CN107604202B - High-performance phosphor bronze strip and preparation method thereof - Google Patents
High-performance phosphor bronze strip and preparation method thereof Download PDFInfo
- Publication number
- CN107604202B CN107604202B CN201710838024.8A CN201710838024A CN107604202B CN 107604202 B CN107604202 B CN 107604202B CN 201710838024 A CN201710838024 A CN 201710838024A CN 107604202 B CN107604202 B CN 107604202B
- Authority
- CN
- China
- Prior art keywords
- annealing
- temperature
- casting
- alloy
- strip
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention relates to a high-performance phosphor bronze band, which comprises the following chemical components in percentage by weight: 10.0-13.0% of Sn10, 0.1-0.65% of Zn, 0.05-0.5% of Ni, 0.1-0.5% of Fe, 0.01-0.5% of P, 0.001-0.02% of RE, 0.005-0.05% of B and the balance of Cu. A process method for preparing a high-performance phosphor bronze strip comprises the following steps: a. the method comprises the following steps of proportioning, feeding, smelting and casting according to mass percentage, b, pre-primary rolling, c, homogenizing annealing, d, milling surface, e, rough rolling, f, intermediate annealing, g, acid washing, h, intermediate rolling, i, continuous annealing, j, finish rolling, k, acid washing, m, stretch bending and straightening, n, low-temperature annealing, o, shearing, p, packaging and warehousing.
Description
Technical Field
The invention relates to the technical field of nonferrous metal processing, in particular to a high-tin phosphor bronze strip which is widely used in the fields of high-end elastic elements and electronic components and a short-process preparation method.
Background
The tin-phosphor bronze has high elasticity, wear resistance, diamagnetism, good cold and hot processing performance, welding and brazing performance, particularly has good corrosion resistance in atmosphere and fresh water, can be used for manufacturing parts such as spring contact pieces, wear-resistant parts, diamagnetic elements and the like, and is widely applied to the fields of radio, electronics, automobiles, communication industry and the like.
The electronic, communication and automobile industries are in a high-speed development stage, the demand of tin-phosphor bronze strips is increased sharply, and meanwhile, elastic components are developed towards the directions of micro, thin, high elasticity, complex bending formability, wear resistance, corrosion resistance and stress relaxation resistance, and particularly the tensile strength is more than 1000 MPa; meanwhile, the material is required to have certain conductivity and stress relaxation resistance. Therefore, the development trend of copper-based elastic materials is high-strength, high-elasticity and low-stress relaxation alloy. The existing phosphor bronze alloy generally has low electric conductivity which is only 12-16% IACS, and the strength is about 600-800MPa, so that the use requirements of materials such as intelligent automobiles and homes are difficult to meet, and when the strength is improved to more than 1000MPa, the plasticity and toughness are poor, the stamping forming performance cannot be met, so that the functional effect of the elastic material is influenced. The traditional phosphor bronze alloy has excellent elasticity and good stress relaxation resistance, and occupies the half-wall Jiangshan of an elastic material, so how to perform alloy component modification treatment on the basis of the phosphor bronze alloy to obtain a high-performance high-tin phosphor bronze alloy material with tensile strength of more than 1000MPa and excellent comprehensive performance, and the phosphor bronze alloy material meets the use requirements of elastic component materials and realizes industrial production thereof, and has important significance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to make up the disadvantages of insufficient strength, poor bending forming performance and the like of the existing phosphor bronze alloy, and on the basis of the traditional phosphor bronze alloy, a small amount of trace elements such as iron, nickel, zinc and the like are added to improve the microstructure, and the preparation process and method of phosphor bronze are optimized, so that the segregation degree of tin element is obviously improved, the comprehensive performance of the alloy is improved, and the complex Cu-Sn-Fe-Ni-Zn-P alloy with high strength and high elasticity, excellent bending forming performance and excellent stress relaxation resistance is obtained.
In order to achieve the purpose, the invention provides the following technical scheme:
a high-performance phosphor bronze band comprises the following chemical components in percentage by weight: 10.0-13.0% of Sn0, 0.1-0.65% of Zn0.05-0.5% of Ni, 0.1-0.5% of Fe, 0.01-0.5% of P, 0.001-0.02% of RE, 0.005-0.05% of B and the balance of Cu.
The improved material comprises the following chemical components, by weight, 10.5-11.5% of Sns, 0.1-0.35% of Zn, 0.1-0.2% of Ni, 0.1-0.2% of Fe, 0.01-0.05% of P, 0.005-0.01% of RE, 0.015-0.03% of B, and the balance of Cu.
The function of the added alloy elements is as follows:
nickel: the copper-nickel alloy is infinitely solid-dissolved, and the nickel element has double effects of grain refinement and solid solution strengthening, and is beneficial to improving the mechanical property of the alloy. And simultaneously, the high-temperature softening point of the phosphor bronze alloy is improved.
Tin: because the radius difference between tin atoms and copper atoms is large, tin elements are added into the copper alloy, so that large lattice distortion can be caused, the movement of dislocation is effectively hindered, and the strength and the elastic property of the alloy are improved. In addition, the corrosion resistance of the alloy can be obviously improved by adding the tin element.
Phosphorus: trace phosphorus element not only can play a role in removing oxygen, but also can form a copper-phosphorus compound with copper to improve the softening temperature resistance and the stress relaxation resistance of the alloy, but because the phosphorus element can deteriorate the conductive property of the alloy, the content of the phosphorus element in the alloy needs to be strictly controlled;
zinc: in order to prolong the service life and improve the welding performance of the high-strength elastic component, the surface of the high-strength elastic component is usually subjected to tinning treatment, and trace zinc element is added, so that the surface wetting angle and affinity of the alloy can be obviously improved, and the reliability and stability of a coating are obviously improved.
Iron: the iron element can effectively adjust the size of the alloy grain structure, improve the uniformity of the structure and improve the stress corrosion resistance sensitivity of the alloy, particularly, the iron and nickel alloy elements are added simultaneously, the temperature range of a solid-liquid line can be obviously reduced, the segregation condition of the tin element is improved, a casting blank with good metallurgical quality is obtained, the grain of the alloy is obviously refined, and the phosphor bronze alloy with excellent conductivity can be obtained by refining the grain and improving the tin segregation.
