A method for preparing CuP alloy based on self-propagating-stirring injection

Abstract

The present application relates to a kind of preparation CuP alloy based on self-propagating-stirring injection method, belong to copper intermediate alloy technical field.The present application uses CuO as raw material, Al powder as reducing agent, CaO as slagging agent, KClO3 as heating agent, obtains high-temperature melt by aluminum thermal self-propagating reaction, carries out heat preservation smelting by additional induction coil, so that slag and copper melt are fully separated, and make the slag cover on copper melt, insulate air and play protective role.P high-temperature steam is carried into high-temperature copper melt inside by inert carrier gas in the form of bottom blowing or top blowing, while using asymmetric mechanical stirring, promote P steam and Cu melt in melt fully mixed and uniform, realize the rapid dispersion of P addition, and prepare CuP intermediate alloy.The present application has the advantages of short process, low energy consumption, simple operation, etc., and the copper phosphorus intermediate alloy prepared has stable properties, and the self-generated slag shell protects the outside air, so that the oxygen, nitrogen, hydrogen and other impurity elements in the alloy are effectively controlled and reduced.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of copper intermediate alloy, and particularly relates to a method for preparing CuP alloy based on self-propagating-stirring injection. BACKGROUND

[0002] CuP alloy is a copper-based intermediate alloy, and its main components are copper and phosphorus. Generally, the phosphorus content is 5% to 15%; CuP alloy has many excellent properties and applications; high strength: CuP alloy has higher strength than ordinary copper and has better mechanical properties. Wear resistance: CuP alloy has good wear resistance and can be used in high-speed mechanical devices. Corrosion resistance: CuP alloy has good corrosion resistance and performs well in some chemical media. Electrical conductivity: Since copper is a good conductor of electricity, CuP alloy has excellent electrical conductivity. Good weldability: CuP alloy can be welded with other metal materials and has good weldability.

[0003] Copper intermediate alloy refers to an alloy composed of copper and other metals or non-metallic elements. Copper intermediate alloy generally has good mechanical properties, electrical conductivity, corrosion resistance and processability, and is widely used in various industrial applications. Phosphor brass alloy has good processability and corrosion resistance, phosphor bronze alloy has high strength and hardness, and hard copper phosphor alloy has extremely high strength and hardness.

[0004] Copper phosphorus intermediate alloy has a wide range of applications in various industries. Phosphor brass alloy is usually used to manufacture pipes, valves, watch parts, ornaments, etc. Phosphor bronze alloy is usually used to manufacture ships, automobiles, electrical equipment, etc. Hard copper phosphor alloy is usually used to manufacture cutters, bearings, springs, etc.

[0005] The current CN202210130969.5 patent is a new method for processing high-conductivity and easy-to-weld phosphor copper alloy, which solves the problem of decreased electrical conductivity and thermal conductivity as the phosphorus content increases. Copper and old materials are melted and refined; phosphor copper intermediate alloy is added, and then stirring refining is carried out; the ingot is heated, and then hot extrusion, drawing and bright annealing are carried out in sequence. In the process of pure copper smelting, phosphor copper intermediate alloy and rare earth yttrium technology are added. CN202220877593.X discloses a corrosion-resistant high-strength copper phosphor alloy strip. The stability is high, the external wear resistance is improved, the aluminum alloy material of the heat-resistant layer has high strength and fire resistance, and the stability of use is improved. However, the cost is high, the process is long, and a new method for efficiently, stably and low-costly preparing CuP alloy is proposed for the current preparation method of copper phosphor alloy.

