in percentage by weight: 64-66% of Ni, 1-1.5% of Fe, 0.5-1.0% of Mn, 0.08-0.12% of C, 2.0-3.0% of Al, 1.2-2.2% of Si, 0.6-0.7% of Ti, 4-5% of Cr, 0.5-0.7% of Zr, 0.3-0.6% of V, more than or equal to 1.0% of Zr and V, and the balance of Cu. According to the invention, chromium, zirconium and vanadium elements with specified proportions are added into the Monel K500 alloy, and the silicon element is added to obviously improve the corrosion performance of the new alloy in oxygen-containing hydrofluoric acid, so that the limitation that the conventional Monel K500 alloy cannot be used in the oxygen-containing hydrofluoric acid is broken through. The flaw detection qualification rate of the new alloy is improved by limiting the elements of carbon and titanium, the first-time flaw detection qualification rate is improved from 70% to more than 90%, and the high yield strength of the alloy is ensured.
Description
Technical Field
The invention belongs to the field of improvement of Monel K500, and particularly relates to Monel K500A alloy with corrosion resistance in oxygen-containing hydrofluoric acid.
Background
Monel K500 has higher mechanical strength and hardness, better heat-resisting corrosion resistance and long-term structure stability. The room temperature mechanical properties of Monel K500 alloy are as follows: the hardness of the bar is generally 140-315 HB, the hardness of a thin plate, a strip and a pipe is generally less than or equal to 85HRB, the hardness of a medium plate is 260-337 HB, and the processing states are slightly different. The Monel K500 alloy has good low-temperature ductility and toughness, so that cold machining cannot feel any difficulty, but the forming temperature is 871-1149 ℃ in the aspect of hot machining, the alloy solution annealing temperature is 793-971 ℃, and good comprehensive performance can be obtained.
The Monel K500 alloy comprises the following chemical components in percentage by weight: less than or equal to 0.25 percent of carbon C, 63-67 percent of nickel Ni, 2.0-4.0 percent of aluminum Al, 0.25-1.00 percent of titanium Ti, less than or equal to 2.0 percent of iron Fe, less than or equal to 1.5 percent of manganese Mn, less than or equal to 1.00 percent of silicon Si, less than or equal to 0.01 percent of sulfur S, 0.08-0.12 percent of magnesium Mg, and the balance of copper Cu. Mechanical properties of Monel alloy Monel K500 in solid solution state: tensile strength of 70-90 MPa, yield strength (0.2% Offset) of 482-621 ksi, and elongation of 25-60%. Generally, the mechanical property is improved after the aging hardening heat treatment.
The high-strength Monel alloy Monel K500 has the double advantages of Ni and Cu, and is more corrosion resistant than Ni-based alloy in a reducing medium and more corrosion resistant than Ni and Cu in an oxidizing medium. The greatest application advantage of the composite material for one hundred years is the best metal material resisting corrosion of hydrofluoric acid except platinum and silver. However, when oxygen is present in hydrofluoric acid, the resistance to corrosion by hydrofluoric acid is drastically lowered. The corrosion is improved by 5-200 times along with the increase of the oxygen content, and the service life of hydrofluoric acid resistant equipment in an oxygen-containing production environment is seriously limited.
Disclosure of Invention
The invention aims to provide a Monel K500A alloy with corrosion resistance in oxygen-containing hydrofluoric acid, which obviously improves the corrosion performance of a new alloy in the oxygen-containing hydrofluoric acid by adding chromium, zirconium and vanadium elements with specified proportion into the Monel K500 alloy.
The technical scheme of the invention is as follows:
the Monel K500A alloy with corrosion resistance in oxygen-containing hydrofluoric acid comprises the following improved Monel K500A alloy chemical components in percentage by weight:
64 to 66 percent of Ni, 1 to 1.5 percent of Fe, 0.5 to 1.0 percent of Mn, 0.08 to 0.12 percent of C, 2.0 to 3.0 percent of Al, 1.2 to 2.2 percent of Si, 0.6 to 0.7 percent of Ti, 4 to 5 percent of Cr, 0.5 to 0.7 percent of Zr, 0.3 to 0.6 percent of V, and the balance of Cu.