Boron: during the alloy smelting process, a proper amount of boron is added to have the functions of degassing and deoxidizing, so that the quality of a smelting billet is improved. Meanwhile, boron is used as a nucleation particle, so that the Sn element and a matrix structure can be promoted to keep a semi-coherent crystal face, and dislocation expansion is hindered. However, boron has a very low solubility in copper, and excess boron tends to aggregate at grain boundaries, resulting in work embrittlement.
RE is rare earth alloy element in the tin-phosphor bronze alloy, which mainly purifies the melt, improves the density and the fluidity of the melt, is favorable for eliminating the loose structure defect of casting and improves the quality of the melt.
Iron, nickel and rare earth elements: the addition of the three elements can mainly play a role in refining the grain size and reducing the tin segregation degree. When the three elements are added into the alloy together, the three elements have the interaction among the elements, so that the crystal grains can be obviously refined and the tin segregation can be improved, the effect is better than that of adding the two alloy elements, and the high-tin phosphor bronze alloy with excellent comprehensive quality can be obtained.
A process method for preparing a high-performance phosphor bronze strip comprises the following steps: a. the method comprises the following steps of proportioning, feeding, smelting and casting according to mass percentage, b, pre-primary rolling, c, homogenizing annealing, d, milling surface, e, rough rolling, f, intermediate annealing, g, acid washing, h, intermediate rolling, i, continuous annealing, j, finish rolling, k, acid washing, m, stretch bending and straightening, n, low-temperature annealing, o, shearing, p, packaging and warehousing.
As the improvement of the invention, firstly adding copper (Cu), nickel (Ni) and iron (Fe), melting, then adding tin (Sn) and zinc ingots (Zn) at low temperature, adding copper-phosphorus (Cu-P), Rare Earth (RE) alloy and nickel-boron (NiB) alloy (adding intermediate alloy after melting zinc element, mainly aiming at reducing oxidation burning loss and realizing uniform and stable components), testing the components to be qualified, cleaning the furnace slag, and covering charcoal with baked furnace slag; casting by using a power frequency induction furnace in a non-vacuum environment, controlling the casting temperature to be 1190-1210 ℃, casting in a horizontal continuous casting mode, testing components to be qualified, cleaning slag, and covering by using baked charcoal; and casting by adopting a power frequency induction furnace in a non-vacuum environment, controlling the casting temperature to be 1190-1210 ℃, and casting by adopting a horizontal continuous casting mode.
As a further improvement of the invention, the horizontal continuous casting process is required to be controlled by adopting a drawing length of 10.0 ~ 12.0.0 mm, a drawing time of 0.6 ~ 0.9.9 s, a middle stop of 2.5 ~ 3.2.2 s, a return pushing length of 1.0 ~ 2.0.0 mm, a return pushing time of 0.2 ~ 0.4.4 s, a casting speed of 120 ~ 170mm/min and a strip billet outlet temperature of 250 ~ 400 ℃, a tin-phosphor bronze strip billet of 13.5 ~ 15.5mm in thickness, 430 ~ 650mm in width and 70-150 m.
Preferably, in the step b, pre-blooming is performed in an arc control mode, the deformation amount is 30-35%, in the step c, the annealing temperature is 610-630 ℃, and the heat preservation time is 8-10 h.
As a further preferred aspect of the present invention, in step i, an ultra-fine grain control technique is adopted, and the tensile strength is controlled to be 500-560 MPa. When the steel plate is bent by 90 degrees, R/T is zero, and the steel plate is not cracked when bent.
In the specific technical scheme of the invention, in the step j, the finish rolling processing rate is 30-50%.
As an improvement of the invention, in the step m, the stretch bending straightening adopts an elongation control mode, and the given elongation is 2.5-4.5%; in step n, the temperature of the low-temperature annealing is 400 ℃, and the speed is 35-45 m/min. A method of combining and regulating stretch bending correction and low-temperature tension annealing is adopted; on the one hand, the residual stress of the strip is eliminated, and on the other hand, the elasticity limit value of the material is improved.
Compared with the prior art, the invention has the advantages that: compared with the traditional phosphor bronze alloy, the Cu-Sn-Fe-Ni-Zn-P alloy has the characteristics of high strength, excellent bending forming performance and excellent stress relaxation resistance, and has good cold processing characteristics. (1) The preferable alloy components of the invention are 10.5-11.5% of Sns, 0.1-0.35% of Zn, 0.1-0.2% of Ni, 0.1-0.2% of Fe, 0.01-0.05% of P, 0.005-0.01% of RE, 0.015-0.03% of B and the balance of Cu, and Fe and Ni alloy elements added in trace amount in the alloy can remarkably reduce the temperature range of a solid-liquid phase line and combine the effects of refining a grain structure, remarkably improve the segregation condition of tin and improve the metallurgical quality of cast ingots; the RE and B alloy elements are added to improve the flow characteristic of the melt, refine the crystal grains and reduce the segregation of tin;
(2) the method directly performs pre-blooming treatment by microalloying treatment and optimizing the processing technology of horizontal continuous casting, can avoid homogenization treatment of the strip (the temperature of the homogenization annealing process of the strip is 670 ~ 710 ℃, the heat preservation time is generally 16 ~ 20 hours, a large amount of manpower, liquid ammonia and liquid nitrogen are consumed), adopts microalloy and a temperature gradient combination treatment technology in the solidification process, inhibits segregation and grain refinement of tin elements, inhibits nucleation of eutectic brittle phases, reduces the production and manufacturing cost, and realizes short-flow preparation.
(3) By adopting the processing technology control technology of ultra-fine grains and cold plastic deformation, the comprehensive performance of the strip can be obviously improved, particularly the complex bending formability and the elongation percentage, and the high-strength high-elasticity elastic material with the comprehensive performance is obtained;
(4) by adopting a combined adjusting process of stretch bending correction and low-temperature tension annealing, on one hand, the plate shape can be obviously improved and the residual stress can be reduced, on the other hand, the elasticity limit value is increased, the increase of the elasticity limit value can meet the use requirement of a part material with a high elasticity limit material, and the plugging times and the fatigue-resistant service life of the part material are obviously improved; meanwhile, compared with the traditional process control of low-temperature tension annealing and stretch bending straightening, the method can obviously improve the stress relaxation resistance and prolong the service life.
