CN114250391A - Anodic oxidation high-magnesium aluminum alloy material and preparation method thereof - Google Patents
Anodic oxidation high-magnesium aluminum alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention provides an anodizable high magnesium aluminum alloy material and a preparation method thereof, wherein the material comprises the following chemical materials in percentage by weight: less than or equal to 0.08 percent of Si, less than or equal to 0.12 percent of Fe, 0.03-0.15 percent of Cu, Mn: 0.1-0.25%, Mg: 5.2-6.0%, Cr is less than or equal to 0.05%, Zn is less than or equal to 0.1%, Ti: 0.005-0.015%, Na is less than or equal to 0.0001%, Be: 0.001-0.005% and the balance of AL, the finished product made according to the alloy composition can meet the requirements of terminal customers, and the anode has the characteristics of good anode effect, no material grains, light weight, high strength and good forming.
Description
Technical Field
The invention belongs to the technical field of high magnesium aluminum alloy materials, and particularly relates to an anodizable high magnesium aluminum alloy material and a preparation method thereof.
Background
With the development of electronic 3C products, the 3C products are more pursuing light weight and beauty. This requires a reduction in unit weight while also increasing the strength of the product housing member and the aesthetic appearance of the appearance member. The aluminum alloy material has the advantages of small specific gravity, good corrosion resistance, good processing and forming performance, high heat conductivity, good anodic oxidation coloring effect and the like.
The appearance material used by domestic pen and electricity products, low-strength 5 series material or 6061T6, the main alloy is 5052 or 5252 alloy, the anode effect is good, the defect is that the material strength is low, and the material strength used in the current market is tensile strength: 230-255Mpa, yield strength: 155-175 MPa. The 6061T6 material has the defects of poor formability, easy cracking, non-uniformity and the like after heat treatment, and has the advantage of good anodic oxidation effect; the product is required to be light in weight and thin in thickness in the 3C field, the appearance quality is not reduced, in order to adapt to market demands and light development of the product, an aluminum alloy material capable of replacing stainless steel needs to be found out, and the surface of the aluminum alloy material can meet the requirements of anodic oxidation coloring and is novel aluminum alloy material with high strength and formability while meeting the strength requirements.
Document No. CN 111235442 a discloses an anodizable die-casting aluminum alloy for thin-wall products, which effectively adjusts the mass percentage of each element in the aluminum alloy, and utilizes the synergistic effect of Ti element and Ni element with other components to achieve the effects of high strength, good fluidity, no sticking to the mold, and retention of good casting performance and mechanical performance, but has no significant improvement in light weight, product thickness and the requirement of surface energy satisfying the coloring of the anodic oxidation.
Disclosure of Invention
The invention aims to provide an anodizable high magnesium aluminum alloy material and a preparation method thereof, wherein the anodizable high magnesium aluminum alloy material has high strength, high toughness and high elongation and can meet the requirement that a No. 150 sand blasting anode has no material grains.
In order to achieve the above object, the technical solution of the present invention is as follows: the invention provides an anodizable high magnesium aluminum alloy material, which comprises the following chemical components: less than or equal to 0.08 percent of Si, less than or equal to 0.12 percent of Fe, 0.03-0.15 percent of Cu, Mn: 0.1-0.25%, Mg: 5.2-6.0%, Cr is less than or equal to 0.05%, Zn is less than or equal to 0.1%, Ti: 0.005-0.015%, Na is less than or equal to 0.0001%, Be: 0.001-0.005% and the balance of Al.