[0006] The preparation methods of copper intermediate alloy include melting method, powder metallurgy method, chemical reduction method, and electrodeposition method, and the specific preparation method depends on the alloy composition and application requirements. It is crucial to obtain a method for reducing the preparation cost and stably controlling the copper-phosphorus alloy. SUMMARY

[0007] As the mainstream method for preparing copper-phosphorus alloy, powder metallurgy has the disadvantages of high cost and high energy consumption. In order to solve this situation, the present application proposes a new method for preparing CuP alloy based on self-propagating-stirring injection: taking CuO as raw material, Al powder as reducing agent, CaO as slagging agent, and KClO3 as heating agent, a high-temperature melt is obtained through aluminum thermal self-propagating reaction, and the slag is fully separated from the copper melt through additional induction coil for heat preservation smelting. The high-temperature P vapor is carried into the high-temperature copper melt by inert carrier gas in the form of bottom blowing or top blowing, and at the same time, asymmetric mechanical stirring is adopted to promote the uniform mixing of P vapor and Cu melt in the melt, realize the rapid dispersion of P, and prepare CuP intermediate alloy. This method has the advantages of short process, low energy consumption, and simple operation, and the prepared copper-phosphorus intermediate alloy has stable properties; at the same time, the in-situ reduction of self-generated slag shell protects the outside air, so that the impurity elements such as oxygen, nitrogen and hydrogen in the alloy are effectively controlled and reduced.

[0008] A method for preparing CuP alloy based on self-propagating-stirring injection, comprising the following steps:

[0009] (1) preparing the raw materials CuO, Al powder, CaO, and KClO3 required for the reaction, drying CuO, CaO, and KClO3 in an oven at 150 DEG C for 24 hours, mixing CuO, Al powder, CaO, and KClO3 according to the proportion and ball milling to obtain a mixture;

[0010] (2) placing the mixture in a reactor, using 10-20g of magnesium powder as an igniter, and obtaining Cu melt and calcium aluminate reduction slag through CuO+Al=Cu+Al2O3 aluminum thermal reduction self-propagating reaction;

[0011] (3) adjusting and refining the alloy melt under the protection of electromagnetic induction and calcium aluminate reduction slag to obtain high-temperature Cu melt, the smelting temperature is 1500-1650 DEG C, and the time is 15-30min;

[0012] (4) through the bottom blowing or top blowing mode, the inert carrier gas carries the P vapor into the high-temperature Cu melt, at the same time, the asymmetric stirring is adopted to promote the uniform mixing of P vapor and high-temperature Cu melt, realize the rapid dispersion of P, obtain CuP alloy melt, and rapidly solidify the CuP alloy melt under the action of water cooling to obtain high-quality copper-phosphorus alloy.

[0013] Further, the CuO in step (1) is raw material, the Al powder is reducing agent, the CaO is slagging agent, and the KClO3 is heating agent, and the mass ratio is 1.0:(0.18-0.38):(0.08-0.18):(0.10-0.12).

[0014] Further, the ball milling in step (1) is that the mixture is mixed on a ball mill for 30-50 min, the particle size of the CuO powder after ball milling is ≤1000 μm, the particle size of the Al powder is ≤5 mm, the particle size of the CaO is ≤2 mm, and the particle size of the KClO3 is ≤2 mm.

[0015] Further, in the Cu melt obtained by the self-propagating reaction of the aluminothermic reduction in step (2), the mass fraction of Cu is 99.0-99.5%, and the in-situ reduction autogenous protective slag shell is obtained to isolate the melt from air, so that the contents of oxygen, nitrogen and hydrogen in the copper melt are reduced to below 0.1%, 0.001% and 0.001% respectively.

[0016] Further, the frequency of the electromagnetic field in step (3) is ≥1000 Hz, so that the temperature of the high-temperature melt is kept at 1550-1650 ℃ all the time to keep the melt in a molten state, the slag-gold separation is further promoted, and the mass fraction of inclusions is reduced from 0.5% to 0.05-0.2%.

[0017] Further, the content of the P vapor in step (4) is 0.2-0.35 g / L, the temperature of the P vapor is 200-300 ℃, the inert carrier gas is high-purity argon with a purity of ≥99.95%, the gas flow rate of the inert carrier gas is 5-20 L / min, and the inert carrier gas blowing time is 10-25 min.

