A process for preparing phosphor bronze rods using phosphonate-amide composite purifier as a quenching aid.

Abstract

This invention relates to a process for preparing phosphorus copper rods using a phosphonate-amide composite purifying agent as a quenching aid, belonging to the field of non-ferrous metallurgical technology. The invention involves mixing phosphorus pentoxide and sodium carbonate to form a molten salt, cooling and grinding it, then adding it along with scrap copper to an alumina crucible for rapid heating. Compressed air is blown in, and after holding at this temperature and allowing it to settle, slag is removed. A mixed gas is then blown into the melt for reduction refining. Calcium boride is added to the melt for further refining. The refined copper liquid is then continuously cast and rolled. The continuously cast and rolled phosphorus copper rods are rapidly immersed in a quenching aid solution for quenching. The quenched phosphorus copper rods are then blown dry and baked to obtain high-conductivity phosphorus copper rods. The high-purity phosphorus copper rods prepared by this invention exhibit excellent performance in key indicators such as copper content, phosphorus content, and conductivity, achieving the expected high purity and high conductivity requirements.

Description

Technical Field

[0001] This invention relates to the field of non-ferrous metal metallurgy technology, and in particular to a process for preparing phosphor bronze rods using phosphonate-amide composite purifying agent as a quenching aid. Background Technology

[0002] In industries such as wire and cable manufacturing, copper rods are an important raw material, requiring high purity and conductivity. Traditional copper smelting often employs a complex method of oxidation-reduction, electrolytic refining, and cathode copper purification. This method first oxidizes and removes some oxygen-loving and volatile metals, then electrolytically refines to obtain cathode copper. After melting the cathode copper, refining agents are added for purification before rod making. Although this method can achieve a copper purity of over 99.95% and good electrical and mechanical properties, the process is lengthy and energy-intensive.

[0003] Chinese Patent CN202028899U: Includes a metal induction furnace and an upward continuous casting machine. The crystallizer of the upward continuous casting machine extends into the induction furnace to draw molten copper upward. The system is characterized by further including a straightening machine, a continuous extrusion press, and a continuous stamping forging machine. The copper rod cast from the upward continuous casting machine is drawn to the straightening machine through the outlet of the upward continuous casting machine. The copper rod straightened by the straightening machine is drawn to the continuous extrusion press through the outlet of the straightening machine. The copper rod is extruded into the required size in the continuous extrusion press and is extruded into a fine-grained state both inside and out. It is then drawn to the continuous stamping forging machine.

[0004] Chinese Patent CN100482822C: A method for preparing phosphorus copper alloy rods, which involves continuous melting, alloying, heat preservation storage, continuous casting, and continuous rolling to produce phosphorus copper alloy rods with a phosphorus content of 400-650 PPM and an oxygen content of 10-50 PPM.

[0005] With the increasing demand for scrap copper recycling, some wire and cable companies have attempted to produce recycled copper rods using some scrap copper under traditional continuous casting processing conditions. However, because the impurity content of recycled copper exceeds that of virgin copper, the resulting electrical copper rods not only have lower yields but also exhibit inferior physical properties compared to virgin copper, such as resistivity, elongation, and tensile strength. Furthermore, the internal structure is prone to defects like porosity and air bubbles. Especially in the preparation of high-conductivity, high-purity phosphorus copper rods, existing processes struggle to effectively remove impurities from the scrap copper while precisely controlling the content of elements like phosphorus to meet the requirements for high conductivity and other performance characteristics. Summary of the Invention

[0006] To address the aforementioned problems, this invention provides a process for preparing phosphor bronze rods using a phosphonate-amide composite purifier as a quenching aid. The operation steps are as follows, in parts by weight:

[0007] S1 Oxidation Refining: Mix 4.5-7.5 parts of phosphorus pentoxide and 55-75 parts of sodium carbonate, and boil them at 800-900℃ to make a uniform molten salt. After cooling and grinding the molten salt, mix it evenly with 150-200 parts of scrap copper and add it to a corundum crucible. Place the crucible in a sealed heating furnace and heat it rapidly to 1150-1220℃. Start blowing compressed air in, and stop blowing after 40-60 minutes. After holding the temperature and letting it stand for 15-20 minutes, remove the slag, take a sample, and cool it.

