Amorphous alloy shaped charge liner and preparation method thereof

Abstract

The invention relates to an amorphous alloy shaped charge liner and a preparation method thereof, the chemical formula of the amorphous alloy shaped charge liner is (Cu47Zr45Al8) aMb, a and b are molar ratios, and M is a rare earth element; the preparation method comprises the following steps of burdening, smelting, material ball acid pickling, die casting, cooling treatment and computer digital control processing. Compared with the prior art, the amorphous alloy shaped charge liner has both thermal stability and forming ability.

Description

Technical Field

[0001] The invention relates to the technical field of amorphous alloy materials, and discloses an amorphous alloy medicine liner and a preparation method thereof. Background Art

[0002] For a long time, shaped charge warheads have been widely used in various fields, such as oil exploration, penetration of fortifications, etc. The liner is the core component of the shaped charge warhead, and the performance of its material is the key factor that determines the armor-piercing ability of the shaped charge warhead. After the high-energy explosive is detonated, the liner is crushed to form a jet, which penetrates and damages the target. The longer the jet length, the greater the density, the higher the speed, and the better the continuity, the stronger the armor-piercing ability. Therefore, the continuity, speed and length of the jet have an important influence on the armor-piercing performance of the shaped charge warhead against the target.

[0003] Amorphous alloy liners have high density and high sound velocity, which helps to improve the penetration ability of the jet. At the same time, the strength, hardness and elastic limit of amorphous alloys are generally better than those of traditional materials, which makes the liner less likely to break during the explosion. On the other hand, amorphous alloys exhibit good plasticity and toughness under high-speed impact, which helps to form a high-speed and stable metal jet during the explosion. Under high strain rate conditions, amorphous alloys can still maintain a certain plastic deformation ability, reducing the risk of jet breakage.

[0004] Therefore, in view of the above research background, it should be a natural advantage to develop an amorphous alloy liner material suitable for large-scale promotion and use, which takes into account thermal stability, forming ability, mechanical properties and corrosion resistance. Summary of the invention

[0005] The first technical problem to be solved by the present invention is to provide an amorphous alloy liner with good thermal stability in view of the above technical status.

[0006] The second technical problem to be solved by the present invention is to provide a method for preparing an amorphous alloy liner in view of the above technical status.

[0007] The technical solution adopted by the present invention to solve the above-mentioned first technical problem is: an amorphous alloy liner, characterized in that: the chemical formula of the amorphous alloy liner is (Cu 47 Zr 45 Al8) a M b , where a and b are molar ratios, and M is a rare earth element. Adding trace amounts of rare earth elements to the Cu-Zr-Al amorphous alloy system can purify the alloy melt. The addition of rare earth elements can effectively increase the degree of disorder and mixing enthalpy between components, and improve the thermal stability and amorphous forming ability of the amorphous alloy system; in addition, amorphous alloys have high strength, high hardness, and good corrosion resistance.

[0008] Preferably, a and b satisfy: 96≤a≤100, 0≤b≤4. a and b are the composition ranges of rare earth element microalloying. When a is less than 96, the melt cannot be purified. When a is within the range of 96≤a≤100, the cost of raw materials can be reduced while the degree of chaos of the alloy system can be improved. On the other hand, when the content is greater than b, the atoms may form an orderly arrangement and form intermetallic compounds, which will affect the amorphous forming ability.

[0009] Preferably, the rare earth element M is one or more of Y, Dy, Gd and Er.

[0010] The technical solution adopted by the present invention to solve the above second technical problem is: a method for preparing an amorphous alloy liner, characterized in that it comprises the following steps:

[0011] S1. Ingredients: weigh the raw materials according to the weight percentage of each component;

[0012] S2, smelting: the raw materials prepared in step S1 are smelted into pellets by vacuum induction;

[0013] S3, pickling of the balls: pickling the balls;

[0014] S4, die casting: the ball after pickling in step S3 is subjected to vacuum pressure casting to obtain a casting;

[0015] S5, cooling treatment: placing the casting obtained in step S4 into water for cooling to obtain a casting mold;

[0016] S6, digital processing: The casting obtained in step S5 is processed by computer digital control to obtain an amorphous alloy liner.