[0018] Further, the asymmetric continuous stirring rate in step (4) is 90-120 r / min.

[0019] Further, the water cooling speed in step (4) is 7-9 ℃ / s.

[0020] Further, the mass fraction of P in the high-quality copper-phosphorus alloy obtained in step (4) is 5wt.%-15wt.%.

[0021] Compared with the prior art, the present application has the following advantages:

[0022] (1) The present application uses in-situ reduction of CuO to obtain a metal Cu melt, and the use of Cu powder as raw material in powder metallurgy greatly reduces the preparation cost.

[0023] (2) The present application adopts a top blowing or bottom blowing method, and utilizes inert carrier gas to carry P vapor to spray into a high-temperature copper melt, so that P is mixed with the Cu melt. Compared with the existing Cu powder and white phosphorus pressing and sintering method, the relative contact area of P and Cu is increased, the utilization rate of P is improved, and the preparation efficiency is increased by up to 38%.

[0024] (3) The present application adopts asymmetric stirring to promote the mixing of P vapor and Cu melt in the melt, so that P is rapidly dispersed and added. Compared with the symmetric mechanical vortex stirring, the dispersion of P vapor in the high-temperature Cu melt is improved, and the mixing is more uniform. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 A flowchart of a method for preparing a CuP alloy based on self-propagating-stirring spraying according to the present application. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0027] In order to facilitate the understanding of the present application, the present application will be described more fully below with reference to the related drawings, and several embodiments of the present application are given. However, the present application can be realized in many different forms, and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thorough and comprehensive.

[0028] Embodiment 1

[0029] A method for preparing a CuP alloy based on self-propagating-stirring spraying, as shown in Figure 1 , comprises the following steps:

[0030] Step 1: Material pretreatment

[0031] The target product is CuP5 alloy, and CuO powder, Al powder, slag-making agent CaO and heat-producing agent KClO3 are prepared according to the composition of the ingot. The CuO powder, slag-making agent CaO and heat-producing agent KClO3 are placed in a 150℃ oven and dried for 24h; after the material drying is completed, the CuO powder, A1 powder, KClO3 and CaO are placed in a mixing tank in a mass ratio of 1:0.28:0.13:0.10 and mixed for 40min, in order to reduce the particle size of the raw materials of the aluminothermic reduction reaction and improve the heat release, thereby improving the yield of the alloy; the mixed material is placed in the reactor, and a small amount of Mg powder is placed on the surface of the reduced material.

[0032] Step 2: self-propagating in-situ synthesis reaction

[0033] Ignite 10-20 g of magnesium powder to initiate the aluminothermic reduction reaction, continuously charge the reactor to maintain the stable progress of the self-propagating reaction, and obtain a high-temperature melt composed of Cu melt and calcium aluminate reduction slag under the protection of an inductively heated heat source;

[0034] Step 3: holding and blowing P

[0035] Continue to hold and smelt the high-temperature melt under the action of the induction coil, with a smelting temperature of 1600℃ and a smelting time of 15 min, the upper layer forms a reduction slag to isolate air, and the lower layer forms an alloy melt; adopt bottom blowing or top blowing mode, and carry out blowing of P vapor in the alloy melt through argon gas carrier, with a flow rate of 5 L / min; at the same time, adopt 100 r / min asymmetric stirring to promote the full mixing of P vapor and Cu melt in the melt, and realize the rapid dispersion of P;

[0036] Step 4: casting into ingot

[0037] After blowing P, stop stirring, turn off the induction furnace power, and perform rapid solidification at 8℃ / s under the action of water cooling to obtain CuP5 intermediate alloy, the chemical composition of the copper-phosphorus alloy obtained in the present example is: 5.25% P, 0.02% O, N content <0.01%, and the balance is Cu.