The Monel K500A alloy with corrosion resistance in the oxygen-containing hydrofluoric acid is preferably that Zr + V is more than or equal to 1.0 percent.
The Monel K500A alloy with corrosion resistance in oxygen-containing hydrofluoric acid and the preparation method of the Monel K500A alloy are as follows:
(1) preparing raw materials according to the chemical components of Monel K500A alloy for batching;
(2) melting and refining the prepared raw materials in a vacuum medium-frequency induction furnace, wherein the refining vacuum degree is 10-1 Pa, the refining temperature is 1450-1550 ℃, and the refining time is 60-80 minutes; sampling assay components, adjusting the pouring temperature to pour the electrode when the chemical components are qualified, wherein the pouring temperature is 1450-1470 ℃, the diameter of a pouring water gap is 15-18 mm, and the pouring vacuum degree is 40-20 Pa;
(3) placing the electrode into an electroslag furnace for electroslag remelting, wherein the electroslag furnace needs to have a protective atmosphere function, argon is adopted as protective gas, and pre-melted slag is selected;
(4) placing the electroslag ingot into an electric furnace for heating and forging, wherein the forging temperature is 900-1150 ℃, and cooling in water after forging; machining the bar into a finished product, and performing ultrasonic flaw detection to be qualified;
(5) the finished bar becomes a final product for use after age hardening heat treatment; the parameters of the age hardening heat treatment are as follows: the room temperature is heated to 300 +/-10 ℃ along with the furnace, homogenization heat preservation treatment is carried out for 0.5-1.5 hours, then the temperature is heated to 580-595 ℃, heat preservation is carried out for 8-16 hours, and the temperature is reduced to 400 ℃ at the cooling rate of 10-20 ℃/hour for air cooling.
The Monel K500A alloy with corrosion resistance in the oxygen-containing hydrofluoric acid has the forging ratio range of 4-6 and the final hot forging deformation amount of 20-30% in the step (4).
The design idea of the invention is as follows:
the invention must add chromium, zirconium, vanadium element of the prescribed proportion at the same time, the synergistic reaction that has among the three is: chromium forms Cr with oxygen in hydrofluoric acid containing oxygen2O3The passivation film prevents the damage of protection oxidation to the self passivation film of the MonelK500 alloy, thereby achieving the purpose of resisting the corrosion of the hydrofluoric acid containing oxygen. But Cr2O3The passivation film is easy to be gradually corroded by hydrofluoric acid, the newly added oxygen element can continuously damage the MonelK500 alloy passivation film, the single chromium element is added to have inconspicuous passivation stability of the alloy in the oxygen-containing hydrofluoric acid, and the corrosion rate of the oxygen-containing hydrofluoric acid cannot be greatly reduced even if the chromium content is increased. The addition of zirconium and vanadium can reduce the galvanic reaction of the alloy material in the hydrofluoric acid containing oxygen and strengthen the corrosion resistance of chromium oxide in the hydrofluoric acid containing oxygen, thereby stabilizing the passive film and improving the corrosion resistance of the alloy material in the hydrofluoric acid containing oxygen.
When Cr is present<At 4 wt%, the chromium forms Cr with oxygen in hydrofluoric acid containing oxygen2O3The density of the passive film is not enough to protect the damage of oxidation to the passive film of the MonelK500 alloy; when Cr is present>At 5 wt%, the residual chromium content weakens the hydrofluoric acid corrosion resistance of the alloy. When Zr<At 0.5 wt%, the reaction of zirconium and vanadium on the alloy primary battery is not weakened enough, so that the corrosion resistance of chromium oxide to hydrofluoric acid is not enough, and the alloy passivation film is not protected enough by oxygen damage, so that the corrosion resistance is not improved enough. In the same way, when V<0.3 wt%, the same as above. When Zr>When the weight percent of the chromium oxide is 0.7 percent, the past time is not too late, the reaction of the redundant zirconium, vanadium and chromium is not weakened enough, and the auxiliary chromium oxide is not enough to resist the hydrofluoric acid corrosion, so thatThe alloy passivation film is not protected enough by oxygen damage, so the corrosion resistance is not improved enough. In the same way, when V>0.6 wt%, the same as above. When Zr + V<At 1.0 wt%, the total amount of zirconium and vanadium is insufficient, so that the reaction of the alloy primary battery is not weakened sufficiently, and the corrosion resistance of the chromium oxide to hydrofluoric acid is not sufficient, so that the alloy passivation film is not protected sufficiently by oxygen, and the corrosion resistance is not improved sufficiently. Therefore, the invention controls 4-5 wt% of Cr, 0.5-0.7 wt% of Zr, 0.3-0.6 wt% of V and more than or equal to 1.0 wt% of Zr + V.