[0008] S2 reduction refining: At a temperature of 1150-1220℃, a mixed gas is bubbled into the melt obtained from S1; after 20-30 minutes, the gas flow is stopped, and the temperature is maintained for 10-15 minutes.

[0009] S3 refining agent refining: At a temperature of 1150-1220℃, add 0.05-0.2 parts of calcium boride to the melt obtained from S2, and at the same time blow in high-purity argon gas to stir the melt; after 20-30 minutes, stop the gas flow, let it stand and keep warm for another 20-30 minutes, remove the slag, take a sample, and cool.

[0010] S4 casting and molding: After stirring the refined copper liquid for 5-10 minutes, it is continuously cast and rolled.

[0011] S5 quenching treatment:

[0012] Preparation of quenching medium: Add 0.3-0.8 parts of phosphonate-amide composite purifier to 30-40 parts of deionized water and stir until completely dissolved to form a uniform quenching aid solution;

[0013] Quenching operation: The phosphor bronze rod after continuous casting and rolling is quickly immersed in the above quenching aid solution, and the cooling rate is controlled at 40-80℃ / s, so that the phosphor bronze rod is cooled to 90-100℃ within 1-3 minutes.

[0014] S6 Post-treatment: Remove the quenched phosphor bronze rod from the quenching aid solution, blow dry the residual solution on the surface with compressed air, and dry it at 120-150℃ for 20-30 minutes to obtain a high conductivity phosphor bronze rod.

[0015] Preferably, the compressed air flow rate of S1 is 0.4-0.5 L / min, and the pressure is 0.3-0.4 MPa.

[0016] Preferably, the mixed gas of S2 is carbon monoxide and nitrogen in a volume ratio of 1:9.

[0017] Preferably, the flow rate of the mixed gas in S2 is 0.2-0.3 L / min, and the pressure is 0.2-0.3 MPa.

[0018] Preferably, the flow rate of high-purity argon gas in S3 is 0.2-0.3 L / min, and the pressure is 0.2-0.3 MPa.

[0019] Preferably, the preparation method of the phosphonate-amide composite purifier is as follows:

[0020] H1: Add 12-18 parts of aminotrimethylenephosphonic acid, 8-12 parts of sebacic acid dichloroisocyanurate, and 0.01-0.06 parts of 4-aminopyridine-2,6-dicarboxylic acid to 100-150 parts of N,N-dimethylformamide and mix under nitrogen protection;

[0021] H2: Add 2-3 parts of pyridine binder and stir at 30-40℃ for 5-7 hours to generate N,N'-bis(phosphonate methyl) sebacamide;

[0022] H3: Filter and distill under reduced pressure to obtain phosphonate-amide composite purifier.

[0023] Reaction mechanism:

[0024] When phosphonate-amide composite purifiers are used as additives during the quenching stage, their mechanism of action is as follows:

[0025] Low-temperature chelation purification: In the initial stage of quenching at 300-500℃, trace amounts of molten copper and incompletely removed Fe remain on the surface of the phosphor bronze rod. 3+ Pb 2+ Impurities such as phosphonic acid groups and dicarboxylic acid groups in the purifier can directionally chelate these impurities at low temperatures to form stable complexes (compared to the high-temperature stage, the low-temperature environment is more conducive to the stable existence of complexes).

[0026] Interface modification and protection: Long-chain amide groups are adsorbed onto the surface of the phosphor bronze rod through intermolecular forces, forming a dense protective film. On the one hand, this prevents the oxidation of the copper rod surface by oxygen in the air during quenching, and on the other hand, it reduces stress concentration caused by sudden temperature changes during cooling, thus inhibiting the formation of microcracks.

[0027] Synergistic strengthening effect: The chelated complex detaches from the surface of the copper rod with the quenching solution, achieving secondary removal of impurities; at the same time, the presence of the protective film makes the internal structure of the copper rod more uniform during rapid cooling, avoiding grain coarsening and further improving the density of the material.

[0028] Technical effects:

[0029] This invention provides a process for preparing phosphor bronze rods using a phosphonate-amide composite purifying agent as a quenching aid. Compared with existing technologies, this invention has the following significant advantages:

[0030] 1. During the quenching process, the interface protection effect of the purifying agent reduces stress concentration, thereby increasing the tensile strength and elongation of the phosphor bronze rod; at the same time, the removal of secondary impurities further reduces the obstruction to electron conduction, thus improving the electrical conductivity.

