Wide-range damping and corrosion-resistant Fe-Ga-based high-damping alloy and heat treatment method thereof

Abstract

The invention relates to the field of high-damping alloy materials, in particular to a wide-range damping and corrosion-resistant Fe-Ga-based high-damping alloy and a heat treatment method thereof, the chemical formula of the alloy is (Fe100-xGax) 100-yMy, M is an alloying element or a compound, x and y are mass fractions of corresponding components, x is larger than or equal to 27 and smaller than or equal to 33, and y is larger than or equal to 1 and smaller than or equal to 10. According to the method, the heat treatment process of step-by-step cooling and heat preservation is adopted, the internal stress and defects in the material are eliminated to a great extent while the proportion of the steady-state L12 phase is increased, and the damping performance and the corrosion resistance of the material are synchronously improved. The material has the advantages that the material has high damping performance in a wide amplitude range, and meanwhile, the material is endowed with excellent corrosion resistance, so that the vibration reduction requirement in corrosive environments such as ocean and the like is met.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high damping alloy materials, and particularly relates to a Fe-Ga-based high damping alloy with wide-range damping and corrosion resistance and a heat treatment method thereof. BACKGROUND

[0002] In the field of marine engineering, the underwater sonar transducer of a ship is a core device for realizing underwater detection, communication and target identification, and the material thereof needs to cope with the dual challenges of vibration interference affecting detection accuracy and corrosion erosion shortening service life. The corrosion resistance is the premise for the damping performance to play a role. If the material is corroded and aged, the damping performance will be attenuated. The damping performance is the core for the transducer to break through environmental interference. Even if the material has excellent corrosion resistance, if it cannot suppress vibration transmission, it will still reduce the signal-to-noise ratio of the sonar detection. At the same time, the damping requirement is not for a single fixed amplitude, but needs to adapt to a wide range of vibration scenarios from small amplitude to large amplitude during ship navigation. This wide amplitude characteristic is not only a result of the ship's power system and navigation environment, but also directly determines whether the transducer can break through the vibration interference to realize accurate detection of underwater targets. Therefore, the material needs to have both wide-range stable damping and excellent corrosion resistance to ensure that it can continuously suppress vibration interference and resist corrosion erosion in the complex marine environment, and provide long-term reliable working guarantee for sonar transducers and other devices.

[0003] As a new type of magnetostrictive material, the ferromagnetic Fe-Ga-based alloy has a high magnetostrictive coefficient, excellent mechanical properties, a low saturation magnetic field strength and other advantages, and can be used to make various devices such as sonar transducers and displacement sensors, and is expected to be practically applied on ships. Generally, the ferromagnetic alloy can convert mechanical vibration energy into heat energy through the irreversible movement of magnetic domain interfaces under stress, thereby showing high damping effect. Based on this characteristic, the ferromagnetic material with magnetostrictive properties generally has high damping performance. It breaks through the limitation of traditional methods of mitigating vibration noise through additional equipment, and instead utilizes its own large damping properties from the source to achieve vibration and noise attenuation, becoming an ideal functional material for various mechanical equipment and high-precision instruments. At the same time, it has a complex multi-phase structure, such as A2, B2, D03 and L12 metastable phases and L12 stable phases. The commonly seen coexisting phase structure is D03 phase and L12 phase, and the corrosion resistance of the L12 phase is stronger than that of the D03 phase. However, the response sensitivity of the D03 phase to vibration is higher than that of the L12 phase, that is, the D03 phase shows high damping effect at a lower vibration amplitude, while the L12 phase shows high damping effect at a higher vibration amplitude. By adjusting the proportion of the two phases, the wide-range damping requirement can be theoretically realized.

[0004] However, existing Fe-Ga-based alloy research focuses on optimizing a single performance, and fails to achieve a synergistic improvement in high damping performance and corrosion resistance, and lacks a systematic solution for marine corrosion environments. SUMMARY

[0005] To overcome the above problems of the prior art, the purpose of the present application is to provide a Fe-Ga-based high-damping alloy with wide-range vibration reduction and corrosion resistance and a heat treatment method thereof, which achieves a simultaneous improvement in damping performance and corrosion resistance by synergistic optimization of component design and multi-stage heat treatment process to control phase composition while eliminating material defects and internal stress.

[0006] To solve the above technical problems, the present application adopts the following technical solutions: A Fe-Ga-based high-damping alloy with wide-range vibration reduction and corrosion resistance, the chemical formula of the alloy is (Fe 100- x Ga x ) 100-y M y , wherein M is an alloying element or compound, x, y are the mass fractions of the corresponding components, 27≤x≤33, 1≤y≤10.