The silicon element is added into the alloy so that in the hydrofluoric acid containing oxygen, silicon and oxygen form silicon oxide to prevent further damage of oxygen to the alloy passivation film. When the silicon content is less than 1.2 wt%, the amount of silicon oxide formed is insufficient, and the alloy passivation film is not sufficiently protected. When silicon >2.2 wt%, deterioration of alloy hot workability due to silicon occurs. Therefore, the invention controls the addition of 1.2-2.2 wt% of silicon simultaneously.
In addition, when C is less than 0.08 wt%, the alloy yield strength decreases, and the alloy needs to be used under high strength conditions. When C >0.12 wt%, deterioration of hot workability of the alloy due to carbon may occur. The titanium is used for refining alloy grains and carrying out aging heat treatment to form precipitation phase to strengthen the alloy strength and optimize the cold and hot processing performance of the alloy. When Ti is less than 0.6 wt%, the refined crystal grains are insufficient and the precipitation strengthening phase is insufficient. When Ti >0.7 wt%, deterioration of hot workability of the alloy due to titanium occurs. When Mg is added, the low-temperature strength of the alloy is reduced. Therefore, the invention controls 0.08-0.12 wt% of optimized C and 0.6-0.7 wt% of optimized Ti, and avoids adding Mg element.
The invention has the advantages and beneficial effects that:
monel k500 alloy is an age-hardened high-strength Monel alloy which is the preferred material for hydrofluoric acid resistance, and has been in the past century. But poor use for corrosion resistance in hydrofluoric acid containing oxygen is limited. The invention solves the problem of improving the corrosion resistance of the alloy material in the oxygen-containing hydrofluoric acid through the following technical characteristics, and optimizes the corrosion-resistant material in the medium environment. Meanwhile, the alloy is difficult to process and easy to form cracks due to the material, so that the problem of low flaw detection qualification rate is greatly improved. The comprehensive interaction formed by strictly quantitative proportions of chromium, zirconium, vanadium, silicon and carbon balances technical indexes of hot working, grain control, strengthening phase precipitation, hydrofluoric acid corrosion resistance, oxygen-containing hydrofluoric acid corrosion resistance and the like.
(1) The invention adds chromium, zirconium and vanadium elements with strict quantitative proportion to ensure that the alloy elements of the chromium, the zirconium and the vanadium have synergistic effect, and the reaction strength of the primary battery is reduced by the zirconium and the vanadium to ensure that the chromium and the oxygen form Cr in the hydrofluoric acid containing oxygen2O3On the premise that the passive film is stable in corrosion resistance, the damage of protection oxidation to the passive film of the MonelK500 alloy is prevented, and therefore the purpose of resisting the corrosion of the hydrofluoric acid containing oxygen is achieved.
(2) According to the invention, silicon and oxygen form silicon oxide in hydrofluoric acid containing oxygen by adding a strictly quantitative silicon element, so that further damage of the alloy passivation film by the oxygen is prevented. Meanwhile, the silicon enhances the fluidity of the alloy melt, so that the crystal grains of the alloy are refined in the solidification process, the alloy forging performance is improved, and the non-destructive inspection qualified rate is increased.
(3) According to the invention, the yield strength of the material is ensured by strictly controlling the carbon content, and the flaw detection qualification rate is ensured by balancing the hot working performance.
(4) According to the invention, by controlling the content of the titanium element, the grain refinement and precipitation age hardening indexes of the material are ensured, and meanwhile, the hot processing performance is balanced to ensure the flaw detection qualification rate.
(5) The existing smelting technology for producing the MonelK500 alloy needs to add magnesium to refine grains, but the low-temperature strength of the alloy is reduced due to the magnesium residue. The alloy is sometimes used at low temperatures, so the present invention avoids the addition of magnesium by the addition of silicon instead of magnesium fining.