[0017] Preferably, in step S1, the weighed raw material is placed in an ultrasonic cleaner, cleaned with alcohol for 10 to 15 minutes, and then placed in a drying furnace and kept warm at 200° C. for 20 minutes.

[0018] Preferably, in step S2, after the raw materials prepared in step S1 are placed in a vacuum induction furnace, a two-stage mechanical pump is used to evacuate the raw materials and then an inert gas is introduced for smelting; the smelting power is 15-20kw, the smelting temperature is 1300-1500°C, and the holding time is 10-15min. During the casting process, a de-impurity net is added to filter the impurities in the melt; the amorphous alloy master alloy balls are prefabricated by vacuum induction melting, and the de-impurity net is added during the smelting process to further improve the purity of the raw materials and avoid crystallization caused by the introduction of impurity elements into the matrix.

[0019] Preferably, in step S3, the pickling solution is a dilute nitric acid aqueous solution with a mass fraction of 10% to 15%, and the pickling time is 20 to 40 seconds.

[0020] Preferably, in step S4, the mold used is a vacuum die-casting liner mold; the vacuum die-casting liner mold is preheated and kept warm before die-casting, and the preheating temperature is 180-200°C.

[0021] Preferably, in step S4, during die casting, the pickled ball obtained in step S3 is placed in the induction coil of the vacuum die casting machine for melting, and the coil melts the alloy through the induction current, the heating power of the induction coil is 3-6kw, and the melting temperature is 1000-1200℃; the pressure of the die casting injection is 10-12MPa, the injection rate is 0.7-1.8m / s, and the injection time is 1.8-2.2s. The pressure casting method is adopted to promote filling, and the introduction of pressure is conducive to increasing the cooling rate of the melt in the mold and improving the amorphous forming ability; the pressure casting technology can make the material nearly net-shaped, reduce the amount of subsequent processing, and improve the material utilization rate. At the same time, parts with complex shapes and clear contours can be manufactured, which provides greater flexibility for design, and has high production efficiency and high dimensional accuracy, excellent surface quality, high material utilization rate, and is more suitable for large-scale production. The vacuum die casting process has the advantages of high forming efficiency, short production cycle and high precision. In addition, amorphous alloys need to be cooled quickly to form an amorphous structure, which can be met under die casting conditions.

[0022] Preferably, in step S2, the ball mold used is an integrated serial mold, the mass of a single ball obtained by smelting is 98 to 102 g, and the number of balls obtained by smelting per furnace is 100 to 120.

[0023] Compared with the prior art, the advantages of the present invention are:

[0024] ① Organizational uniformity: The organization of amorphous alloys is long-range disordered amorphous, with no grains, grain boundaries, or other common defects in crystalline materials, which is equivalent to infinite grain refinement;

[0025] ② Amorphous alloys have superplastic characteristics in the supercooled liquid phase region, and have deformation characteristics that are completely different from those of conventional crystalline materials, which is conducive to forming a continuous and stable metal jet and improving penetration capability;

[0026] ③ The elements of the amorphous alloy liner include Zr, Cu, Al and rare earth elements, so as to optimize the forming ability, thermal stability, mechanical properties and corrosion resistance of the amorphous alloy; adding trace rare earth elements to the Cu-Zr-Al amorphous alloy system can purify the alloy melt, and the addition of rare earth elements can effectively increase the disorder and mixing enthalpy between components, and improve the thermal stability and amorphous forming ability of the amorphous alloy system. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 X-ray diffractometer (XRD) images of Examples 1-4. DETAILED DESCRIPTION

[0028] The present invention is further described in detail below with reference to the embodiments.

[0029] Example 1

[0030] The alloy composition of the amorphous alloy material of this embodiment is: (Cu 47 Zr 45 Al8) 98 Y2 (components are all molar ratios, the same below)

[0031] S1. Ingredients: Ingredients are prepared according to the composition of the amorphous alloy material. Industrial-grade sponge zirconium, electrolytic copper, pure aluminum and rare earth element Y are prepared according to the composition ratio. The raw materials are placed in an ultrasonic cleaner and cleaned with alcohol for 10 minutes. Then, the raw materials are placed in a drying furnace and kept at 200°C for 20 minutes. The dried raw materials are loaded into an induction melting furnace.