[0031] 2. Improved surface quality and corrosion resistance: The formation of a protective film on the surface reduces the surface roughness of the phosphor bronze rod and improves its corrosion resistance in humid environments, reducing the need for surface treatment processes in subsequent processing.

[0032] 3. The high-purity phosphorus copper rod prepared by this invention exhibits excellent performance in key indicators such as copper content, phosphorus content, and electrical conductivity, achieving the expected high purity and high electrical conductivity requirements. Detailed Implementation

[0033] To further illustrate the technical means and effects adopted by the present invention to achieve the intended purpose, the following detailed description is provided in conjunction with embodiments and comparative examples:

[0034] 1. Copper content: Detected using chemical titration.

[0035] 2. Phosphorus content: Detected using spectrophotometry.

[0036] 3. Conductivity: Detected using a digital conductivity meter.

[0037] Example 1

[0038] A process for preparing phosphor bronze rods using phosphonate-amide composite purifying agent as a quenching aid, comprising the following steps:

[0039] S1 Oxidation Refining: Mix 4.5g of phosphorus pentoxide and 55g of sodium carbonate, and boil them at 800℃ to make a uniform molten salt. After cooling and grinding the molten salt, mix it evenly with 150g of scrap copper and add it to a corundum crucible. Place the crucible in a sealed heating furnace and heat it rapidly to 1150℃. Start blowing compressed air in, and stop blowing after 40 minutes. After holding the temperature and letting it stand for 15 minutes, remove the slag, take a sample, and cool it.

[0040] S2 reduction refining: At a temperature of 1150℃, a mixed gas is bubbled into the melt obtained from S1; after 20 minutes, the gas flow is stopped and the temperature is maintained for 10 minutes.

[0041] S3 refining agent refining: At a temperature of 1150℃, add 0.05g of calcium boride to the melt obtained from S2, and at the same time blow in high-purity argon gas to stir the melt; after 20 minutes, stop the gas flow, let it stand and keep warm for another 20 minutes, remove the slag, take a sample, and cool.

[0042] S4 casting and molding: After stirring the refined copper liquid for 5 minutes, it is continuously cast and rolled.

[0043] S5 quenching treatment:

[0044] Preparation of quenching medium: Add 0.3g of phosphonate-amide composite purifier to 30g of deionized water and stir until completely dissolved to form a uniform quenching aid solution;

[0045] Quenching operation: The phosphor bronze rod after continuous casting and rolling is quickly immersed in the above quenching agent solution, and the cooling rate is controlled at 40℃ / s, so that the phosphor bronze rod is cooled to 90℃ within 1 minute;

[0046] S6 Post-treatment: The quenched phosphor bronze rod is removed from the quenching aid solution, the residual solution on the surface is dried with compressed air, and then dried at 120℃ for 20 minutes to obtain a high conductivity phosphor bronze rod.

[0047] The compressed air flow rate of S1 is 0.4 L / min, and the pressure is 0.3 MPa.

[0048] The S2 mixture is carbon monoxide and nitrogen in a volume ratio of 1:9.

[0049] The flow rate of the mixed gas in S2 is 0.2 L / min, and the pressure is 0.2 MPa.

[0050] The high-purity argon gas in S3 has a flow rate of 0.2 L / min and a pressure of 0.2 MPa.

[0051] The preparation method of the phosphonate-amide composite purifier is as follows:

[0052] H1: Add 12g of aminotrimethylenephosphonic acid (CAS No.: 6419-19-8), 8g of sebacic acid dichloroisocyanurate (CAS No.: 111-19-3), and 0.01g of 4-aminopyridine-2,6-dicarboxylic acid to 100g of N,N-dimethylformamide and mix under nitrogen protection;

[0053] H2: Add 2g of pyridine binder and stir at 30℃ for 5 hours to generate N,N'-bis(phosphonate methyl) sebacamide;

[0054] H3: Filter and distill under reduced pressure to obtain phosphonate-amide composite purifier.