[0038] Example 2

[0039] A method for preparing CuP alloy based on self-propagating-stirring blowing, comprising the following steps:

[0040] Step 1: material pretreatment

[0041] The target product is CuP8 alloy, CuO powder, Al powder, slagging agent CaO and exothermic agent KClO3 are prepared according to the composition of the ingot, except Al powder, which is placed in a 150℃ oven for drying for 24h; after the material drying is completed, the CuO powder, A1 powder, KClO3 and CaO are placed in a mixing tank in a mass ratio of 1:0.28:0.13:0.10 and mixed for 40 min, and the mixed material is placed in the reactor, and a small amount of Mg powder is placed on the surface of the reduction material;

[0042] Step 2: self-propagating in-situ synthesis reaction

[0043] Ignite 10-20 g of magnesium powder to initiate the aluminothermic reduction reaction, continuously charge the reactor to maintain the stable progress of the self-propagating reaction, and obtain a high-temperature melt composed of Cu melt and calcium aluminate reduction slag under the protection of an inductively heated heat source;

[0044] Step 3: P blowing under insulation

[0045] The high-temperature melt is continuously kept under insulation by the induction coil, the smelting temperature is 1600℃, the smelting time is 18 min, the upper layer forms a reducing slag to isolate air, and the lower layer forms an alloy melt; P vapor is blown into the alloy melt by argon gas carrier in a bottom blowing or top blowing manner, the flow rate of argon gas is 7.5 L / min, and the blowing time is 18 min; at the same time, asymmetric stirring at 100 r / min is adopted to promote the full mixing of P vapor and Cu melt in the melt to achieve rapid dispersion of P;

[0046] Step 4: Casting into ingot

[0047] After P blowing is completed, stop stirring, turn off the induction furnace power, and perform rapid solidification at 8℃ / s under the action of water cooling to obtain CuP8 intermediate alloy. The chemical composition of the copper-phosphorus alloy obtained in this example is as follows: 7.89% P, 0.024% O, N content <0.002%, and the balance is Cu.

[0048] Example 3

[0049] A method for preparing CuP alloy based on self-propagating-stirring blowing, comprising the following steps:

[0050] Step 1: Material pretreatment

[0051] The target product is CuP10 alloy. CuO powder, Al powder, slagging agent CaO and exothermic agent KClO3 are prepared according to the composition of the ingot. Except for Al powder, all are placed in a 150℃ oven for drying for 24h. After the material drying is completed, the CuO powder, A1 powder, KClO3 and CaO are placed in a mixing tank in a mass ratio of 1:0.28:0.13:0.10 and mixed for 40 min. The mixed material is placed in the reactor, and a small amount of Mg powder is placed on the surface of the reducing material;

[0052] Step 2: In-situ synthesis reaction by self-propagation

[0053] Ignite 10-20g of magnesium powder to initiate the aluminothermic reduction reaction, continuously add material to the reactor to maintain the stable progress of the self-propagating reaction, and obtain a high-temperature melt composed of Cu melt and calcium aluminate reduction slag under the protection of an induction heating heat source;

[0054] Step 3: P blowing under insulation

[0055] The high-temperature melt is continuously kept at a temperature of 1600°C for 20 min under the action of the induction coil to form a reduced slag on the upper layer and an alloy melt on the lower layer; P vapor is sprayed into the alloy melt by means of bottom blowing or top blowing in a manner carried by argon gas, the flow rate of the argon gas is 9 L / min, and the spraying time is 20 min; meanwhile, asymmetric stirring at 110 r / min is adopted to promote the P vapor and the Cu melt to be fully mixed and uniformly distributed, so that the P is rapidly dispersed and added;

[0056] Step 4: Casting into ingots

[0057] After the spraying of P is completed, the stirring is stopped, the power of the induction furnace is turned off, and the CuP8 intermediate alloy is rapidly solidified at a rate of 8°C / s under the action of water cooling; the chemical composition of the copper-phosphorus alloy obtained in the example is as follows in terms of mass percentage: 7.89% P, 0.024% O, N content <0.002%, and the balance Cu.