[0032] S2. Induction melting of master alloy balls: The alloy raw materials prepared in step S1 are melted into polygonal balls by vacuum induction. The dried raw materials are placed in a vacuum induction furnace, evacuated by a two-stage mechanical pump, and inert gas is introduced for melting. The ball mold used is an integrated tandem mold. The mass of a single ball obtained by melting is about 100g, and the number of balls obtained by melting in each furnace is 100-120. The melting power is 15kw, the melting temperature is 1350°C, and the insulation time is 10min.

[0033] S3, pickling of the pellets: the pellets obtained in step S2 are pickled, the pickling solution is a dilute nitric acid aqueous solution with a mass fraction of 10%, and the pickling time is 25 seconds.

[0034] S4, die casting of amorphous alloy liner: the ball obtained in step S3 is formed by vacuum pressure casting, the mold preheating temperature is 200°C, the vacuum degree of the die casting system is 5Pa, and inert gas argon is introduced for protection. The induction coil heating power is 5kw, and the melting temperature is 1100°C. The injection pressure of the die casting process is 10MPa, the injection rate is 0.9m / s, and the injection time is 2s.

[0035] S5, cooling treatment: putting the casting obtained in step S4 into water to cool it, obtaining a casting mold, and reducing the casting stress.

[0036] S6. Digital processing of castings: The casting obtained in step S5 is processed by computerized numerical control (CNC) to obtain an amorphous alloy liner sample, thereby removing burrs and flow channels.

[0037] The method of removing burrs and flow channels by CNC machining is a conventional method in the art and will not be described in detail.

[0038] Example 2

[0039] The alloy composition of the amorphous alloy material of this embodiment is: (Cu 47 Zr 45 Al8)qEr2.

[0040] S1. Raw material batching: According to the composition of the amorphous alloy material, industrial-grade sponge zirconium, electrolytic copper, pure aluminum and rare earth element Er are batched according to the composition ratio and put into an ultrasonic cleaner, cleaned with alcohol for 15 minutes, and then put into a drying furnace at 200°C for 20 minutes. The dried raw materials are loaded into an induction melting furnace.

[0041] S2. Induction melting of master alloy balls: The alloy raw material prepared in step S1 is melted into polygonal balls by vacuum induction. The dried raw material is placed in a vacuum induction furnace, evacuated by a two-stage mechanical pump, and inert gas is introduced for melting. The ball mold used is an integrated tandem mold. The mass of a single ball obtained by melting is about 100g. The number of balls obtained by melting in each furnace is 100-120. The melting power is 12kw, the melting temperature is 1300°C, and the insulation time is 15min.

[0042] S3, pickling of the pellets: the pellets obtained in step S2 are pickled with a 10% dilute nitric acid aqueous solution for 20 seconds.

[0043] S4, die casting of amorphous alloy liner: the ball obtained in step S3 is formed by vacuum pressure casting, the mold preheating temperature is 200°C, the vacuum degree of the die casting system is 2Pa, and inert gas argon is introduced for protection. The coil heating power is 4kw, and the melting temperature is 1100°C. The injection pressure of the die casting process is 10MPa, the injection rate is 1.2m / s, and the injection time is 2s.

[0044] S5 cooling treatment: placing the casting obtained in step S4 into water for cooling to obtain a casting mold and reduce casting stress.

[0045] S6 casting digital processing: the casting obtained in step S5 is processed by CNC to prepare an amorphous alloy liner sample.

[0046] Example 3

[0047] The alloy composition of the amorphous alloy material of this embodiment is: (Cu 47 Zr 45 Al8) 98 Gd2.