[0055] Example 2

[0056] A process for preparing phosphor bronze rods using phosphonate-amide composite purifying agent as a quenching aid, comprising the following steps:

[0057] S1 Oxidation Refining: Mix 5.5g of phosphorus pentoxide and 60g of sodium carbonate, and boil them at 840℃ to make a uniform molten salt. After cooling and grinding the molten salt, mix it evenly with 160g of scrap copper and add it to a corundum crucible. Place the crucible in a sealed heating furnace and heat it rapidly to 1170℃. Start blowing compressed air in, and stop blowing after 45 minutes. After holding the temperature and letting it stand for 15 minutes, remove the slag, take a sample, and cool it.

[0058] S2 reduction refining: At a temperature of 1170℃, a mixed gas is bubbled into the melt obtained from S1; after 25 minutes, the gas flow is stopped and the temperature is maintained for 10 minutes.

[0059] S3 refining agent refining: At a temperature of 1170℃, add 0.1g of calcium boride to the melt obtained from S2, and at the same time blow in high-purity argon gas to stir the melt; after 25 minutes, stop the gas flow, let it stand and keep warm for another 25 minutes, remove the slag, take a sample, and cool.

[0060] S4 casting and molding: After stirring the refined copper liquid for 5 minutes, it is continuously cast and rolled.

[0061] S5 quenching treatment:

[0062] Preparation of quenching medium: Add 0.4g of phosphonate-amide composite purifier to 34g of deionized water and stir until completely dissolved to form a uniform quenching aid solution;

[0063] Quenching operation: The phosphor bronze rod after continuous casting and rolling is quickly immersed in the above quenching agent solution, and the cooling rate is controlled at 50℃ / s, so that the phosphor bronze rod is cooled to 95℃ within 2 minutes.

[0064] S6 Post-treatment: The quenched phosphor bronze rod is removed from the quenching aid solution, the residual solution on the surface is dried with compressed air, and then dried at 130℃ for 25 minutes to obtain a high conductivity phosphor bronze rod.

[0065] The compressed air flow rate of S1 is 0.4 L / min, and the pressure is 0.3 MPa.

[0066] The S2 mixture is carbon monoxide and nitrogen in a volume ratio of 1:9.

[0067] The flow rate of the mixed gas in S2 is 0.2 L / min, and the pressure is 0.2 MPa.

[0068] The high-purity argon gas in S3 has a flow rate of 0.2 L / min and a pressure of 0.2 MPa.

[0069] The preparation method of the phosphonate-amide composite purifier is as follows:

[0070] H1: Add 14g of aminotrimethylenephosphonic acid (CAS No.: 6419-19-8), 9g of sebacic acid dichloroisocyanurate (CAS No.: 111-19-3), and 0.02g of 4-aminopyridine-2,6-dicarboxylic acid to 110g of N,N-dimethylformamide and mix under nitrogen protection;

[0071] H2: Add 2.5g of pyridine binder and stir at 35℃ for 6 hours to generate N,N'-bis(phosphonate methyl) sebacamide;

[0072] H3: Filter and distill under reduced pressure to obtain phosphonate-amide composite purifier.

[0073] Example 3

[0074] A process for preparing phosphor bronze rods using phosphonate-amide composite purifying agent as a quenching aid, comprising the following steps:

[0075] S1 Oxidation Refining: Mix 6.5g of phosphorus pentoxide and 70g of sodium carbonate, and boil them at 880℃ to make a uniform molten salt. After cooling and grinding the molten salt, mix it evenly with 180g of scrap copper and add it to a corundum crucible. Place the crucible in a sealed heating furnace and heat it rapidly to 1200℃. Start blowing compressed air in, and stop blowing after 55 minutes. After holding the temperature and letting it stand for 20 minutes, remove the slag, take a sample, and cool it.

[0076] S2 reduction refining: At a temperature of 1200℃, a mixed gas is bubbled into the melt obtained from S1; after 25 minutes, the gas flow is stopped, and the temperature is maintained for 15 minutes.

[0077] S3 refining agent refining: At a temperature of 1200℃, add 0.15g of calcium boride to the melt obtained from S2, and at the same time blow in high-purity argon gas to stir the melt; after 25 minutes, stop the gas flow, let it stand and keep warm for another 25 minutes, remove the slag, take a sample, and cool.

[0078] S4 casting: After stirring the refined copper liquid for 10 minutes, it is continuously cast and rolled.