[0007] In a preferred embodiment of the present application, the alloy is composed of Fe, Ga and alloying elements, wherein the mass fraction of Ga is 27wt.%-33wt.%, the alloying elements are at least one of Cr, Mo, Nb, Cu, Ni, Al, La and Ce, and the total addition amount of alloying elements is 1wt.%-10wt.%.

[0008] In a preferred embodiment of the present application, the alloy is composed of Fe, Ga and compounds, the mass fraction of Ga is 27wt.%-33wt.%, the compounds are at least one of Ni3Al, Fe3Mo and Al2O3, and the total addition amount of compounds is 1wt.%-10wt.%.

[0009] In a preferred embodiment of the present application, the alloy has a D03 and L12 dual-phase structure, wherein the volume fraction of L12 phase is 75%-95%.

[0010] A heat treatment method for a Fe-Ga-based high-damping alloy with wide-range vibration reduction and corrosion resistance, comprising the following steps: After the raw materials are weighed and mixed according to the mass fraction, a vacuum arc melting furnace is used to melt and prepare a as-cast sample.

[0011] The obtained as-cast sample is subjected to first-step heat treatment, placed in a tube furnace under argon protection, and subjected to homogenization treatment to homogenize the sample.

[0012] Then, the second heat treatment is performed, and the internal stress and defects in the material are eliminated by continuous cooling and holding.

[0013] Finally, the fourth heat treatment is performed, and the alloy is transformed from the metastable D03 phase to the stable L12 phase by isothermal aging treatment in the L12 phase transformation temperature range, so that the Fe-Ga-based high-damping alloy with wide-range damping and corrosion resistance is obtained after cooling.

[0014] In the preferred embodiment of the present application, the temperature of the first heat treatment is 1100 o C-1200 o C, and the treatment time is 1h-4h.

[0015] The temperature of the second heat treatment is 900 o C-1000 o C, and the treatment time is 0.5h-1.5h.

[0016] The temperature of the third heat treatment is 800 o C-830 o C, and the treatment time is 5h-8h.

[0017] The temperature of the fourth heat treatment is 350 o C-600 o C, and the treatment time is 1h-200h.

[0018] In the preferred embodiment of the present application, the heating rate of the first to fourth heat treatments is 4 o C / min-10 o C / min, and the cooling rate is 2 o C / min-4 o C / min.

[0019] In the preferred embodiment of the present application, the cooling rate is 1 o C / min-3 o C / min.

[0020] Compared with the prior art, the present application has the beneficial effects of: 1. Compared with the prior art, the wide-range damping and corrosion-resistant Fe-Ga-based high-damping alloy of the present application has significantly improved damping performance under wide amplitude conditions, and excellent corrosion resistance, with a damping coefficient greater than 0.01, belonging to high-damping alloy, and a corrosion rate less than 0.01 mm / year, widening the application field of Fe-Ga-based alloy, especially in complex environments such as marine engineering, playing its excellent damping and noise reduction role.

[0021] 2、The preparation method of the application adopts a heat treatment process of step-by-step temperature reduction and holding, first carries out homogenization treatment of components at high temperature to prevent performance decline caused by component segregation. Then, step-by-step temperature reduction and holding is carried out to eliminate internal stress and defects in the material caused by temperature and other factors to the greatest extent. Finally, after steady-state phase transition in the phase transition region, a slow cooling mode with a certain rate is adopted instead of the traditional quenching process, which retains the steady-state phase structure and does not introduce stress caused by temperature and other factors. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 The alloy prepared in Example 1 of the application is subjected to a heat treatment process.

[0023] Figure 2 The XRD pattern of the alloy prepared in Example 1 of the application.

[0024] Figure 3 The internal friction performance test pattern of Example 1 of the application.

[0025] Figure 4 The corrosion performance test pattern of Example 1 of the application.

[0026] Figure 5 The internal friction performance test pattern of Example 2 of the application.

[0027] Figure 6 The corrosion performance test pattern of Example 2 of the application.

[0028] Figure 7 The internal friction performance test pattern of Example 3 of the application.

[0029] Figure 8 The corrosion performance test pattern of Example 3 of the application. DETAILED DESCRIPTION

[0030] The technical solutions in the embodiments of the application will be described in detail below with reference to the preferred embodiments and the accompanying drawings, and it is obvious that the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the application.