[0048] S1. Raw material batching: According to the composition of the amorphous alloy material, industrial-grade sponge zirconium, electrolytic copper, pure aluminum and rare earth element Gd are placed in an ultrasonic cleaner according to the composition ratio, cleaned with alcohol for 12 minutes, and then placed in a drying furnace at 200° C. for 20 minutes. The dried raw materials are loaded into an induction melting furnace.

[0049] S2. Induction melting of master alloy balls: The alloy raw material prepared in step S1 is melted into polygonal balls by vacuum induction. The dried raw material is placed in a vacuum induction furnace, evacuated by a two-stage mechanical pump, and inert gas is introduced for melting. The ball mold used is an integrated tandem mold. The mass of a single ball obtained by melting is about 100g. The number of balls obtained by melting in each furnace is 100-120. The melting power is 18kw, the melting temperature is 1400°C, and the insulation time is 12min.

[0050] S3, pickling of the pellets: the pellets obtained in step S2 are pickled with a 10% dilute nitric acid aqueous solution for 25 seconds.

[0051] S4, die casting of amorphous alloy liner: the ball obtained in step S3 is formed by vacuum pressure casting, the mold preheating temperature is 180°C, the vacuum degree of the die casting system is 10-1Pa, and inert gas argon is introduced for protection. The coil heating power is 6kw, and the melting temperature is 1200°C. The injection pressure of the die casting process is 12MPa, the injection rate is 1.6m / s, and the injection time is 2s.

[0052] S5, cooling treatment: putting the casting obtained in step S4 into water to cool it, obtaining a casting mold, and reducing the casting stress.

[0053] S6. Digital processing of castings: The casting obtained in step S5 is processed by CNC to prepare an amorphous alloy liner sample.

[0054] Example 4

[0055] The alloy composition of the amorphous alloy material of this embodiment is: (Cu 47 Zr 45 Al8) 96 Dy4.

[0056] S1. Raw material batching: According to the composition of the amorphous alloy material, industrial-grade sponge zirconium, electrolytic copper, pure aluminum and rare earth element Dy are placed in an ultrasonic cleaner according to the composition ratio, cleaned with alcohol for 15 minutes, and then placed in a drying furnace at 200° C. for 20 minutes. The dried raw materials are loaded into an induction melting furnace.

[0057] S2. Induction melting of master alloy balls: The alloy raw material prepared in step S1 is melted into polygonal balls by vacuum induction. The dried raw material is placed in a vacuum induction furnace, evacuated by a two-stage mechanical pump, and inert gas is introduced for melting. The ball mold used is an integrated tandem mold. The mass of a single ball obtained by melting is about 100g. The number of balls obtained by melting in each furnace is 100-120. The melting power is 20kw, the melting temperature is 1500°C, and the insulation time is 15min.

[0058] S3, pickling of the pellets: the pellets obtained in step S2 are pickled with a 10% dilute nitric acid aqueous solution for 40 seconds.

[0059] S4, die casting of amorphous alloy liner: the ball obtained in step S3 is formed by vacuum pressure casting, the mold preheating temperature is 190°C, the vacuum degree of the die casting system is 20Pa, and inert gas argon is introduced for protection. The induction coil heating power is 5kw, and the melting temperature is 1150°C. The injection pressure of the die casting process is 11MPa, the injection rate is 1.8m / s, and the injection time is 2s.

[0060] S5, cooling treatment: putting the casting obtained in step S4 into water to cool it, obtaining a casting mold, and reducing the casting stress.

[0061] S6. Digital processing of castings: The casting obtained in step S5 is processed by CNC to prepare an amorphous alloy liner.

[0062] The above specific examples are further detailed descriptions of the present invention, and it cannot be determined that the specific implementation methods of the present invention are limited to these. Without departing from the alloy composition range and pressure casting process proposed by the present invention, appropriate composition adjustments and improvements can be made, but they should all be deemed to fall within the scope of protection of the claims submitted by the present invention.

[0063] The amorphous alloy liner prepared in Example 1-4 was characterized by X-ray diffractometer (XRD). Figure 1 The thermal stability of the amorphous alloy liner prepared in Example 1-4 was characterized by differential scanning calorimetry (DSC), as shown in Table 1.