[0079] S5 quenching treatment:

[0080] Preparation of quenching medium: Add 0.7g of phosphonate-amide composite purifier to 38g of deionized water and stir until completely dissolved to form a uniform quenching aid solution;

[0081] Quenching operation: The phosphor bronze rod after continuous casting and rolling is quickly immersed in the above quenching agent solution, and the cooling rate is controlled at 70℃ / s, so that the phosphor bronze rod is cooled to 95℃ within 2 minutes.

[0082] S6 Post-treatment: The quenched phosphor bronze rod is removed from the quenching aid solution, the residual solution on the surface is dried with compressed air, and then dried at 140℃ for 25 minutes to obtain a high conductivity phosphor bronze rod.

[0083] The compressed air flow rate of S1 is 0.5 L / min, and the pressure is 0.4 MPa.

[0084] The S2 mixture is carbon monoxide and nitrogen in a volume ratio of 1:9.

[0085] The flow rate of the mixed gas in S2 is 0.3 L / min, and the pressure is 0.3 MPa.

[0086] The high-purity argon gas in S3 has a flow rate of 0.3 L / min and a pressure of 0.3 MPa.

[0087] The preparation method of the phosphonate-amide composite purifier is as follows:

[0088] H1: Add 16g of aminotrimethylenephosphonic acid (CAS No.: 6419-19-8), 11g of sebacic acid dichloroisocyanurate (CAS No.: 111-19-3), and 0.05g of 4-aminopyridine-2,6-dicarboxylic acid to 140g of N,N-dimethylformamide and mix under nitrogen protection;

[0089] H2: Add 2.5g of pyridine binder and stir at 35℃ for 6 hours to generate N,N'-bis(phosphonate methyl) sebacamide;

[0090] H3: Filter and distill under reduced pressure to obtain phosphonate-amide composite purifier.

[0091] Example 4

[0092] A process for preparing phosphor bronze rods using phosphonate-amide composite purifying agent as a quenching aid, comprising the following steps:

[0093] S1 Oxidation Refining: Mix 7.5g of phosphorus pentoxide and 75g of sodium carbonate, and boil them at 900℃ to make a uniform molten salt. After cooling and grinding the molten salt, mix it evenly with 200g of scrap copper and add it to a corundum crucible. Place the crucible in a sealed heating furnace and heat it rapidly to 1220℃. Start blowing compressed air in, and stop blowing after 60 minutes. After holding the temperature and letting it stand for 20 minutes, remove the slag, take a sample, and cool it.

[0094] S2 reduction refining: At a temperature of 1220℃, a mixed gas is bubbled into the melt obtained from S1; after 30 minutes, the gas flow is stopped and the temperature is maintained for 15 minutes.

[0095] S3 refining agent refining: At a temperature of 1220℃, add 0.2g of calcium boride to the melt obtained from S2, and simultaneously blow in high-purity argon gas to stir the melt; after 30 minutes, stop the gas flow, let it stand and keep warm for another 30 minutes, remove the slag, take a sample, and cool.

[0096] S4 casting: After stirring the refined copper liquid for 10 minutes, it is continuously cast and rolled.

[0097] S5 quenching treatment:

[0098] Preparation of quenching medium: Add 0.8g of phosphonate-amide composite purifier to 40g of deionized water and stir until completely dissolved to form a uniform quenching aid solution;

[0099] Quenching operation: The phosphor bronze rod after continuous casting and rolling is quickly immersed in the above quenching agent solution, and the cooling rate is controlled at 80℃ / s, so that the phosphor bronze rod is cooled to 100℃ within 3 minutes.

[0100] S6 Post-treatment: The quenched phosphor bronze rod is removed from the quenching aid solution, the residual solution on the surface is dried with compressed air, and then dried at 150℃ for 30 minutes to obtain a high conductivity phosphor bronze rod.

[0101] The compressed air flow rate of S1 is 0.5 L / min, and the pressure is 0.4 MPa.

[0102] The S2 mixture is carbon monoxide and nitrogen in a volume ratio of 1:9.

[0103] The flow rate of the mixed gas in S2 is 0.3 L / min, and the pressure is 0.3 MPa.

[0104] The high-purity argon gas in S3 has a flow rate of 0.3 L / min and a pressure of 0.3 MPa.