[0031] It should be noted that all the professional terms used in the application are only for the purpose of describing the specific embodiments, and are not intended to limit the protection scope of the application. Unless otherwise specified, all the materials, reagents, instruments and equipment used in the following embodiments of the application can be purchased from the market or prepared by the existing methods.

[0032] Example 1 (1) Using Fe with a purity of 99.99%, Ga with a purity of 99.99%, and Cr with a purity of 99.99% as raw materials, prepare a mixture with a nominal composition of (Fe) according to the mass ratio. 70 Ga 30 ) 94 The Cr6 alloy, comprising 59.632 g of pure Fe, 25.556 g of pure Ga, and 5.438 g of pure Cr, was prepared by melting in a vacuum arc furnace.

[0033] (2) The as-cast sample obtained in (1) is subjected to the first step of heat treatment: placed in a tube furnace under argon protection, and heated at 5 o C / min increased from room temperature to 1100 o C homogenization treatment for 2 h.

[0034] (3) The as-cast sample obtained in (2) is subjected to a second heat treatment: with 2 o C / min from 1100 o C drops to 900 o C, heat for 0.5 h to eliminate internal stress and defects inside the material caused by high-temperature cooling.

[0035] (4) The sample obtained in (3) is subjected to a third heat treatment: with 2 o C / min from 900 o C drops to 810 o At C, after holding at that temperature for 5 hours, the defects and internal stresses inside the material can be eliminated to the greatest extent possible, even below the recrystallization temperature.

[0036] (5) The sample obtained in (4) is subjected to the fourth step of heat treatment: with 2 o C / min from 810 o C drops to 480 o The phase transition from metastable D03 phase to stable L12 phase was induced by isothermal aging treatment at C for 5 h.

[0037] (6) The sample obtained in (5) is heated at 480°C. o C at 1.5 o C / min was cooled to room temperature as the furnace cooled.

[0038] Example 2 (1) Using Fe with a purity of 99.99%, Ga with a purity of 99.99%, Cr with a purity of 99.99%, and Al with a purity of 99.99% as raw materials, a mixture with a nominal composition of (Fe) is prepared according to the mass ratio. 69 Ga 31 ) 92The Cr5Al3 alloy, wherein pure Fe: 57.529g; pure Ga: 25.848g; pure Cr: 4.531g; pure Al: 2.719g, was prepared by melting in a vacuum electric arc furnace.

[0039] (2) The as-cast sample obtained in (1) is subjected to the first step of heat treatment: placed in a tube furnace under argon protection, and heated at 5 o C / min increased from room temperature to 1150 o C homogenization treatment for 2.5 hours.

[0040] (3) The as-cast sample obtained in (2) is subjected to a second heat treatment: with 2 o C / min from 1150 o C drops to 900 o C, keep warm for 1 hour to eliminate internal stress and defects inside the material caused by high-temperature cooling.

[0041] (4) The sample obtained in (3) is subjected to a third heat treatment: with 2 o C / min from 900 o C drops to 820 o At C, after holding at this temperature for 6 hours, below the recrystallization temperature, internal defects and internal stresses of the material can be eliminated to the greatest extent.

[0042] (5) The sample obtained in (4) is subjected to the fourth step of heat treatment: with 2 o C / min from 820 o C drops to 550 o C was subjected to isothermal aging treatment for 10 h to induce a phase transition from the metastable D03 phase to the steady-state L12 phase.

[0043] (6) The sample obtained in (5) is heated at 550°C. o C at 1.5 o C / min was cooled to room temperature as the furnace cooled.

[0044] Example 3 (1) Using Ga with a purity of 99.99%, Fe with a purity of 99.99%, and pure Fe3Mo as raw materials, prepare a mixture with a nominal composition of (Fe) according to the mass ratio. 68 Ga 32 ) 95 An alloy of (Fe3Mo)5, wherein pure Fe: 58.545g; pure Ga: 27.550g; pure Fe3Mo: 4.531g, was prepared by melting in a vacuum arc furnace.

[0045] (2) The as-cast sample obtained in (1) is subjected to the first step of heat treatment: placed in a tube furnace under argon protection, and heated at 5 o C / min increased from room temperature to 1200 oC homogenization treatment for 3 h.

[0046] (3) The as-cast sample obtained in step two is subjected to a second heat treatment: with 2 o C / min from 1200 o C drops to 900 o C, heat for 1.5 hours to eliminate internal stress and defects inside the material caused by high-temperature cooling.