The tensile strength sigma b of the obtained novel Cu-Sn-Fe-Ni-Zn-P alloy can reach 1050MPa, the elongation after fracture is more than or equal to 3 percent, the R/T ratio of minimum 90-degree bending is 1.5 (ensuring that the bending does not crack), the elastic limit can reach 820MPa, the stress relaxation resistance rate of 100h at room temperature is 81-86 percent, and the use requirement of an elastic part material formed by complex bending can be met.
Detailed Description
The preparation and processing technology of the high-performance phosphor bronze band comprises the following steps: a. the method comprises the following steps of proportioning, feeding, smelting and casting according to mass percentage, b, pre-primary rolling, c, homogenizing annealing, d, milling surface, e, rough rolling, f, intermediate annealing, g, acid washing, h, intermediate rolling, i, continuous annealing, j, finish rolling, k, acid washing, m, stretch bending and straightening, n, low-temperature annealing, o, shearing, p, packaging and warehousing.
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, ingot slice, iron slice, pure tin, zinc ingot, copper phosphorus alloy, rare earth element RE and nickel boron alloy.
Example 1
The composition of the alloy is shown in table 1, example 1.
In the step a, the specific feeding sequence is as follows: firstly adding copper (Cu), nickel (Ni) and iron (Fe), melting, then adding tin (Sn) and zinc ingots (Zn) at low temperature, adding copper phosphorus (Cu-P), Rare Earth (RE) alloy and nickel boron (NiB) alloy at low temperature after all the components are melted (adding after melting zinc element, the main purpose is to reduce the oxidation burning loss and realize the uniformity and stability of components), testing the components to be qualified, cleaning the furnace slag, and covering with baked charcoal; and casting by using a power frequency induction furnace in a non-vacuum environment, controlling the casting temperature at 1195 ℃, and casting by using a horizontal continuous casting mode.
The horizontal continuous casting process requires the following control: adopting the drawing length of 10.5mm, the drawing time of 0.8s, the intermediate stop of 2.5s, the return pushing length of 1.2mm, the return withdrawing time of 0.2s, the casting speed of 156.0mm/min, the strip billet outlet temperature of 280 ℃, the crystallization line on the surface of the strip billet should be straight and free of visible casting defects such as cracks, gaps, pits, cold shut and the like; tin-phosphor bronze strip coil: 14.5mm thick, 650mm wide and 120m long.
And b, pre-blooming the high-tin bronze casting blank after rolling the blank, and pre-blooming the high-tin bronze casting blank in an arc control mode, wherein the deformation is 35%.
And c, carrying out homogenization annealing on the pre-blooming rolled coil blank, wherein the annealing temperature is 630 ℃, and the heat preservation time is 9h, so that the surface segregation condition of tin is further improved.
In the step d, carrying out face milling treatment on the coil blank subjected to homogenizing annealing, milling 0.6mm on each face in an online or offline manner, and mainly removing surface oxide skin and eliminating a surface segregation layer;
step i, carrying out continuous annealing treatment in an air cushion type annealing furnace, wherein the high-tin phosphor bronze alloy adopts an ultrafine grain control technology, the tensile strength is controlled at 530MPa, when the alloy is bent at 90 degrees, the R/T is zero, and the bent alloy does not crack;
step j, performing finish rolling on the strip subjected to the continuous annealing treatment, wherein the deformation is 40%;
in the step m, the strip subjected to acid cleaning treatment is subjected to stretch bending straightening, an elongation control mode is adopted, the given elongation is 2.5%, on one hand, the strip shape of the strip is straightened, and on the other hand, the elastic limit of the material is favorably improved;
in the step n, performing low-temperature annealing on the stretch-bent and straightened strip, and adopting continuous annealing treatment, wherein the temperature of the low-temperature annealing is 400 ℃, and the speed is 35m/min, so that on one hand, the residual stress of the strip is eliminated, and on the other hand, the comprehensive performance of the material, especially the elongation performance of the material is improved;
after the above-described processing treatments of melting, pre-blooming, homogenizing annealing, surface milling, rough rolling, continuous annealing, finish rolling, stretch-bending leveling, low-temperature tension annealing, etc., the properties thereof are shown in example 1 in table 2.
Example 2
The composition of the alloy is shown in table 1, example 2.
In the step a, the specific feeding sequence is as follows: firstly adding copper (Cu), nickel (Ni) and iron (Fe), melting, then adding tin (Sn) and zinc ingots (Zn) at low temperature, adding copper phosphorus (Cu-P), Rare Earth (RE) alloy and nickel boron (NiB) alloy at low temperature after all the components are melted (adding after melting zinc element, the main purpose is to reduce the oxidation burning loss and realize the uniformity and stability of components), testing the components to be qualified, cleaning the furnace slag, and covering with baked charcoal; and casting by using a power frequency induction furnace in a non-vacuum environment, wherein the casting temperature is controlled at 1210 ℃, and casting is performed by adopting a horizontal continuous casting mode.
The horizontal continuous casting process requires the following control: adopting the drawing length of 11.0mm, the drawing time of 0.6s, the middle stop of 3.0s, the return pushing length of 1.0mm, the return withdrawing time of 0.4s, the casting speed of 145mm/min, the strip billet outlet temperature of 350 ℃, and the crystallization line on the surface of the strip billet should be straight and should have no visible casting defects such as cracks, gaps, pits, cold shut and the like; tin-phosphor bronze strip coil: the thickness is 15.5mm, the width is 650mm, and the length is 150 m.