(6) The invention achieves the best nickel content of hydrofluoric acid resistance of the alloy by limiting the nickel content to 64-66 wt%.
Detailed Description
In the specific implementation, the conventional Monel alloy Monel K500 and the modified Monel alloy Monel K500A (examples 1-3) with the composition formula of the invention are selected for corrosion comparison experiments.
The present invention will be described in further detail below with reference to examples.
Example 1
In this example, the method for preparing the improved Monel alloy Monel K500A having corrosion resistance in a nitric acid environment containing hydrofluoric acid was as follows:
(1) the raw materials were prepared for compounding according to the invention using the chemical composition of MonelK500A alloy Table one of examples 1.
(2) Putting alloy raw materials of nickel, iron, copper and chromium into a magnesium aluminate spinel crucible of a vacuum induction melting furnace with a magnetic stirring function, vacuumizing, and starting to transmit electricity for melting when the vacuum degree reaches 9 Pa.
(3) And continuously vacuumizing until the vacuum degree of the vacuum induction melting furnace is 3Pa, and adding the raw material carbon into a crucible of the vacuum induction melting furnace through a vacuum feeding chamber. After the raw materials are melted, measuring the temperature, adjusting the temperature to 1450 ℃, and preserving the temperature for 15 minutes to obtain a melt;
(4) the melt enters a refining stage. The refining vacuum degree is changed between 10Pa and 1Pa, the refining temperature is 1450 ℃ for 40 minutes, the refining temperature is 1550 ℃ for 10 minutes, and the total refining time is 80 minutes.
(5) Adjusting the temperature to 1450 ℃, and adding silicon, ferrovanadium, aluminum, titanium and zirconium into the vacuum charging chamber after the refining is finished. Sampling is carried out after smelting for 10 minutes.
(6) And analyzing and adjusting the components of the online sampling assay, and adding manganese. And when the chemical components are qualified, adjusting the pouring temperature to 1470 ℃ to pour the electrode, wherein the diameter of a pouring nozzle is 15mm, and the pouring vacuum degree is 20 Pa.
(7) And placing the electrode into an electroslag furnace for electroslag remelting. The electroslag furnace has the function of protecting atmosphere, argon is used as protective gas, and pre-melted slag is selected.
(8) And (4) placing the electroslag ingot into an electric furnace for heating and forging. The initial forging temperature is 1150 ℃ and the final forging temperature is 900 ℃. 4, the final heat forging deformation is 25%, and the forged bar stock is cooled in water. And (3) turning the bar (peeling by adopting a lathe) to obtain a finished product, and performing ultrasonic flaw detection.
(9) And (4) performing age hardening heat treatment on the finished bar to obtain a final product for use. The parameters of the age hardening heat treatment are as follows: the room temperature is heated to 300 ℃ along with the furnace, and the homogenization and heat preservation treatment is carried out for 1 hour. The temperature is raised to 585 ℃ and the temperature is kept for 12 hours. Cooling to 400 ℃ at the cooling rate of 15 ℃/hour for air cooling.
Example 2
In this example, the method for preparing the improved Monel alloy Monel K500A having corrosion resistance in a nitric acid environment containing hydrofluoric acid was as follows:
(1) the raw materials were prepared for compounding according to the present invention using the chemical composition of MonelK500A alloy Table one of examples 2.
(2) Putting alloy raw materials of nickel, iron, copper and chromium into a magnesium aluminate spinel crucible of a vacuum induction melting furnace with a magnetic stirring function, vacuumizing, and starting to transmit electricity for melting when the vacuum degree reaches 10 Pa.
(3) And continuously vacuumizing until the vacuum degree of the vacuum induction melting furnace is 5Pa, and adding the raw material carbon into a crucible of the vacuum induction melting furnace through a vacuum feeding chamber. After the raw materials are melted, measuring the temperature, adjusting the temperature to 1450 ℃, and preserving the temperature for 15 minutes to obtain a melt;
(4) the melt enters a refining stage. The refining vacuum degree is changed between 10Pa and 1Pa, the refining temperature is 1450 ℃ for 30 minutes, the refining temperature is 1500 ℃ for 30 minutes, the refining temperature is 1550 ℃ for 10 minutes, and the total refining time is 70 minutes.