The invention also provides a preparation method of the anodizable high magnesium aluminum alloy material, which comprises the following steps:
(1) preparing materials: si, Fe, Cu, Mn, Mg, Cr, Zn, Ti, Na, Be and AL are adopted for proportioning;
(2) smelting: adding raw aluminum ingots with the purity of 99.9 percent, then heating and smelting, wherein the smelting temperature is 720-760 ℃, adding a manganese agent chromium agent and magnesium ingots after melting the aluminum ingots, then adding an intermediate alloy AL-Be, stirring, refining, and slagging off;
(3) refining and degassing: after the components are qualified, firstly refining by using nitrogen-chlorine mixed gas, ensuring that the sodium content meets the requirement, secondly refining by using argon, and detecting that the hydrogen content of the liquid aluminum alloy is not higher than 0.15 ml/100 gAl;
(4) casting: the casting speed is 40-50mm/min, the water pressure is 0.1-0.2Mpa, and the water temperature is less than or equal to 30 ℃ according to the casting temperature of 690-720 ℃, so as to obtain a flat cast ingot meeting the internal control standard
(5) Homogenizing cast ingots: during the solidification period of casting, the segregation of solute elements causes the aggregation of alloying elements, the homogenization treatment is more uniform and consistent tissue structure, the performance of the final product is consistent, and the segregation of high-solid concentration elements and low-solid concentration elements is reduced or eliminated in the homogenization process;
(6) milling a surface: milling a single surface of the cast ingot by more than 15mm to ensure that a coarse crystal layer on the surface of the cast ingot is milled;
(7) hot rolling: in the front section of cogging rolling, rolling is carried out by using large rolling force so as to ensure that a casting structure is fully crushed and converted into a processing structure;
(8) cold rolling: adopting a natural gas furnace annealing process with the metal temperature of 300-
(9) Sand blasting: the sand blasting pressure is more than 0.28Mpa, and the roughness Ra is more than 1.8 mu m.
The invention is further improved in that: in the step (2), the stirring time is 20-30 min.
The invention is further improved in that: in the step (2), the addition amount of the Al-Be is 15-20 ppm.
The invention is further improved in that: in the step (3), the nitrogen-chlorine mixed gas is refined, wherein the proportion of chlorine gas reaches 8-10%, the refining time is 30min, the refining time is 20-25min during argon refining, and the refining temperature is 750-760 ℃.
The invention is further improved in that: and (4) filtering the obtained material before casting in the step (4), wherein a tubular filter plate is adopted for filtering so as to ensure the purity of the material.
The invention is further improved in that: before the surface milling in the step (6), a two-stage soaking process of 435-.
The invention is further improved in that: in the step (8), the annealing temperature is 280-320 ℃, and the temperature rise rate is more than 40 ℃ per hour.
The invention is further improved in that: and (5) in the step (9), blasting sand by adopting 150#20% sharp-angle and 80% rounded steel grit.
The anodizable high-magnesium aluminum alloy material has the beneficial effects that the material is uniform in grain size, the bending non-cracking toughness and the uniformity after the anode are guaranteed, the anodizable high-magnesium aluminum alloy material is mainly applied to 3C product appearance pieces, the requirements of terminal customers can be met, and the anodizable high-magnesium aluminum alloy material has the characteristics of light weight, high strength, high toughness, high elongation rate, capability of meeting 150# sand blasting, no material grains of the anode and no black lines.
Detailed Description
In order to enhance the understanding of the present invention, the present invention will be described in further detail with reference to the following examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the present invention.
Example 1:
the technical solution of the embodiment is as follows: the embodiment provides an anodizable high magnesium aluminum alloy material, which comprises the following chemical components: 0.08% of Si, 0.12% of Fe0, 0.1% of Cu, Mn: 0.2%, Mg: 5.5%, Cr0.05%, Zn0.1%, Ti: 0.01%, Na0.0001%, Be: 0.003% and the balance of Al.