In the step b, pre-blooming the high-tin bronze casting blank after rolling the blank, and pre-blooming the high-tin bronze casting blank in an arc control mode, wherein the deformation is 35%;
in the step c, carrying out homogenization annealing on the pre-blooming rolled coil blank, wherein the annealing temperature is 610 ℃, the heat preservation time is 10 hours, and the surface layer segregation condition of tin is further improved;
in the step d, carrying out surface milling treatment on the coil blank subjected to homogenizing annealing, carrying out surface milling on line or off line, and milling each surface by 0.65mm, mainly removing surface oxide skin and eliminating a surface segregation layer;
in the step i, continuous annealing treatment is carried out in an air cushion type annealing furnace, the high-tin phosphor bronze alloy adopts an ultrafine grain control technology, the tensile strength is controlled at 500MPa, when the alloy is bent at 90 degrees, the R/T is zero, and the alloy is not cracked when being bent;
step j, performing finish rolling on the strip subjected to the continuous annealing treatment, wherein the deformation is 50%;
in the step m, the strip subjected to acid cleaning treatment is subjected to stretch bending straightening, an elongation control mode is adopted, the given elongation is 3.0%, on one hand, the strip shape of the strip is straightened, and on the other hand, the elastic limit of the material is favorably improved;
in the step n, performing low-temperature annealing on the stretch-bent and straightened strip, and adopting continuous annealing treatment, wherein the low-temperature annealing temperature is 400 ℃, and the speed is 40m/min, so that on one hand, the residual stress of the strip is eliminated, and on the other hand, the comprehensive performance of the material, especially the elongation performance of the material, is improved;
after the above-described processing treatments of melting, pre-blooming, homogenizing annealing, surface milling, rough rolling, continuous annealing, finish rolling, stretch-bending leveling, low-temperature tension annealing, etc., the properties thereof are shown in example 2 in table 2.
Example 3
The composition of the alloy is shown in table 1, example 3.
In the step a, the specific feeding sequence is as follows: firstly adding copper (Cu), nickel (Ni) and iron (Fe), melting, then adding tin (Sn) and zinc ingots (Zn) at low temperature, adding copper phosphorus (Cu-P), Rare Earth (RE) alloy and nickel boron (NiB) alloy at low temperature after all the components are melted (adding after melting zinc element, the main purpose is to reduce the oxidation burning loss and realize the uniformity and stability of components), testing the components to be qualified, cleaning the furnace slag, and covering with baked charcoal; and (3) casting by adopting a power frequency induction furnace in a non-vacuum environment, controlling the casting temperature to be 1205 ℃, and casting by adopting a horizontal continuous casting mode.
The horizontal continuous casting process requires the following control: adopting the drawing length of 12.0mm, the drawing time of 0.9s, the middle stop of 3.2s, the return pushing length of 2.0mm, the return withdrawing time of 0.4s, the casting speed of 170mm/min, the strip billet outlet temperature of 330 ℃, the crystallization line on the surface of the strip billet should be straight and should have no visible casting defects such as cracks, gaps, pits, cold shut and the like; tin-phosphor bronze strip coil: the thickness is 13.5mm, the width is 430mm, and the length is 90 m.
And b, pre-blooming the high-tin bronze casting blank after rolling the blank, and pre-blooming the high-tin bronze casting blank in an arc control mode, wherein the deformation is 30%.
And c, carrying out homogenization annealing on the pre-blooming rolled coil blank, wherein the annealing temperature is 610 ℃, and the heat preservation time is 8h, so that the surface segregation condition of tin is further improved.
In the step d, carrying out face milling treatment on the coil blank subjected to homogenizing annealing, milling 0.6mm on each face in an online or offline manner, and mainly removing surface oxide skin and eliminating a surface segregation layer;
in the step i, continuous annealing treatment is carried out in an air cushion type annealing furnace, the high-tin phosphor bronze alloy adopts an ultrafine grain control technology, the tensile strength is controlled at 560MPa, when the alloy is bent at 90 degrees, the R/T is zero, and the alloy is not cracked when the alloy is bent;
step j, performing finish rolling on the strip subjected to the continuous annealing treatment, wherein the deformation is 45%;
in the step m, the strip subjected to acid cleaning treatment is subjected to stretch bending straightening, an elongation control mode is adopted, the given elongation is 3.5%, on one hand, the strip shape of the strip is straightened, and on the other hand, the elastic limit of the material is favorably improved;
in the step n, performing low-temperature annealing on the stretch-bent and straightened strip, and adopting continuous annealing treatment, wherein the low-temperature annealing temperature is 400 ℃, and the speed is 45m/min, so that on one hand, the residual stress of the strip is eliminated, and on the other hand, the comprehensive performance of the material, especially the elongation performance of the material, is improved;
after the above-described processing treatments of melting, pre-blooming, homogenizing annealing, surface milling, rough rolling, continuous annealing, finish rolling, stretch-bending leveling, low-temperature tension annealing, etc., the properties thereof are shown in example 3 in table 2.
Example 4
The composition of the alloy is shown in table 1, example 4.
In the step a, the specific feeding sequence is as follows: firstly adding copper (Cu), nickel (Ni) and iron (Fe), melting, then adding tin (Sn) and zinc ingots (Zn) at low temperature, adding copper phosphorus (Cu-P), Rare Earth (RE) alloy and nickel boron (NiB) alloy at low temperature after all the components are melted (adding after melting zinc element, the main purpose is to reduce the oxidation burning loss and realize the uniformity and stability of components), testing the components to be qualified, cleaning the furnace slag, and covering with baked charcoal; and casting by using a power frequency induction furnace in a non-vacuum environment, wherein the casting temperature is controlled to 1190 ℃, and casting is performed by adopting a horizontal continuous casting mode.
The horizontal continuous casting process requires the following control: adopting the drawing length of 10.0mm, the drawing time of 0.9s, the middle stop of 3.0s, the return pushing length of 1.8mm, the return withdrawing time of 0.3s, the casting speed of 120mm/min, the strip billet outlet temperature of 280 ℃, the crystallization line on the surface of the strip billet should be straight and should have no visible casting defects such as cracks, gaps, pits, cold shut and the like; tin-phosphor bronze strip coil: the thickness is 13.5mm, the width is 430mm, and the length is 70 m.
And b, pre-blooming the high-tin bronze casting blank after rolling the blank, and pre-blooming the high-tin bronze casting blank in an arc control mode, wherein the deformation is 35%.
And c, carrying out homogenization annealing on the pre-blooming rolled coil blank, wherein the annealing temperature is 630 ℃, and the heat preservation time is 8h, so that the surface segregation condition of tin is further improved.