(5) Adjusting the temperature to 1450 ℃, finishing refining, adding silicon, ferrovanadium, aluminum, titanium and zirconium into the vacuum feeding chamber, smelting for 10 minutes, and then sampling.
(6) And analyzing and adjusting the components of the online sampling assay, and adding manganese. And when the chemical components are qualified, adjusting the pouring temperature to 1470 ℃ to pour the electrode, wherein the diameter of a pouring nozzle is 16mm, and the pouring vacuum degree is 25 Pa.
(7) And placing the electrode into an electroslag furnace for electroslag remelting. The electroslag furnace has the function of protecting atmosphere, argon is used as protective gas, and pre-melted slag is selected.
(8) And (4) placing the electroslag ingot into an electric furnace for heating and forging. The initial forging temperature is 1150 ℃ and the final forging temperature is 900 ℃. And 5, forging, wherein the deformation of the last hot forging is 23%, the forging temperature is 1050-900 ℃, and the forged bar stock is cooled in water. And (5) machining the bar into a finished product by using a lathe leather, and performing ultrasonic flaw detection.
(9) And (4) performing age hardening heat treatment on the finished bar to obtain a final product for use. The parameters of the age hardening heat treatment are as follows: the room temperature is heated to 300 ℃ along with the furnace, and the homogenization and heat preservation treatment is carried out for 1 hour. The temperature is raised to 585 ℃ and the temperature is kept for 12 hours. Cooling to 400 ℃ at the cooling rate of 15 ℃/hour for air cooling.
Example 3
In this example, the method for preparing the improved Monel alloy Monel K500A having corrosion resistance in a nitric acid environment containing hydrofluoric acid was as follows:
(1) the raw materials were prepared for compounding according to the present invention using the chemical composition of MonelK500A alloy Table one of examples 3.
(2) Putting alloy raw materials of nickel, iron, copper and chromium into a magnesium aluminate spinel crucible of a vacuum induction melting furnace with a magnetic stirring function, vacuumizing, and starting to transmit electricity for melting when the vacuum degree reaches 8 Pa.
(3) And continuously vacuumizing until the vacuum degree of the vacuum induction melting furnace is 2Pa, and adding the raw material carbon into a crucible of the vacuum induction melting furnace through a vacuum feeding chamber. After the raw materials are melted, measuring the temperature, adjusting the temperature to 1450 ℃, and preserving the temperature for 15 minutes to obtain a melt;
(4) the melt enters a refining stage. The refining vacuum degree is changed between 10Pa and 1Pa, the refining temperature is 1450 ℃ for 30 minutes, the refining temperature is 1550 ℃ for 10 minutes, and the total refining time is 70 minutes.
(5) Adjusting the temperature to 1450 ℃, and adding silicon, ferrovanadium, aluminum, titanium and zirconium into the vacuum charging chamber after the refining is finished. Sampling is carried out after smelting for 10 minutes.
(6) And analyzing and adjusting the components of the online sampling assay, and adding manganese. And when the chemical components are qualified, adjusting the pouring temperature to 1470 ℃ to pour the electrode, wherein the diameter of a pouring nozzle is 15mm, and the pouring vacuum degree is 22 Pa.
(7) And placing the electrode into an electroslag furnace for electroslag remelting. The electroslag furnace has the function of protecting atmosphere, argon is used as protective gas, and pre-melted slag is selected.
(8) And (4) placing the electroslag ingot into an electric furnace for heating and forging. The initial forging temperature is 1150 ℃ and the final forging temperature is 900 ℃. The forging ratio is 4.5, the deformation of the last hot forging is 25%, the forging temperature is 1050-900 ℃, and the forged bar stock is cooled in water. And (5) machining the bar into a finished product by using a lathe leather, and performing ultrasonic flaw detection.
(9) And (4) performing age hardening heat treatment on the finished bar to obtain a final product for use. The parameters of the age hardening heat treatment are as follows: the room temperature is heated to 300 ℃ along with the furnace, and the homogenization and heat preservation treatment is carried out for 1 hour. The temperature is raised to 585 ℃ and the temperature is kept for 12 hours. Cooling to 400 ℃ at the cooling rate of 15 ℃/hour for air cooling.