[0105] The preparation method of the phosphonate-amide composite purifier is as follows:

[0106] H1: Add 18g of aminotrimethylenephosphonic acid (CAS No.: 6419-19-8), 12g of sebacic acid dichloroisocyanurate (CAS No.: 111-19-3), and 0.06g of 4-aminopyridine-2,6-dicarboxylic acid to 150g of N,N-dimethylformamide and mix under nitrogen protection;

[0107] H2: Add 3g of pyridine binder and stir at 40℃ for 7 hours to generate N,N'-bis(phosphonate methyl) sebacamide;

[0108] H3: Filter and distill under reduced pressure to obtain phosphonate-amide composite purifier.

[0109] Comparative Example 1

[0110] A process for preparing phosphor bronze rods using phosphonate-amide composite purifying agent as a quenching aid, comprising the following steps:

[0111] S1 Oxidation Refining: Mix 4.5g of phosphorus pentoxide and 55g of sodium carbonate, and boil them at 800℃ to make a uniform molten salt. After cooling and grinding the molten salt, mix it evenly with 150g of scrap copper and add it to a corundum crucible. Place the crucible in a sealed heating furnace and heat it rapidly to 1150℃. Start blowing compressed air in, and stop blowing after 40 minutes. After holding the temperature and letting it stand for 15 minutes, remove the slag, take a sample, and cool it.

[0112] S2 reduction refining: At a temperature of 1150℃, a mixed gas is bubbled into the melt obtained from S1; after 20 minutes, the gas flow is stopped and the temperature is maintained for 10 minutes.

[0113] S3 refining agent refining: At a temperature of 1150℃, add 0.05g of calcium boride to the melt obtained from S2, and at the same time blow in high-purity argon gas to stir the melt; after 20 minutes, stop the gas flow, let it stand and keep warm for another 20 minutes, remove the slag, take a sample, and cool.

[0114] S4 casting and molding: After stirring the refined copper liquid for 5 minutes, it is continuously cast and rolled.

[0115] S5 quenching treatment: The phosphor bronze rod after continuous casting and rolling is quickly immersed in 30g of deionized water, and the cooling rate is controlled at 40℃ / s, so that the phosphor bronze rod is cooled to 90℃ within 1min.

[0116] S6 Post-treatment: The quenched phosphor bronze rod is taken out of the deionized water, dried with compressed air, and dried at 120℃ for 20 minutes to obtain a high conductivity phosphor bronze rod.

[0117] The compressed air flow rate of S1 is 0.4 L / min, and the pressure is 0.3 MPa.

[0118] The S2 mixture is carbon monoxide and nitrogen in a volume ratio of 1:9.

[0119] The flow rate of the mixed gas in S2 is 0.2 L / min, and the pressure is 0.2 MPa.

[0120] The high-purity argon gas in S3 has a flow rate of 0.2 L / min and a pressure of 0.2 MPa.

[0121] Comparative Example 2

[0122] A process for preparing phosphor bronze rods using phosphonate-amide composite purifying agent as a quenching aid, comprising the following steps:

[0123] S1 Oxidation Refining: Mix 4.5g of phosphorus pentoxide and 55g of sodium carbonate, and boil them at 800℃ to make a uniform molten salt. After cooling and grinding the molten salt, mix it evenly with 150g of scrap copper and add it to a corundum crucible. Place the crucible in a sealed heating furnace and heat it rapidly to 1150℃. Start blowing compressed air in, and stop blowing after 40 minutes. After holding the temperature and letting it stand for 15 minutes, remove the slag, take a sample, and cool it.

[0124] S2 reduction refining: At a temperature of 1150℃, a mixed gas is bubbled into the melt obtained from S1; after 20 minutes, the gas flow is stopped and the temperature is maintained for 10 minutes.

[0125] S3 refining agent refining: At a temperature of 1150℃, add 0.05g of calcium boride to the melt obtained from S2, and at the same time blow in high-purity argon gas to stir the melt; after 20 minutes, stop the gas flow, let it stand and keep warm for another 20 minutes, remove the slag, take a sample, and cool.

[0126] S4 casting and molding: After stirring the refined copper liquid for 5 minutes, it is continuously cast and rolled.

[0127] S5 quenching treatment:

[0128] Preparation of quenching medium: Add 0.3g of composite purifying agent to 30g of deionized water and stir until completely dissolved to form a uniform quenching aid solution;

[0129] Quenching operation: The phosphor bronze rod after continuous casting and rolling is quickly immersed in the above quenching agent solution, and the cooling rate is controlled at 40℃ / s, so that the phosphor bronze rod is cooled to 90℃ within 1 minute;

[0130] S6 Post-treatment: The quenched phosphor bronze rod is removed from the quenching aid solution, the residual solution on the surface is dried with compressed air, and then dried at 120℃ for 20 minutes to obtain a high conductivity phosphor bronze rod.