In the step d, carrying out face milling treatment on the coil blank subjected to homogenizing annealing, milling 0.7mm on each face in an online or offline manner, and mainly removing surface oxide skin and eliminating a surface segregation layer;
in the step i, continuous annealing treatment is carried out in an air cushion type annealing furnace, the high-tin phosphor bronze alloy adopts an ultrafine grain control technology, the tensile strength is controlled at 550MPa, when the alloy is bent at 90 degrees, the R/T is zero, and the alloy is not cracked when being bent;
step j, performing finish rolling on the strip subjected to the continuous annealing treatment, wherein the deformation is 30%;
in the step m, the strip subjected to acid cleaning treatment is subjected to stretch bending straightening, an elongation control mode is adopted, the given elongation is 4.2%, on one hand, the strip shape of the strip is straightened, and on the other hand, the elastic limit of the material is favorably improved;
in the step n, performing low-temperature annealing on the stretch-bent and straightened strip, and performing continuous annealing treatment at the temperature of 400 ℃ and the speed of 38m/min, so that on one hand, the residual stress of the strip is eliminated, and on the other hand, the comprehensive performance of the material, especially the elongation performance of the material is improved;
after the above-described processing treatments of melting, pre-blooming, homogenizing annealing, surface milling, rough rolling, continuous annealing, finish rolling, stretch-bending leveling, low-temperature tension annealing, etc., the properties thereof are shown in example 4 in table 2.
Example 5
The composition of the alloy is shown in table 1, example 5.
In the step a, the specific feeding sequence is as follows: firstly adding copper (Cu), nickel (Ni) and iron (Fe), melting, then adding tin (Sn) and zinc ingots (Zn) at low temperature, adding copper phosphorus (Cu-P), Rare Earth (RE) alloy and nickel boron (NiB) alloy at low temperature after all the components are melted (adding after melting zinc element, the main purpose is to reduce the oxidation burning loss and realize the uniformity and stability of components), testing the components to be qualified, cleaning the furnace slag, and covering with baked charcoal; and casting by using a power frequency induction furnace in a non-vacuum environment, controlling the casting temperature at 1192 ℃, and casting by using a horizontal continuous casting mode.
The horizontal continuous casting process requires the following control: adopting the drawing length of 11.2mm, the drawing time of 0.8s, the intermediate stop of 2.6s, the return pushing length of 1.2mm, the return withdrawal time of 0.3s, the casting speed of 162mm/min, the strip outlet temperature of 400 ℃, the crystallization line on the surface of the strip blank should be straight and should have no visible casting defects such as cracks, gaps, pits, cold shut and the like; tin-phosphor bronze strip coil: the thickness is 15.5mm, the width is 650mm, and the length is 150 m.
And b, pre-blooming the high-tin bronze casting blank after rolling the blank, and pre-blooming the high-tin bronze casting blank in an arc control mode, wherein the deformation is 35%.
And c, carrying out homogenization annealing on the pre-blooming rolled coil blank, wherein the annealing temperature is 630 ℃, and the heat preservation time is 10 hours, so that the surface segregation condition of tin is further improved.
In the step d, carrying out face milling treatment on the coil blank subjected to homogenizing annealing, milling 0.8mm on each face in an online or offline manner, and mainly removing surface oxide skin and eliminating a surface segregation layer;
in the step i, continuous annealing treatment is carried out in an air cushion type annealing furnace, the high-tin phosphor bronze alloy adopts an ultrafine grain control technology, the tensile strength is controlled at 500MPa, when the alloy is bent at 90 degrees, the R/T is zero, and the alloy is not cracked when being bent;
step j, performing finish rolling on the strip subjected to the continuous annealing treatment, wherein the deformation is 30%;
in the step m, the strip subjected to acid cleaning treatment is subjected to stretch bending straightening, an elongation control mode is adopted, the given elongation is 4.5%, on one hand, the strip shape of the strip is straightened, and on the other hand, the elastic limit of the material is favorably improved;
in the step n, performing low-temperature annealing on the stretch-bent and straightened strip, and adopting continuous annealing treatment, wherein the temperature of the low-temperature annealing is 400 ℃, and the speed is 35m/min, so that on one hand, the residual stress of the strip is eliminated, and on the other hand, the comprehensive performance of the material, especially the elongation performance of the material is improved;
after the above-described processing treatments of melting, pre-blooming, homogenizing annealing, surface milling, rough rolling, continuous annealing, finish rolling, stretch-bending leveling, low-temperature tension annealing, etc., the properties thereof are shown in example 5 in table 2.
Example 6
The composition of the alloy is shown in table 1, example 6.
In the step a, the specific feeding sequence is as follows: firstly adding copper (Cu), nickel (Ni) and iron (Fe), melting, then adding tin (Sn) and zinc ingots (Zn) at low temperature, adding copper phosphorus (Cu-P), Rare Earth (RE) alloy and nickel boron (NiB) alloy at low temperature after all the components are melted (adding after melting zinc element, the main purpose is to reduce the oxidation burning loss and realize the uniformity and stability of components), testing the components to be qualified, cleaning the furnace slag, and covering with baked charcoal; and casting by adopting a power frequency induction furnace in a non-vacuum environment, wherein the casting temperature is controlled at 1206 ℃, and casting is carried out by adopting a horizontal continuous casting mode.
The horizontal continuous casting process requires the following control: adopting the drawing length of 11.8mm, the drawing time of 0.8s, the intermediate stop of 2.8s, the return pushing length of 1.5mm, the return withdrawing time of 0.3s, the casting speed of 158mm/min, the strip billet outlet temperature of 360 ℃, the crystallization line on the surface of the strip billet should be straight and should have no visible casting defects such as cracks, gaps, pits, cold shut and the like; tin-phosphor bronze strip coil: the thickness is 14.5mm, the width is 430mm, and the length is 80 m.
And b, pre-blooming the high-tin bronze casting blank after rolling the blank, and pre-blooming the high-tin bronze casting blank in an arc control mode, wherein the deformation is 35%.
And c, carrying out homogenization annealing on the pre-blooming rolled coil blank, wherein the annealing temperature is 620 ℃, the heat preservation time is 9h, and further improving the surface segregation condition of tin.