[0064] Table 1 Thermal stability of the examples

[0065] sample <![CDATA[T g / K]]> <![CDATA[T x / K]]> <![CDATA[T m / K]]> <![CDATA[T l / K]]> <![CDATA[ΔT x / K]]> <![CDATA[T rg ]]> γ Example 1 714.2 770.1 1103.6 1145.9 55.9 0.623 0.414 Example 2 715.2 765.9 1105.1 1142.5 50.7 0.626 0.412 Example 3 713.3 772.2 1101.1 1167.2 66.2 0.621 0.425 Example 4 733.2 785.8 1135.9 1179.8 52.6 0.621 0.411

[0066] It can be seen from Table 1 that the T g 713~734K, T x 765~789K, T m 1100~1136K, T l1140~1180K, ΔT x 50~68K, T rg is 0.62-0.63, and γ is 0.41-0.43. Therefore, it can be seen that the glass transition temperature, crystallization start temperature, melting temperature and liquidus temperature of the amorphous alloy liner are all high, and the amorphous alloy liner has good thermal stability and is not easy to decompose at low temperatures.

Claims

1. An amorphous alloy liner, characterized in that: The chemical formula of the amorphous alloy liner is (Cu 47 Zr 45 Al8) a M b , where a and b are molar ratios; M is a rare earth element.

2. The amorphous alloy liner according to claim 1, characterized in that: The a and b satisfy: 96≤a≤100, 0≤b≤4.

3. The amorphous alloy liner according to claim 1, characterized in that: The rare earth element M is one or more of Y, Dy, Gd and Er.

4. A method for preparing the amorphous alloy liner according to any one of claims 1 to 3, characterized in that: The following steps are involved: S1. Ingredients: weigh the raw materials according to the weight percentage of each component; S2, smelting: the raw materials prepared in step S1 are smelted into pellets by vacuum induction; S3, pickling of the balls: pickling the balls; S4, die casting: the ball after pickling in step S3 is subjected to vacuum pressure casting to obtain a casting; S5, cooling treatment: placing the casting obtained in step S4 into water for cooling to obtain a casting mold; S6, digital processing: The casting obtained in step S5 is processed by computer digital control to obtain an amorphous alloy liner.

5. The method for preparing an amorphous alloy liner according to claim 4, characterized in that: In step S1, the weighed raw materials are placed in an ultrasonic cleaner, cleaned with alcohol for 10 to 15 minutes, and then placed in a drying furnace and kept at 200° C. for 20 minutes.

6. The method for preparing an amorphous alloy liner according to claim 4, characterized in that: In step S2, the raw materials prepared in step S1 are placed in a vacuum induction furnace, evacuated by a two-stage mechanical pump, and then inert gas is introduced for smelting; the smelting power is 15-20kw, the smelting temperature is 1300-1500°C, and the insulation time is 10-15min.

7. The method for preparing an amorphous alloy liner according to claim 4, characterized in that: In step S3, the pickling solution is a dilute nitric acid aqueous solution with a mass fraction of 10% to 15%, and the pickling time is 20 to 40 seconds.

8. The method for preparing an amorphous alloy liner according to claim 4, characterized in that: In step S4, the mold used is a vacuum die-casting liner mold; the vacuum die-casting liner mold is preheated and kept warm before die-casting, and the preheating temperature is 180-200°C.

9. The method for preparing an amorphous alloy liner according to claim 4 or 8, characterized in that: In step S4, during die casting, the pickled ball obtained in step S3 is placed in the induction coil of the vacuum die-casting machine for melting. The coil melts the alloy through the induced current. The heating power of the induction coil is 3 to 6 kW, and the melting temperature is 1000 to 1200°C. The injection pressure of the die casting is 10 to 12 MPa, the injection rate is 0.7 to 1.8 m / s, and the injection time is 1.8 to 2.2 s.

10. The method for preparing an amorphous alloy liner according to claim 4, characterized in that: In step S2, the ball mold used is an integrated serial mold, the mass of a single ball obtained by smelting is 98-102 g, and the number of balls obtained by smelting per furnace is 100-120.

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