The preparation method of the anodizable high magnesium aluminum alloy material specifically comprises the following steps:
(1) preparing materials: the alloy comprises the following materials in percentage by weight, namely Si0.08%, Fe0.12%, Cu 0.1%, Mn: 0.2%, Mg: 5.5%, Cr0.05%, Zn0.1%, Ti: 0.01%, Na0.0001%, Be: 0.003% of Al, and the balance of Al;
(2) smelting: adding raw aluminum ingots with the purity of 99.9 percent, then heating and smelting, wherein the smelting temperature is 750 ℃, adding a manganese agent chromium agent and magnesium ingots after melting the aluminum ingots, then adding 18ppm of intermediate alloy AL-Be, stirring for 25min, refining, and slagging off;
(3) refining and degassing: refining with mixed gas of nitrogen and chlorine for the first time after the components are qualified, wherein the proportion of chlorine reaches 9%, refining is carried out for 30min, and the content of sodium is ensured to meet the requirement, refining is carried out with argon for the second time, the refining time is 22min, the refining temperature is 755 ℃, and the hydrogen content of the liquid aluminum alloy is detected to be not higher than 0.15 ml/100 gAl;
(4) and (3) filtering: the tubular filter plate is adopted for filtering, so that the purity of the material is ensured;
(5) casting: performing the processes according to the casting temperature of 700 ℃, the casting speed of 45mm/min, the water pressure of 0.15Mpa and the water temperature of 30 ℃ to obtain flat ingots meeting the internal control standard;
(6) homogenizing cast ingots: during the solidification period of casting, the segregation of solute elements causes the aggregation of alloying elements, the homogenization treatment is more uniform and consistent tissue structure, the performance of the final product is consistent, and the segregation of high-solid concentration elements and low-solid concentration elements is reduced or eliminated in the homogenization process;
(7) soaking the raw materials: carrying out ingot casting soaking treatment by adopting a two-stage soaking process of 440 ℃/10h +505 ℃/12h so as to reduce the segregation in the crystal;
(8) milling a surface: milling a single surface of the cast ingot by more than 15mm to ensure that a coarse crystal layer on the surface of the cast ingot is milled;
(9) hot rolling: in the front section of cogging rolling, rolling is carried out by using large rolling force so as to ensure that a casting structure is fully crushed and converted into a processing structure;
(10) cold rolling: through a small furnace annealing experiment, the final natural gas furnace annealing process with the metal temperature of 305 ℃/2h and the total time of 13h is determined, and the grain size of the finished product is ensured to be less than or equal to 40 mu m under 35% of total pressure after annealing;
(11) sand blasting: the strength of the material is improved, the surface hardness is improved, the sand effect of sand blasting on the surface of the material is weakened, 150#20% sharp angle and 80% round angle steel sand are used, the sand blasting pressure is 0.28Mpa, and the roughness Ra is more than 1.8 mu m.
In this embodiment, during the casting process, the aluminum alloy forms a dendritic structure during the casting process, the size of the dendritic structure depends on the solidification speed, the aluminum alloy is cooled too fast to form fine columnar crystals, a layer of columnar crystal edge area is usually arranged near the surface of the ingot, and coarse dendritic crystals grow from the wall of the crystallizer to the interior of the ingot. The rough dendrite of the ingot can leave stripes on the surface of the material during rolling, the structural difference caused by different solidification speeds cannot be completely eliminated in subsequent processing, and the casting process implemented according to the implementation can obtain a flat ingot meeting the internal control standard.
In the ingot homogenizing treatment step, eutectic phase particles are positioned among the dendrites, the dispersity of the second phase particles is directly related to the size of finished product crystal grains, and the crystal grains are fine to generate fine particles. During the solidification of casting, the segregation of solute elements causes the aggregation of alloying elements, the homogenization treatment is more uniform and consistent tissue structure, the performance of the final product is consistent, during the homogenization process, high solid concentration elements and low solid concentration elements are required, the former (such as Si, Cu, Mg and Zn) can be dissolved in a large amount, the segregation is reduced or eliminated, the primary particles of the low solid concentration elements are mainly A1FeMnSi type intermetallic compounds, and the coarse particles between dendrites are spheroidized due to the homogenization to form secondary fine dispersed particles.
During hot rolling, the larger primary phase particles are usually hard and brittle particles, and are crushed by hot rolling and cold rolling, the crushed particle fragments are redistributed, and the meaning of the fine grain structure is that the primary phase particles are correspondingly fine, and the particles are uniformly distributed by hot rolling and cold rolling. The primary phase points are located at the grains and grain boundaries and extend as lines. The higher the deformation ratio, the closer the lines are and the fewer the number of particles per line. In the early stage of cogging, high rolling force is used for rolling, so that the cast structure is fully crushed and converted into a processed structure. And the trace element Na has obvious influence on the fracture behavior of the alloy, the hot rolling plasticity of the alloy is improved when the Na content is lower, and the fracture hardly occurs in the hot rolling process, which has influence on the elongation of subsequent finished products.