In the step d, carrying out face milling treatment on the coil blank subjected to homogenizing annealing, milling 0.7mm on each face in an online or offline manner, and mainly removing surface oxide skin and eliminating a surface segregation layer;
step i, carrying out continuous annealing treatment in an air cushion type annealing furnace, wherein the high-tin phosphor bronze alloy adopts an ultrafine grain control technology, the tensile strength is controlled at 530MPa, when the alloy is bent at 90 degrees, the R/T is zero, and the bent alloy does not crack;
step j, performing finish rolling on the strip subjected to the continuous annealing treatment, wherein the deformation is 35%;
in the step m, the strip subjected to acid cleaning treatment is subjected to stretch bending straightening, an elongation control mode is adopted, the given elongation is 3.8%, on one hand, the strip shape of the strip is straightened, and on the other hand, the elastic limit of the material is favorably improved;
in the step n, performing low-temperature annealing on the stretch-bent and straightened strip, and performing continuous annealing treatment at the temperature of 400 ℃ and the speed of 38m/min, so that on one hand, the residual stress of the strip is eliminated, and on the other hand, the comprehensive performance of the material, especially the elongation performance of the material is improved;
after the above-described processing treatments of melting, pre-blooming, homogenizing annealing, surface milling, rough rolling, continuous annealing, finish rolling, stretch-bending leveling, low-temperature tension annealing, etc., the properties thereof are shown in example 6 in table 2.
Example 7
The composition of the alloy is shown in table 1, example 7.
In the step a, the specific feeding sequence is as follows: firstly adding copper (Cu), nickel (Ni) and iron (Fe), melting, then adding tin (Sn) and zinc ingots (Zn) at low temperature, adding copper phosphorus (Cu-P), Rare Earth (RE) alloy and nickel boron (NiB) alloy at low temperature after all the components are melted (adding after melting zinc element, the main purpose is to reduce the oxidation burning loss and realize the uniformity and stability of components), testing the components to be qualified, cleaning the furnace slag, and covering with baked charcoal; and casting by using a power frequency induction furnace in a non-vacuum environment, wherein the casting temperature is controlled at 1210 ℃, and casting is performed by adopting a horizontal continuous casting mode.
The horizontal continuous casting process requires the following control: adopting the drawing length of 10.0mm, the drawing time of 0.7s, the intermediate stop of 2.9s, the return pushing length of 2mm, the return withdrawal time of 0.2s, the casting speed of 125mm/min, the strip outlet temperature of 250 ℃, the crystallization line on the surface of the strip blank should be straight and should have no visible casting defects such as cracks, gaps, pits, cold shut and the like; tin-phosphor bronze strip coil: the thickness is 13.5mm, the width is 430mm, and the length is 80 m.
And b, pre-blooming the high-tin bronze casting blank after rolling the blank, and pre-blooming the high-tin bronze casting blank in an arc control mode, wherein the deformation is 35%.
And c, carrying out homogenization annealing on the pre-blooming coil blank, wherein the annealing temperature is 615 ℃, and the heat preservation time is 8h, so that the surface segregation condition of tin is further improved.
In the step d, carrying out face milling treatment on the coil blank subjected to homogenizing annealing, milling 0.5mm on each face in an online or offline manner, and mainly removing surface oxide skin and eliminating a surface segregation layer;
in the step i, continuous annealing treatment is carried out in an air cushion type annealing furnace, the high-tin phosphor bronze alloy adopts an ultrafine grain control technology, the tensile strength is controlled at 500MPa, when the alloy is bent at 90 degrees, the R/T is zero, and the alloy is not cracked when being bent;
step j, performing finish rolling on the strip subjected to the continuous annealing treatment, wherein the deformation is 30%;
in the step m, the strip subjected to acid cleaning treatment is subjected to stretch bending straightening, an elongation control mode is adopted, the given elongation is 2.5%, on one hand, the strip shape of the strip is straightened, and on the other hand, the elastic limit of the material is favorably improved;
in the step n, performing low-temperature annealing on the stretch-bent and straightened strip, and adopting continuous annealing treatment, wherein the low-temperature annealing temperature is 400 ℃, and the speed is 45m/min, so that on one hand, the residual stress of the strip is eliminated, and on the other hand, the comprehensive performance of the material, especially the elongation performance of the material, is improved;
after the above-described processing treatments of melting, pre-blooming, homogenizing annealing, surface milling, rough rolling, continuous annealing, finish rolling, stretch-bending leveling, low-temperature tension annealing, etc., the properties thereof are shown in example 7 in table 2.
Example 8
The composition of the alloy is shown in table 1, example 8.
In the step a, the specific feeding sequence is as follows: firstly adding copper (Cu), nickel (Ni) and iron (Fe), melting, then adding tin (Sn) and zinc ingots (Zn) at low temperature, adding copper phosphorus (Cu-P), Rare Earth (RE) alloy and nickel boron (NiB) alloy at low temperature after all the components are melted (adding after melting zinc element, the main purpose is to reduce the oxidation burning loss and realize the uniformity and stability of components), testing the components to be qualified, cleaning the furnace slag, and covering with baked charcoal; and casting by using a power frequency induction furnace in a non-vacuum environment, controlling the casting temperature at 1198 ℃, and casting by using a horizontal continuous casting mode.
The horizontal continuous casting process requires the following control: adopting the drawing length of 10.8mm, the drawing time of 0.7s, the middle stop of 3.0s, the return pushing length of 1.2mm, the return withdrawing time of 0.2s, the casting speed of 148mm/min, the strip billet outlet temperature of 310 ℃, the crystallization line on the surface of the strip billet should be straight and should have no visible casting defects such as cracks, gaps, pits, cold shut and the like; tin-phosphor bronze strip coil: the thickness is 14.5mm, the width is 430mm, and the length is 80 m.
And b, pre-blooming the high-tin bronze casting blank after rolling the blank, and pre-blooming the high-tin bronze casting blank in an arc control mode, wherein the deformation is 35%.
And c, carrying out homogenization annealing on the pre-blooming rolled coil blank, wherein the annealing temperature is 620 ℃, the heat preservation time is 8h, and further improving the surface segregation condition of tin.