[0047] (4) Perform a third heat treatment on the sample obtained in step three: with 2 o C / min from 900 o C drops to 810 o At C, after holding at this temperature for 7 hours, below the recrystallization temperature, internal defects and internal stresses of the material can be eliminated to the greatest extent.

[0048] (5) Perform the fourth heat treatment on the sample obtained in step four: with 2 o C / min from 810 o C drops to 580 o C is subjected to 24h isothermal aging treatment to induce a phase transition from metastable D03 phase to steady-state L12 phase.

[0049] (6) The sample obtained in step five is heated at 580°C. o C at 1.5 o C / min was cooled to room temperature as the furnace cooled.

[0050] Comparative Example 1 For comparison with this patent, the following is a description of the traditional magnetostrictive material Fe. 19 .5Co 79 Preparation process of Mn1Y0.5: (1) Using Fe with a purity of 99.99%, Co with a purity of 99.99%, Mn with a purity of 99.99%, and Y with a purity of 99.99% as raw materials, prepare a solution with a nominal composition of Fe. 19 .5Co 79 The Mn1Y0.5 alloy, wherein pure Fe: 16.98g; pure Co: 71.24g; pure Mn: 0.84g; pure Y: 0.94g, was prepared by melting in a vacuum arc melting furnace.

[0051] (2) Heat-treat the as-cast sample obtained in (1): place it in a tube furnace under hydrogen protection, and heat it at 10 °C. o C / min increased from room temperature to 880 o C homogenization treatment for 4 hours, followed by furnace cooling to 750°C. o C, then 5 o C / min decreased to 300 o C is air-cooled after being removed from the furnace.

[0052] Comparative Example 2 For comparison with this patent, the following is an example of (Fe) in Example 1. 70 Ga 30 ) 94 The preparation process of Cr6 alloy uses a traditional heat treatment process, rather than the step-down cooling and holding and low-rate cooling heat treatment process proposed in this patent. (1) Using Fe with a purity of 99.99%, Ga with a purity of 99.99%, and Cr with a purity of 99.99% as raw materials, prepare a mixture with a nominal composition of (Fe) according to the mass ratio. 70 Ga 30 ) 94 The Cr6 alloy, comprising 59.632 g of pure Fe, 25.556 g of pure Ga, and 5.438 g of pure Cr, was prepared by melting in a vacuum arc furnace.

[0053] (2) The as-cast sample obtained in (1) is subjected to the first step of heat treatment: placed in a tube furnace under argon protection, and heated at 5 o C / min increased from room temperature to 1150 o C homogenization treatment for 2.5 hours.

[0054] (3) The sample obtained in (2) is subjected to a second heat treatment: placed in an argon-protected tube furnace and heated to 500°C. o C / min increased from room temperature to 480 o The phase transition from metastable D03 phase to stable L12 phase is induced by isothermal aging treatment at C for 5 hours.

[0055] (4) The sample obtained in (3) is subjected to water quenching.

[0056] Results Analysis The damping coefficient Q of the material in Comparative Example 1 -1 In 6×10 -4 ~5×10 -3 Its resistance to seawater corrosion is around 0.01, indicating a certain degree of resistance. However, its damping performance is poor and does not meet the requirements for high-damping alloys (Q). -1 >0.01), which cannot achieve the effect of vibration reduction. The damping coefficient Q of the material in Comparative Example 2 is... -1 In 6×10 -3 ~1.5×10 -2 The existing alloy exhibits a seawater corrosion rate of around 0.05, indicating poor seawater corrosion resistance. Furthermore, its damping coefficient remains low, failing to achieve a satisfactory vibration reduction effect. In contrast, the alloy prepared in this application possesses a damping coefficient Q... -1 In 1×10 -2 ~3×10 -2The range of damping coefficients is greater than 0.01, which indicates that it belongs to high-damping alloys. The corrosion rate is less than 0.01 mm / year, which can simultaneously take into account both damping performance and seawater corrosion resistance.

[0057] The alloys prepared in Examples 1-3 were subjected to internal friction performance tests (using a multifunctional inverted pendulum internal friction apparatus) and corrosion performance tests (using the weight loss test method, with the corrosion solution being a 3.5% NaCl solution by mass). The test results are attached. Figures 3-8 As shown in the attached figures, the alloy prepared in this application exhibits a damping coefficient greater than 0.01 under a wide amplitude range, classifying it as a high-damping alloy. The corrosion rate is less than 0.01 mm / year, meeting the application requirements of corrosive environments such as marine environments.