Because the material has high strength, low plasticity and large deformation resistance, the material is not easy to thin in the processing process, the reduction processing rate in the first and second rolling processes is more than 50-60 percent, the reduction processing rate in the third rolling process is 45-55 percent, and the reduction processing rate in the last rolling process is 15-25 percent, and the crystal grains of the material structure are crushed to obtain a finer grain structure. The annealing temperature is 280-320 ℃, the temperature rise rate is more than 40 ℃ per hour, the reduction processing rate between the last rolling process is reduced, namely the reduction processing rate is equal to a fine grain structure after the first three rolling processes, so that the fine grain structure is fiberized, the strength of the material is improved, and the bending toughness of the material is ensured.
In terms of high magnesium aluminum alloy, except for chemical components, the texture structure of the material is greatly influenced by the quality of anodic oxidation, and the texture structure of the material is determined by a processing process, so that the whole production process from casting to machining and forming can be strictly controlled to ensure the quality requirement of the surface of a final product, and in a hot rolling and cold rolling processing section, crystal grains are crushed through large reduction cold deformation to obtain a more uniform texture structure, so that performance guarantee is provided for subsequent processing and use of the material, and after stamping, the mechanical properties need to meet the following requirements:
example 2: the difference between the example 2 and the example 1 is only the ratio of the chemical components and the different parameters of the steps in the preparation process, and the specific operation is as follows:
(1) preparing materials: the alloy is prepared from the following materials in percentage by weight, namely 0.05% of Si, 0.1% of Fe0, 0.03% of Cu, and Mn: 0.1%, Mg: 5.2%, Cr0.03%, Zn0.05%, Ti: 0.005%, Na0.0001%, Be: 0.001% and the balance of AL;
(2) smelting: adding raw aluminum ingots with the purity of 99.9 percent, then heating and smelting, wherein the smelting temperature is 720 ℃, adding a manganese agent chromium agent and magnesium ingots after melting the aluminum ingots, then adding 15ppm of intermediate alloy AL-Be, stirring for 20min, refining, and slagging off;
(3) refining and degassing: refining with nitrogen-chlorine mixed gas for the first time after the components are qualified, wherein the proportion of chlorine reaches 8%, refining for 30min, and ensuring that the sodium content meets the requirement; refining with argon for the second time at 750 deg.C for 20min, and detecting that the hydrogen content of the liquid aluminum alloy is not higher than 0.15 ml/100 gAl;
(4) and (3) filtering: the tubular filter plate is adopted for filtering, so that the purity of the material is ensured;
(5) casting: performing the processes according to the casting temperature of 690 ℃, the casting speed of 40mm/min, the water pressure of 0.1Mpa and the water temperature of 25 ℃ to obtain flat ingots meeting the internal control standard;
(6) homogenizing cast ingots: during the solidification period of casting, the segregation of solute elements causes the aggregation of alloying elements, the homogenization treatment is more uniform and consistent tissue structure, the performance of the final product is consistent, and the segregation of high-solid concentration elements and low-solid concentration elements is reduced or eliminated in the homogenization process;
(7) soaking the raw materials: carrying out ingot casting soaking treatment by adopting a double-stage soaking process of 435 ℃/10h +500 ℃/12h so as to reduce the segregation in the crystal;
(8) milling a surface: milling a single surface of the cast ingot by more than 15mm to ensure that a coarse crystal layer on the surface of the cast ingot is milled;
(9) hot rolling: in the front section of cogging rolling, rolling is carried out by using large rolling force so as to ensure that a casting structure is fully crushed and converted into a processing structure;
(10) cold rolling: through a small furnace annealing experiment, the final natural gas furnace annealing process with the metal temperature of 300 ℃/2h and the total time of 12h is determined, and the grain size of the finished product is ensured to be less than or equal to 40 mu m under the total pressure of 25 percent after annealing;
(11) sand blasting: the strength of the material is improved, the surface hardness is improved, the sand effect of sand blasting on the surface of the material is weakened, 150#20% sharp angle and 80% round angle steel sand are used, the sand blasting pressure is 0.28Mpa, and the roughness Ra is more than 1.8 mu m.