In the step d, carrying out surface milling treatment on the coil blank subjected to homogenizing annealing, carrying out surface milling on line or off line, and milling each surface by 0.65mm, mainly removing surface oxide skin and eliminating a surface segregation layer;
step i, carrying out continuous annealing treatment in an air cushion type annealing furnace, wherein the high-tin phosphor bronze alloy adopts an ultrafine grain control technology, the tensile strength is controlled at 520MPa, and when the alloy is bent at 90 degrees, R/T is zero, and the alloy is not cracked when being bent;
step j, performing finish rolling on the strip subjected to the continuous annealing treatment, wherein the deformation is 30%;
in the step m, the strip subjected to acid cleaning treatment is subjected to stretch bending straightening, an elongation control mode is adopted, the given elongation is 3.4%, on one hand, the strip shape of the strip is straightened, and on the other hand, the elastic limit of the material is favorably improved;
in the step n, performing low-temperature annealing on the stretch-bent and straightened strip, and adopting continuous annealing treatment, wherein the low-temperature annealing temperature is 400 ℃, and the speed is 39m/min, so that on one hand, the residual stress of the strip is eliminated, and on the other hand, the comprehensive performance of the material, especially the elongation performance of the material, is improved;
after the above-described processing treatments of melting, pre-blooming, homogenizing annealing, surface milling, rough rolling, continuous annealing, finish rolling, stretch-bending leveling, low-temperature tension annealing, etc., the properties thereof are shown in example 8 in table 2.
Composition of alloy in Table 1, examples 1 to 8 (wt%)
| Examples | Sn | Zn | Ni | Fe | P | RE | B | Cu |
| Example 1 | 10.0 | 0.2 | 0.05 | 0.12 | 0.02 | 0.008 | 0.02 | Balance of |
| Example 2 | 10.5 | 0.3 | 0.2 | 0.12 | 0.05 | 0.005 | 0.015 | Balance of |
| Example 3 | 12.2 | 0.45 | 0.5 | 0.25 | 0.02 | 0.006 | 0.03 | Balance of |
| Example 4 | 12.5 | 0.1 | 0.12 | 0.5 | 0.01 | 0.01 | 0.02 | Balance of |
| Example 5 | 11.4 | 0.55 | 0.18 | 0.1 | 0.02 | 0.01 | 0.03 | Balance of |
| Example 6 | 13 | 0.15 | 0.13 | 0.16 | 0.035 | 0.006 | 0.018 | Balance of |
| Example 7 | 11.6 | 0.1 | 0.4 | 0.1 | 0.01 | 0.05 | 0.015 | Balance of |
| Example 8 | 11.0 | 0.65 | 0.35 | 0.35 | 0.035 | 0.075 | 0.023 | Balance of |
TABLE 2 alloy Properties of examples 1-8
| Examples | Tensile strength (MPa) | Elongation (%) | 90 degree R/T value (No cracking) | Elastic limit (MPa) | Stress relaxation Rate at Room temperature (100 h) |
| Example 1 | 1020 | 4.5 | 1.0 | 760 | 83 |
| Example 2 | 980 | 6.0 | 1.0 | 680 | 84.5 |
| Example 3 | 1060 | 4 | 1.2 | 790 | 82.5 |
| Example 4 | 1120 | 3 | 1.5 | 850 | 81 |
| Example 5 | 1090 | 3 | 1.5 | 795 | 82.5 |
| Example 6 | 1020 | 5.5 | 1.5 | 730 | 83.5 |
| Example 7 | 960 | 5.0 | 1.0 | 660 | 86 |
| Example 8 | 1100 | 3.5 | 1.5 | 820 | 82 |
The above description of the preferred embodiments of the present invention is provided to enable those skilled in the art to make various changes and modifications without departing from the spirit of the present invention, and these changes and modifications should be construed as being included in the scope of the present invention.
Claims (8)
1. A high-performance phosphor bronze band comprises the following chemical components in percentage by weight: 10.0-11.6% of Sn10, 0.1-0.65% of Zn, 0.05-0.5% of Ni, 0.1-0.5% of Fe, 0.01-0.5% of P, 0.001-0.02% of RE, 0.005-0.05% of B and the balance of Cu; the preparation method of the high-performance phosphor bronze band comprises the following steps: a. preparing materials, feeding materials, smelting and casting according to mass percentage, b, pre-primary rolling, c, homogenizing annealing, d, milling surfaces, e, rough rolling, f, intermediate annealing, g, acid washing, h, intermediate rolling, i, continuous annealing, j, finish rolling, k, acid washing, m, stretch bending and straightening, n, low-temperature annealing, o, shearing, p, packaging and warehousing; in the step m, the stretch bending straightening adopts an elongation control mode, and the given elongation is 2.5-4.5%; in step n, the temperature of the low-temperature annealing is 400 ℃, and the speed is 35-45 m/min.
2. The high performance phosphor bronze band according to claim 1, wherein: the alloy comprises the following chemical components, by weight, 10.5-11.5% of Sns, 0.1-0.35% of Zn, 0.1-0.2% of Ni, 0.1-0.2% of Fe, 0.01-0.05% of P, 0.005-0.01% of RE, 0.015-0.03% of B, and the balance of Cu.
3. A process for making the high performance phosphor bronze strip of claim 1, comprising the steps of: a. the method comprises the following steps of proportioning, feeding, smelting and casting according to mass percentage, b, pre-primary rolling, c, homogenizing annealing, d, milling surface, e, rough rolling, f, intermediate annealing, g, acid washing, h, intermediate rolling, i, continuous annealing, j, finish rolling, k, acid washing, m, stretch bending and straightening, n, low-temperature annealing, o, shearing, p, packaging and warehousing.
4. A process according to claim 3, characterized in that: adding copper, nickel and iron, melting, adding tin and zinc ingots at low temperature, adding copper phosphorus, rare earth alloy and nickel-boron alloy at low temperature after all the materials are melted, testing the components to be qualified, cleaning slag, and covering with baked charcoal; and casting by adopting a power frequency induction furnace in a non-vacuum environment, controlling the casting temperature to be 1190-1210 ℃, and casting by adopting a horizontal continuous casting mode.
5. A process as claimed in claim 4, wherein the horizontal continuous casting process is controlled by drawing length of 10.0 ~ 12.0.0 mm, drawing time of 0.6 ~ 0.9.9 s, stop time of 2.5 ~ 3.2.2 s, push back length of 1.0 ~ 2.0.0 mm, push back time of 0.2 ~ 0.4.4 s, casting speed of 120 ~ 170mm/min, strip outlet temperature of 250 ~ 400 ℃, tin-phosphor bronze strip of 13.5 ~ 15.5.5 mm in thickness, 430 ~ 650mm in width and 70-150m in length.