The conventional Monel K500 alloy and Monel K500A alloys of the compositional formulations of examples 1-3 of the present invention have the following table one:
watch 1
| wt％ | Ni | Cu | Fe | Mn | C | Al | Ti | Si | Cr | Zr | V | Mg |
| Monel K500 | 65.0 | 29.3 | 1 | 0.7 | 0.08 | 2.95 | 0.77 | 0.08 | ─ | ─ | ─ | 0.12 |
| Example 1 | 64.0 | 24.3 | 1 | 0.65 | 0.10 | 2.20 | 0.65 | 1.5 | 4.5 | 0.6 | 0.5 | ─ |
| Example 2 | 65.0 | 21.6 | 1.5 | 0.7 | 0.08 | 2.52 | 0.7 | 1.8 | 5.0 | 0.5 | 0.6 | ─ |
| Example 3 | 66.0 | 21.5 | 1.2 | 0.8 | 0.12 | 2.78 | 0.6 | 2.0 | 4.0 | 0.7 | 0.3 | ─ |
The corrosion resistance of conventional MonelK500 alloys and MonelK500A alloys formulated according to the compositions of examples 1 to 3 of the present invention in oxygen-free hydrofluoric acid is comparable to the following table two:
watch two
The corrosion resistance of conventional MonelK500 alloys and MonelK500A alloys of the composition formulas of examples 1 to 3 of the present invention in hydrofluoric acid with saturated air is compared as shown in table three below:
watch III
The corrosion resistance of conventional MonelK500 alloys and MonelK500A alloys of the composition of the invention according to examples 1 to 3 in hydrofluoric acid purged with nitrogen containing 1 vol% of oxygen versus the following table four:
watch four
The conventional MonelK500 alloy and the MonelK500A alloy with the composition formula of the invention of the examples 1-3 use oxygen content of 1 vol% and SO content2Amount 1.5 vol% of corrosion resistance in hydrofluoric acid purged with nitrogen versus temperature is given in the following table five:
watch five
The conventional MonelK500 alloy and the MonelK500A alloy with the formula of the components of the invention of the examples 1 to 3 have nondestructive testing on the following six:
watch six
The mechanical properties of conventional MonelK500 alloys and MonelK500A alloys of the present invention with the composition of examples 1-3 in the as-forged direct age-hardened state are as follows:
watch seven
| Kind of alloy | Yield strength (0.2%) Mpa | Tensile strength MPa | Elongation percentage% |
| Monel K500 | 692 | 965 | 19 |
| Example 1 | 750 | 990 | 25 |
| Example 2 | 800 | 1050 | 23 |
| Example 3 | 745 | 1000 | 25 |
The results of the examples show that the corrosion resistance of the conventional Monel K500 alloy and the Monel K500A alloy of the invention formula in oxygen-free hydrofluoric acid is basically equivalent (see Table II). The comparison of the corrosion resistance in hydrofluoric acid with saturated air shows that the corrosion rate of the Monel K500A alloy is only one fourth of that of the conventional Monel K500 alloy, and the corrosion resistance is greatly improved (see Table III). Using oxygen content of 1 vol% and SO2Comparison of corrosion resistance in hydrofluoric acid purified by nitrogen in an amount of 1.5 vol% shows that the corrosion rate of the Monel K500A alloy of the invention is only one third of that of the conventional Monel K500 alloy in a gas-phase medium and only one half of that of the conventional Monel K500 alloy in a liquid-phase medium, and the corrosion resistance is obviously improved (see Table IV). Using oxygen content of 1 vol% and SO2Comparison of corrosion resistance in hydrofluoric acid purified with nitrogen in an amount of 1.5 vol% shows that the corrosion rate of Monel K500A alloy of the invention in the gas phaseOnly one-half of the conventional Monel K500 alloy was present in the medium (see Table five). The Monel K500 alloy is a high-yield-strength alloy, and the addition of silicon, chromium, zirconium and vanadium can partially replace the aging strengthening effect of aluminum elements, so that the Monel K500A alloy formula disclosed by the invention can still meet the use requirement that the yield strength is more than 690MPa while the aluminum content is reduced. It can be seen from Table VII that the yield strength, tensile strength and elongation of the alloy of the present invention are all improved compared with those of the conventional MonelK500 alloy. Meanwhile, the titanium and carbon contents are optimized. The design result greatly improves the flaw detection qualification rate of Monel K500, and the one-time flaw detection qualification rate is improved from 70% to more than 90%, because the low aluminum content reduces the cracking tendency of alloy cold and hot processing, the material is easier to process, the yield is improved, and the flaw detection qualification rate is improved.