Example 3:
example 3 is different from examples 1 and 2 only in the ratio of chemical components and the parameters of each step in the preparation process, and the specific operation is as follows:
(1) preparing materials: the alloy proportioning is carried out by adopting the following materials by weight percent, namely Si0.06 percent, Fe0.11 percent, Cu 0.15 percent, Mn: 0.25%, Mg: 6.0%, Cr0.04%, Zn0.07%, Ti: 0.015%, Na0.0001%, Be: 0.005% and the balance of AL;
(2) smelting, namely adding raw aluminum ingots with the purity of 99.9 percent, then heating and smelting, wherein the smelting temperature is 760 ℃, melting the aluminum ingots, then adding a manganese agent chromium agent and magnesium ingots in sequence, then adding 20ppm of intermediate alloy AL-Be, then stirring, stirring for 30min, refining, and slagging off;
(3) refining and degassing: refining with nitrogen-chlorine mixed gas for the first time after the components are qualified, wherein the proportion of chlorine reaches 10%, and refining for 30min to ensure that the sodium content meets the requirement; refining with argon for the second time at the refining temperature of 760 ℃ for 25min, and detecting that the hydrogen content of the liquid aluminum alloy is not higher than 0.15 ml/100 gAl;
(4) and (3) filtering: the tubular filter plate is adopted for filtering, so that the purity of the material is ensured;
(5) casting: performing the processes according to the casting temperature of 720 ℃, the casting speed of 50mm/min, the water pressure of 0.2Mpa and the water temperature of 30 ℃ to obtain flat ingots meeting the internal control standard;
(6) homogenizing cast ingots: during the solidification period of casting, the segregation of solute elements causes the aggregation of alloying elements, the homogenization treatment is more uniform and consistent tissue structure, the performance of the final product is consistent, and the segregation of high-solid concentration elements and low-solid concentration elements is reduced or eliminated in the homogenization process;
(7) soaking the raw materials: carrying out ingot casting soaking treatment by adopting a two-stage soaking 445 ℃/10h +510 ℃/12h process to reduce the segregation in the crystal;
(8) milling a surface: milling a single surface of the cast ingot by more than 15mm to ensure that a coarse crystal layer on the surface of the cast ingot is milled;
(9) hot rolling: in the front section of cogging rolling, rolling is carried out by using large rolling force so as to ensure that a casting structure is fully crushed and converted into a processing structure;
(10) cold rolling: through a small furnace annealing experiment, the final natural gas furnace annealing process with the metal temperature of 310 ℃/2h and the total time of 12h is determined, and the grain size of the finished product is ensured to be less than or equal to 40 mu m under the total pressure of 45 percent after annealing;
(11) sand blasting: the strength of the material is improved, the surface hardness is improved, the sand effect of sand blasting on the surface of the material is weakened, 150#20% sharp angle and 80% round angle steel sand are used, the sand blasting pressure is 0.3Mpa, and the roughness Ra is more than 1.8 mu m.
It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. An anodizable high magnesium aluminum alloy material is characterized in that: the material comprises the following chemical materials in percentage by weight: less than or equal to 0.08 percent of Si, less than or equal to 0.12 percent of Fe, 0.03-0.15 percent of Cu, Mn: 0.1-0.25%, Mg: 5.2-6.0%, Cr is less than or equal to 0.05%, Zn is less than or equal to 0.1%, Ti: 0.005-0.015%, Na is less than or equal to 0.0001%, Be: 0.001-0.005% and the balance of Al.