[0131] The compressed air flow rate of S1 is 0.4 L / min, and the pressure is 0.3 MPa.

[0132] The S2 mixture is carbon monoxide and nitrogen in a volume ratio of 1:9.

[0133] The flow rate of the mixed gas in S2 is 0.2 L / min, and the pressure is 0.2 MPa.

[0134] The high-purity argon gas in S3 has a flow rate of 0.2 L / min and a pressure of 0.2 MPa.

[0135] The preparation method of the composite purifying agent is as follows:

[0136] H1: Add 8g of sebacic acid dichloro(CAS No.: 111-19-3) and 0.01g of 4-aminopyridine-2,6-dicarboxylic acid to 100g of N,N-dimethylformamide and mix under nitrogen protection;

[0137] H2: Add 2g of pyridine binding acid agent, stir and react at 30℃ for 5 hours, filter, and distill under reduced pressure to obtain the composite purifying agent.

[0138] Comparative Example 3

[0139] A process for preparing phosphor bronze rods using phosphonate-amide composite purifying agent as a quenching aid, comprising the following steps:

[0140] S1 Oxidation Refining: Mix 4.5g of phosphorus pentoxide and 55g of sodium carbonate, and boil them at 800℃ to make a uniform molten salt. After cooling and grinding the molten salt, mix it evenly with 150g of scrap copper and add it to a corundum crucible. Place the crucible in a sealed heating furnace and heat it rapidly to 1150℃. Start blowing compressed air in, and stop blowing after 40 minutes. After holding the temperature and letting it stand for 15 minutes, remove the slag, take a sample, and cool it.

[0141] S2 reduction refining: At a temperature of 1150℃, a mixed gas is bubbled into the melt obtained from S1; after 20 minutes, the gas flow is stopped and the temperature is maintained for 10 minutes.

[0142] S3 refining agent refining: At a temperature of 1150℃, add 0.05g of calcium boride to the melt obtained from S2, and at the same time blow in high-purity argon gas to stir the melt; after 20 minutes, stop the gas flow, let it stand and keep warm for another 20 minutes, remove the slag, take a sample, and cool.

[0143] S4 casting and molding: After stirring the refined copper liquid for 5 minutes, it is continuously cast and rolled.

[0144] S5 quenching treatment:

[0145] Preparation of quenching medium: Add 0.3g of composite purifying agent to 30g of deionized water and stir until completely dissolved to form a uniform quenching aid solution;

[0146] Quenching operation: The phosphor bronze rod after continuous casting and rolling is quickly immersed in the above quenching agent solution, and the cooling rate is controlled at 40℃ / s, so that the phosphor bronze rod is cooled to 90℃ within 1 minute;

[0147] S6 Post-treatment: The quenched phosphor bronze rod is removed from the quenching aid solution, the residual solution on the surface is dried with compressed air, and then dried at 120℃ for 20 minutes to obtain a high conductivity phosphor bronze rod.

[0148] The compressed air flow rate of S1 is 0.4 L / min, and the pressure is 0.3 MPa.

[0149] The S2 mixture is carbon monoxide and nitrogen in a volume ratio of 1:9.

[0150] The flow rate of the mixed gas in S2 is 0.2 L / min, and the pressure is 0.2 MPa.

[0151] The high-purity argon gas in S3 has a flow rate of 0.2 L / min and a pressure of 0.2 MPa.

[0152] The preparation method of the composite purifying agent is as follows:

[0153] H1: Add 12g of aminotrimethylenephosphonic acid (CAS No.: 6419-19-8) and 8g of sebacic acid dichloroisocyanurate (CAS No.: 111-19-3) to 100g of N,N-dimethylformamide and mix under nitrogen protection;

[0154] H2: Add 2g of pyridine binding acid agent, stir and react at 30℃ for 5 hours, filter, and distill under reduced pressure to obtain the composite purifying agent.