[0058] in: Figure 1 The figure shows the heat treatment process of the alloy prepared in Example 1 of the present invention. As can be seen from the figure, the heat treatment process involves homogenization at high temperature, followed by a step-by-step cooling and holding method, and finally slow cooling at a certain rate in the furnace.

[0059] Figure 2 The image shows the XRD pattern of the alloy prepared in Example 1 of this invention. As can be seen from the image, the prepared sample has obvious diffraction peaks of DO3 phase and L12 phase, and the sample is a composite structure of DO3 phase and L12 phase.

[0060] Figure 3 , Figure 5 and Figure 7 The figures show the internal friction performance test results of Embodiments 1, 2, and 3 of this invention. As can be seen from the figures, the internal friction value of the sample gradually increases with the increase of strain amplitude. At the same time, the internal friction value is always greater than 0.01 under the condition of the entire amplitude range, which is within the high damping range.

[0061] Figure 4 , Figure 6 and Figure 8 The figures show the corrosion performance test results for Examples 1, 2, and 3 of this invention. As can be seen from the figures, the mass of the sample gradually decreases with the extension of immersion time, but the rate of decrease gradually slows down with the extension of time. The corrosion rate values ​​calculated from this are all less than 0.01 mm / year, which meets the application conditions of corrosive environments such as the ocean.

[0062] It should be noted that when numerical ranges are involved in this invention, it should be understood that both endpoints of each numerical range and any value between the two endpoints can be selected. Since the steps and methods used are the same as in the embodiments, preferred embodiments are described here to avoid redundancy. Although preferred embodiments of the invention have been described, those skilled in the art, once they understand the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments as well as all changes and modifications falling within the scope of this invention.

[0063] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A wide-range damping and corrosion-resistant Fe-Ga-based high-damping alloy, characterized in that, The chemical formula of the alloy is (Fe 100-x Ga x ) 100-y M y , wherein M is an alloying element or compound, x, y are the mass fractions of the corresponding components, 27≤x≤33, 1≤y≤10; The alloying elements are at least one of Cr, Mo, Nb, Cu, Ni, Al, La, Ce; The compound is at least one of Ni3Al, Fe3Mo, Al2O3.

2. The wide field damping and corrosion resistant Fe-Ga based high damping alloy according to claim 1, characterized in that, The alloy has a D03 and L12 dual-phase structure, wherein the volume fraction of the L12 phase is 75%-95%.

3. The heat treatment method of wide field damping and corrosion resistant Fe-Ga based high damping alloy according to claim 1, characterized in that, The method comprises the following steps: The raw materials are weighed and mixed according to the mass fraction, and then smelted to prepare a cast sample; The obtained cast sample is subjected to a first heat treatment to homogenize the sample; A second heat treatment is performed to eliminate internal stress and internal defects of the material caused by high-temperature cooling; A third heat treatment is continuously performed to reduce the sample to below the recrystallization temperature and above the L12 phase transition temperature for heat preservation; Finally, a fourth heat treatment is performed to make the alloy transform from the metastable D03 phase to the stable L12 phase, and a wide-range damping and corrosion-resistant Fe-Ga-based high-damping alloy is obtained after cooling.

4. The heat treatment method of wide-range damping and corrosion-resistant Fe-Ga based high-damping alloy according to claim 3, characterized in that, The temperature of the first heat treatment is 1100 o C-1200 o C, the treatment time is 1h-4h; The temperature of the second heat treatment is 900 o C-1000 o C, the treatment time is 0.5h-1.5h; The temperature of the third heat treatment is 800 o C-830 o C, the treatment time is 5h-8h; The temperature of the fourth heat treatment is 350 o C-600 o C, and the treatment time is 1 h-200 h.

5. The heat treatment method of wide-range damping and corrosion-resistant Fe-Ga based high-damping alloy according to claim 3, characterized in that, The heating rate of the first to fourth steps is 4 o C / min-10 o C / min, and the cooling rate is 2 o C / min-4 o C / min.

6. The heat treatment method of wide-range damping and corrosion-resistant Fe-Ga based high-damping alloy according to claim 3, characterized in that, The cooling rate of the cooling is 1 o C / min-3 o C / min.

7. Application of the wide-range damping and corrosion-resistant Fe-Ga-based high-damping alloy of claim 1 in the preparation of damping and noise reduction equipment in complex corrosion environments of marine engineering.

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