2. The method of claim 1, wherein the anodized high magnesium aluminum alloy material is prepared by: the method specifically comprises the following steps:
preparing materials: si, Fe, Cu, Mn, Mg, Cr, Zn, Ti, Na, Be and AL are adopted for proportioning;
smelting: adding raw aluminum ingots with the purity of 99.9 percent, then heating and smelting, wherein the smelting temperature is 720-760 ℃, adding a manganese agent chromium agent and magnesium ingots after melting the aluminum ingots, then adding an intermediate alloy AL-Be, stirring, refining, and slagging off;
refining and degassing: after the components are qualified, firstly refining by using nitrogen-chlorine mixed gas, ensuring that the sodium content meets the requirement, secondly refining by using argon, and detecting that the hydrogen content of the liquid aluminum alloy is not higher than 0.15 ml/100 gAl;
casting: performing the process according to the casting temperature of 690-720 ℃, the casting speed of 40-50mm/min, the water pressure of 0.1-0.2Mpa and the water temperature of less than or equal to 30 ℃ to obtain a flat ingot meeting the internal control standard;
homogenizing cast ingots: during the solidification period of casting, the segregation of solute elements causes the aggregation of alloying elements, the homogenization treatment is more uniform and consistent tissue structure, the performance of the final product is consistent, and the segregation of high-solid concentration elements and low-solid concentration elements is reduced or eliminated in the homogenization process;
milling a surface: milling a single surface of the cast ingot by more than 15mm to ensure that a coarse crystal layer on the surface of the cast ingot is milled;
hot rolling: in the front section of cogging rolling, rolling is carried out by using large rolling force so as to ensure that a casting structure is fully crushed and converted into a processing structure;
cold rolling: adopting a natural gas furnace annealing process with the metal temperature of 300-;
sand blasting: the sand blasting pressure is more than 0.28Mpa, and the roughness Ra is more than 1.8 mu m.
3. The method of claim 1, wherein the anodized high magnesium aluminum alloy material is prepared by: in the step (2), the stirring time is 20-30 min.
4. The method of claim 1, wherein the anodized high magnesium aluminum alloy material is prepared by: in the step (2), the addition amount of the Al-Be is 15-20 ppm.
5. The method of claim 1, wherein the anodized high magnesium aluminum alloy material is prepared by: in the step (3), the nitrogen-chlorine mixed gas is refined, wherein the proportion of chlorine gas reaches 8-10%, the refining time is 30min, the refining time is 20-25min during argon refining, and the refining temperature is 750-760 ℃.
6. The method of claim 1, wherein the anodized high magnesium aluminum alloy material is prepared by: the material obtained is filtered before the casting in step (4), using a tube filter plate.
7. The method of claim 1, wherein the anodized high magnesium aluminum alloy material is prepared by: and (4) carrying out ingot casting heat soaking treatment by adopting a two-stage heat soaking process of 435-.
8. The method of claim 1, wherein the anodized high magnesium aluminum alloy material is prepared by: in the step (8), the annealing temperature is 280-320 ℃, and the temperature rise rate is more than 40 ℃ per hour.
9. The method of claim 1, wherein the anodized high magnesium aluminum alloy material is prepared by: and (5) in the step (9), blasting sand by adopting 150#20% sharp-angle and 80% rounded steel grit.
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| CN114517277A (en) * | 2022-04-21 | 2022-05-20 | 中铝材料应用研究院有限公司 | Aluminum alloy thick plate and preparation method thereof |
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| GB2245591A (en) * | 1990-06-05 | 1992-01-08 | Sky Aluminium | Diaphragm aluminum alloy plates and their preparation |
| CN111593236A (en) * | 2020-06-22 | 2020-08-28 | 中铝瑞闽股份有限公司 | High-strength high-elongation Al-Mg alloy plate for automobile and preparation process thereof |
| CN112322945A (en) * | 2020-10-29 | 2021-02-05 | 大力神铝业股份有限公司 | Aluminum alloy material for 3C product and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114517277A (en) * | 2022-04-21 | 2022-05-20 | 中铝材料应用研究院有限公司 | Aluminum alloy thick plate and preparation method thereof |
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