[0155] The test results of the examples and comparative examples are shown in Table 1;

[0156] Table 1

[0157]

[0158]

[0159] Through data analysis of the above embodiments and comparative examples, the high-purity phosphorus copper rod prepared by the present invention exhibits excellent performance in key indicators such as copper content, phosphorus content, and electrical conductivity, achieving the expected requirements for high purity and high electrical conductivity.

[0160] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A process for preparing phosphor bronze rods using phosphonate-amide composite purifying agent as a quenching aid, characterized in that: The operation steps are as follows, according to the mass fraction: S1: oxidizing refining: 4.5-7.5 parts of phosphorus pentoxide, 55-75 parts of sodium carbonate are mixed, then melted into a uniform molten salt at 800-900 DEG C, the molten salt is cooled, ground and mixed with 150-200 parts of waste copper, then put into a corundum crucible; the crucible is put into a sealed heating furnace, rapidly heated to 1150-1220 DEG C, then compressed air is blown in, the blowing is stopped after 40-60 min; after 15-20 min of heat preservation, slag is removed, sampling and cooling; S2: reducing refining: mixed gas is blown into the melt obtained in S1 at a temperature of 1150-1220 DEG C; the gas blowing is stopped after 20-30 min, and heat preservation is carried out for 10-15 min; S3: refining agent refining: 0.05-0.2 parts of calcium boride is added into the melt obtained in S2 at a temperature of 1150-1220 DEG C, and high-purity argon is blown to stir the melt; the gas blowing is stopped after 20-30 min, and heat preservation is carried out for 20-30 min, then slag is removed, sampling and cooling; S4: casting forming: after the refined copper liquid is stirred for 5-10 min, continuous casting and rolling are carried out; S5: quenching treatment: Quenching medium preparation: 0.3-0.8 parts of phosphonate-amide composite purifying agent is added into 30-40 parts of deionized water, stirred until completely dissolved, and a uniform quenching aid solution is formed; Quenching operation: the phosphor copper rod after continuous casting and rolling is quickly immersed in the above quenching aid solution, and the cooling speed is controlled at 40-80 DEG C / s, so that the phosphor copper rod is cooled to 90-100 DEG C within 1-3 min; S6: post-treatment: the phosphor copper rod after quenching is taken out from the quenching aid solution, the surface residual solution is blown dry with compressed air, and is baked at 120-150 DEG C for 20-30 min, so that the high-conductivity phosphor copper rod is obtained; The phosphonate-amide composite purifying agent is prepared by reaction of aminotrimethylene phosphonic acid, sebacic acid dichloride, 4-aminopyridine-2,6-dicarboxylic acid and pyridine complexing agent.

2. The process for preparing phosphorous copper rod with phosphonate-amide complex scavenger as quenching aid according to claim 1, characterized in that: The compressed air flow of S1 is 0.4-0.5 L / min, and the pressure is 0.3-0.4 Mpa.

3. The process for preparing phosphorous copper rod with phosphonate-amide complex scavenger as quenching aid according to claim 1, characterized in that: The mixed gas of S2 is carbon monoxide and nitrogen, and the volume ratio is 1:

9.

4. The process as claimed in claim 1, wherein the phosphonate-amide complex scavenger is used as a quenching aid for preparing phosphorous copper rods. The mixed gas flow of S2 is 0.2-0.3 L / min, and the pressure is 0.2-0.3 Mpa.

5. The process as claimed in claim 1, wherein the phosphonate-amide complex scavenger is used as a quenching aid for the preparation of phosphorous copper rods. The high-purity argon flow of S3 is 0.2-0.3 L / min, and the pressure is 0.2-0.3 Mpa.

6. The process as claimed in claim 1, wherein the phosphonate-amide complex scavenger is used as a quenching aid for the preparation of phosphorous copper rods. The preparation method of the phosphonate-amide composite purifying agent is as follows: H1: 12-18 parts of aminotrimethylene phosphonic acid, 8-12 parts of sebacic acid dichloride and 0.01-0.06 parts of 4-aminopyridine-2,6-dicarboxylic acid are added into 100-150 parts of N,N-dimethylformamide, and mixed under nitrogen protection; H2: 2-3 parts of pyridine complexing agent is added, and stirred at 30-40 DEG C for 5-7 hours to generate N,N'-bis(phosphonate methyl) sebacic amide; H3: filtration and reduced pressure distillation are carried out to obtain the phosphonate-amide composite purifying agent.

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