Claims (3)
1. The Monel K500A alloy with corrosion resistance in oxygen-containing hydrofluoric acid is characterized in that the modified Monel K500A alloy comprises the following chemical components in percentage by weight:
64-66% of Ni, 1-1.5% of Fe, 0.5-1.0% of Mn, 0.08-0.12% of C, 2.0-3.0% of Al, 1.2-2.2% of Si, 0.6-0.7% of Ti, 4-5% of Cr, 0.5-0.7% of Zr, 0.3-0.6% of V, and the balance of Cu, wherein Zr + V is more than or equal to 1.0%.
2. The Monel K500A alloy having corrosion resistance in hydrofluoric acid containing oxygen of claim 1, wherein the Monel K500A alloy is prepared by the following method:
(1) preparing raw materials according to the chemical components of Monel K500A alloy for batching;
(2) melting and refining the prepared raw materials in a vacuum medium-frequency induction furnace, wherein the refining vacuum degree is 10-1 Pa, the refining temperature is 1450-1550 ℃, and the refining time is 60-80 minutes; sampling assay components, adjusting the pouring temperature to pour the electrode when the chemical components are qualified, wherein the pouring temperature is 1450-1470 ℃, the diameter of a pouring water gap is 15-18 mm, and the pouring vacuum degree is 40-20 Pa;
(3) placing the electrode into an electroslag furnace for electroslag remelting, wherein the electroslag furnace needs to have a protective atmosphere function, argon is adopted as protective gas, and pre-melted slag is selected;
(4) placing the electroslag ingot into an electric furnace for heating and forging, wherein the forging temperature is 900-1150 ℃, and cooling in water after forging; machining the bar into a finished product, and performing ultrasonic flaw detection to be qualified;
(5) the finished bar becomes a final product for use after age hardening heat treatment; the parameters of the age hardening heat treatment are as follows: the room temperature is heated to 300 +/-10 ℃ along with the furnace, homogenization heat preservation treatment is carried out for 0.5-1.5 hours, then the temperature is heated to 580-595 ℃, heat preservation is carried out for 8-16 hours, and the temperature is reduced to 400 ℃ at the cooling rate of 10-20 ℃/hour for air cooling.
3. The Monel K500A alloy having corrosion resistance in an oxygen-containing hydrofluoric acid according to claim 2, wherein in the step (4), the forging ratio is in the range of 4 to 6, and the final hot forging deformation is 20 to 30%.
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| CN112030041B true CN112030041B (en) | 2021-11-30 |
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| JP2777319B2 (en) * | 1993-07-30 | 1998-07-16 | 財団法人電気磁気材料研究所 | Wear-resistant high-permeability alloy, method for producing the same, and magnetic recording / reproducing head |
| JPH083667A (en) * | 1994-06-15 | 1996-01-09 | Mitsubishi Materials Corp | Nickel-base alloy excellent in corrosion resistance |
| CN1095501C (en) * | 1999-06-30 | 2002-12-04 | 中国科学院金属研究所 | Alloy resisting against corrosion of hot concentrated hydrochloric acid |
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| CN109022926B (en) * | 2018-10-19 | 2020-02-21 | 江苏启迪合金有限公司 | High-temperature-resistant corrosion-resistant thermal spraying wire and preparation method thereof |
| CN110306080A (en) * | 2019-08-06 | 2019-10-08 | 北方工业大学 | A kind of new type corrosion resistant nickel-base alloy and its production technology |
| CN110564990A (en) * | 2019-10-30 | 2019-12-13 | 丹阳润泽新材料科技有限公司 | nickel-based corrosion-resistant alloy and preparation method thereof |
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