[0058] Example 4

[0059] A method for preparing a CuP alloy based on self-propagating-stirring spraying, comprising the following steps:

[0060] Step 1: Material pretreatment

[0061] The target product is a CuP12 alloy, CuO powder, Al powder, slagging agent CaO and exothermic agent KClO3 are prepared according to the composition of the ingot, and all the materials except the Al powder are placed in a 150°C oven for drying for 24 h; after the material drying is completed, the CuO powder, A1 powder, KClO3 and CaO are placed in a mixing tank in a mass ratio of 1:0.28:0.13:0.10 and mixed for 40 min, and the mixed material is placed in the reactor, and a small amount of Mg powder is placed on the surface of the reduced material;

[0062] Step 2: Self-propagating in-situ synthesis reaction

[0063] 10-20 g of magnesium powder is ignited to initiate the aluminothermic reduction reaction, the material is continuously added to the reactor to maintain the stable progress of the self-propagating reaction, and a high-temperature melt composed of a Cu melt and a calcium aluminate reduction slag is obtained under the protection of the induction heating heat source;

[0064] Step 3: Keeping temperature and spraying P

[0065] The high-temperature melt is continuously kept at a temperature of 1650°C for 22 min under the action of the induction coil to form a reducing slag on the upper layer and an alloy melt on the lower layer, which is isolated from air. P vapor is sprayed into the alloy melt by argon gas carrier in a bottom or top blowing manner at a flow rate of 10 L / min for 22 min. Asymmetric stirring at 110 r / min is simultaneously adopted to promote the mixing of P vapor and Cu melt in the melt to realize the rapid dispersion of P.

[0066] Step 4: Casting into ingots

[0067] After the spraying of P is completed, the stirring is stopped, the power of the induction furnace is turned off, and the CuP12 intermediate alloy is rapidly solidified at a rate of 8°C / s under the action of water cooling. The chemical composition of the copper-phosphorus alloy obtained in the example is as follows in terms of mass percentage: 13.18% P, 0.038% O, N content <0.001%, and the balance Cu.

[0068] Example 5

[0069] A method for preparing a CuP alloy based on self-propagating-stirring spraying, comprising the following steps:

[0070] Step 1: Material pretreatment

[0071] The target product is a CuP15 alloy. CuO powder, Al powder, slagging agent CaO, and heat generating agent KClO3 are prepared according to the composition of the ingot. Except for the Al powder, all the materials are placed in a 150°C oven for drying for 24 h. After the material drying is completed, the CuO powder, Al powder, KClO3 and CaO are placed in a mixing tank in a mass ratio of 1:0.28:0.13:0.10 and mixed for 40 min. The mixed material is placed in the reactor, and a small amount of Mg powder is placed on the surface of the reducing material.

[0072] Step 2: Self-propagating in-situ synthesis reaction

[0073] 10-20 g of magnesium powder is ignited to initiate the aluminothermic reduction reaction. The material is continuously added to the reactor to maintain the stable progress of the self-propagating reaction. Under the protection of the induction heating heat source, a high-temperature melt composed of Cu melt and calcium aluminate reduction slag is obtained.

[0074] Step 3: Keeping temperature and spraying P

[0075] The high-temperature melt is continuously kept at a temperature of 1650°C for 25 min under the action of the induction coil to form a reduced slag on the upper layer and an alloy melt on the lower layer. The alloy melt is sprayed with P vapor carried by argon gas in a bottom or top blowing manner, with the flow rate of the argon gas being 10 L / min and the spraying time being 25 min. Meanwhile, the melt is stirred at a speed of 120 r / min to promote the mixing of the P vapor and the Cu melt and realize the rapid dispersion of P.

[0076] Step 4: Casting into an ingot

[0077] After the spraying of P is completed, the stirring is stopped, the power of the induction furnace is turned off, and the CuP15 intermediate alloy is rapidly solidified at a rate of 8°C / s under the action of water cooling. The chemical composition of the copper-phosphorus alloy obtained in the example is as follows: 15.52% P, 0.032% O, N content <0.001%, and the balance Cu.

Claims

1. A method for producing a CuP alloy based on self-propagating-stirring injection, characterized by, The method comprises the following steps: (1) preparing raw materials CuO, Al powder, CaO, KClO3 required for the reaction, drying CuO, CaO, KClO3 in an oven at 150°C for 24 hours, and mixing CuO, Al powder, CaO, KClO3 according to the ratio and ball milling to obtain a mixture; (2) placing the mixture in a reactor, using 10-20g of magnesium powder as an igniter, and obtaining Cu melt and calcium aluminate reduction slag through CuO+Al=Cu+Al2O3 aluminothermic reduction self-propagating reaction; (3) performing alloy melt conditioning and refining of the Cu melt under electromagnetic induction and protection of the calcium aluminate reduction slag to obtain high-temperature Cu melt, the smelting temperature being 1500-1650°C, and the time being 15-30min; (4) spraying P vapor into the high-temperature Cu melt through a bottom blowing or top blowing mode through an inert carrier gas, simultaneously using asymmetric stirring to promote the P vapor and the high-temperature Cu melt to be fully mixed and uniform, realizing rapid dispersion of P, and obtaining CuP alloy melt, and rapidly solidifying the CuP alloy melt under water cooling to obtain high-quality copper-phosphorus alloy; In step (1), the CuO is a raw material, the Al powder is a reducing agent, the CaO is a slag forming agent, and the KClO3 is a heating agent, and the mass ratio is 1.0:(0.18-0.38):(0.08-0.18):(0.10-0.12).

2. The method for producing CuP alloy based on self-propagating-stirring injection according to claim 1, characterized in that, In step (1), the ball milling is that the mixture is mixed on a ball mill for 30-50min, the particle size of the ball-milled CuO is ≤1000μm, the particle size of the Al powder is ≤5mm, the particle size of the CaO is ≤2mm, and the particle size of the KClO3 is ≤2mm.

3. The method for preparing CuP alloy based on self-propagating-stirring injection according to claim 1, characterized in that, In step (2), the Cu melt obtained through the aluminothermic reduction self-propagating reaction has a Cu mass fraction of 99.0-99.5%, and an in-situ reduction autogenous protective slag shell is generated to isolate the melt from air contact and reduce the oxygen, nitrogen and hydrogen contents in the copper melt to below 0.1%, 0.001% and 0.001% respectively.

4. The method for preparing CuP alloy based on self-propagating-stirring injection according to claim 1, characterized in that, In step (3), the frequency of the electromagnetic field of the electromagnetic induction is ≥1000Hz, the temperature of the high-temperature melt is kept at 1550-1650°C all the time to keep the melt in a molten state, the slag-gold separation is further promoted, and the inclusion mass fraction is reduced from 0.5% to 0.05-0.2%.

5. The method for preparing CuP alloy based on self-propagating-stirring injection according to claim 1, characterized in that, In step (4), the content of the P vapor is 0.2-0.35g / L, the temperature of the P vapor is 200-300°C, the inert carrier gas is high-purity argon with a purity of ≥99.95%, the gas flow rate of the inert carrier gas is 5-20L / min, and the inert carrier gas spraying time is 10-25min.

6. The method for preparing CuP alloy based on self-propagating-stirring injection according to claim 1, characterized in that, In step (4), the asymmetric continuous stirring rate is 90-120r / min.

7. The method for preparing CuP alloy based on self-propagating-stirring injection according to claim 1, characterized in that, In step (4), the water cooling speed is 7-9°C / s.

8. The method for preparing CuP alloy based on self-propagating-stirring injection according to claim 1, characterized in that, In step (4), the high-quality copper-phosphorus alloy obtained has a P mass fraction of 5 wt.%-15 wt.%.

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