6. A process according to claim 3, characterized in that: in the step b, pre-blooming is carried out in an arc control mode, the deformation amount is 30-35%, in the step c, the annealing temperature is 610-630 ℃, and the heat preservation time is 8-10 h.
7. A process according to claim 3, characterized in that: in the step j, the finish rolling processing rate is 30 to 50%.
8. A process according to claim 3, characterized in that: in the step m, the stretch bending straightening adopts an elongation control mode, and the given elongation is 2.5-4.5%; in step n, the temperature of the low-temperature annealing is 400 ℃, and the speed is 35-45 m/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710838024.8A CN107604202B (en) | 2017-09-18 | 2017-09-18 | High-performance phosphor bronze strip and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710838024.8A CN107604202B (en) | 2017-09-18 | 2017-09-18 | High-performance phosphor bronze strip and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107604202A CN107604202A (en) | 2018-01-19 |
| CN107604202B true CN107604202B (en) | 2020-01-21 |
Family
ID=61060494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710838024.8A Active CN107604202B (en) | 2017-09-18 | 2017-09-18 | High-performance phosphor bronze strip and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107604202B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109280802B (en) * | 2018-10-09 | 2019-12-03 | 松阳县景顺实业有限公司 | A kind of high performance high strength copper strips and its production method |
| CN109266877B (en) * | 2018-11-01 | 2019-11-08 | 福建紫金铜业有限公司 | A kind of preparation method of high property copper alloy |
| CN109266898B (en) * | 2018-11-21 | 2020-10-27 | 中航力源液压股份有限公司 | Cast tin bronze for friction pair of aviation hydraulic pump and smelting method thereof |
| CN113106290B (en) * | 2021-03-23 | 2022-04-26 | 宁波金田铜业(集团)股份有限公司 | High-performance tin-phosphor bronze strip and preparation method thereof |
| CN113369824B (en) * | 2021-06-30 | 2022-04-29 | 福建紫金铜业有限公司 | Production process of novel copper alloy plate strip material for welding |
| CN114032416A (en) * | 2021-11-18 | 2022-02-11 | 浙江惟精新材料股份有限公司 | Ultrahigh-strength tin-phosphor bronze and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100535737B1 (en) * | 2000-12-28 | 2005-12-09 | 닛꼬 긴조꾸 가꼬 가부시키가이샤 | High strength copper alloy excellent in bendability and method for producing the same and terminal and connector using the same |
| CN1180106C (en) * | 2002-06-14 | 2004-12-15 | 宁波博威集团有限公司 | Copper base high tin boron alloy |
| CN101525704B (en) * | 2008-03-07 | 2010-11-10 | 杭州钱王机械配件有限公司 | Alloy for manufacturing bush and method for manufacturing bush thereof |
| CN106636729A (en) * | 2016-10-05 | 2017-05-10 | 宁波兴业盛泰集团有限公司 | Polybasic copper alloy plate and strip for power battery connector and preparation method thereof |
-
2017
- 2017-09-18 CN CN201710838024.8A patent/CN107604202B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107604202A (en) | 2018-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107604202B (en) | High-performance phosphor bronze strip and preparation method thereof | |
| CN108796384B (en) | High-surface-quality aluminum-clad plate strip easy to punch and process and production method thereof | |
| CN110106428B (en) | High-entropy alloy with banded precipitated phases and preparation method thereof | |
| CN100425717C (en) | Copper alloy for lead-wire frame and its production | |
| CN107881427B (en) | Low-yield-strength aluminum-coated substrate with excellent plasticity | |
| CN100469923C (en) | High temperature copper alloy for lead frame and its making process | |
| CN109266901B (en) | Preparation method of Cu15Ni8Sn high-strength wear-resistant alloy rod/wire | |
| CN112874058B (en) | Copper-steel solid-liquid composite bimetallic material for buildings and preparation method thereof | |
| CN107699730A (en) | A kind of corrosion resistant high-strength tin copper-phosphorus alloy and its forming technology | |
| CN109161793A (en) | A kind of low yield strength ratio high-strength weathering steel and its production method | |
| CN105274386A (en) | High-performance complex multi-element phosphor bronze alloy material and preparation method thereof | |
| CN101654749A (en) | Easily-cutting brass and processing method of strips thereof | |
| CN108690921A (en) | A kind of high-performance phosphorus bronze band and preparation method thereof | |
| CN107974574B (en) | Stress relaxation-resistant complex brass alloy and preparation method thereof | |
| CN114262854A (en) | Preparation method of high-strength tin bronze alloy | |
| CN110306077B (en) | Corrosion-resistant copper alloy for electric connector and preparation method thereof | |
| CN103421980B (en) | A kind of high-strength elastic brass and preparation method thereof | |
| CN102321827B (en) | Preparation method for high-conductivity and low-tin bronze strip | |
| CN107619964B (en) | High-conductivity copper-silver-tin-chromium alloy plate strip and preparation and processing method thereof | |
| CN113981338B (en) | Structure control method of iron-rich aluminum alloy | |
| CN113969364B (en) | High-strength high-conductivity copper-niobium alloy and preparation method thereof | |
| CN109722604B (en) | Tin plate for two-piece spray can and manufacturing method thereof | |
| CN112877564B (en) | Copper-steel solid-liquid composite bimetallic material for hot extrusion die and preparation method thereof | |
| CN113385549A (en) | Composite processing method of high-strength high-conductivity pure copper wire | |
| CN114507793A (en) | High-strength high-conductivity Cu-Zn-Cr-Zr copper alloy, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Liu Feng Inventor after: Fu Bowen Inventor after: Shi Yangnong Inventor after: Ma Jimiao Inventor after: Ma Wanjun Inventor after: Chen Jianhua Inventor after: Xiong Weixuan Inventor after: Zhang Ligui Inventor after: Cheng Wanlin Inventor after: Chen Wensong Inventor after: Lei Fuqing Inventor before: Liu Feng Inventor before: Ma Jimiao Inventor before: Zhang Ligui Inventor before: Cheng Wanlin Inventor before: Fu Bowen Inventor before: Chen Wensong Inventor before: Shi Yangnong |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |