CN115717207A - 6-series aluminum alloy for hard anodic oxidation and manufacturing method thereof - Google Patents
6-series aluminum alloy for hard anodic oxidation and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses a 6-series aluminum alloy for hard anodic oxidation, which contains Al and inevitable impurities, and also contains the following chemical elements in percentage by mass: si:0.45-0.6%, cu:0.1-0.2%, mn:0.06-0.12%, mg:0.74-1.0%, cr:0.05-0.15%, zr:0.07-0.14%, more than 0 and less than or equal to 0.15% of Ti, and less than or equal to 0.25% of Fe. Correspondingly, the invention also discloses a manufacturing method of the 6-series aluminum alloy, which comprises the following steps: smelting and casting to obtain an aluminum alloy ingot; (2) heating: controlling the heating speed to be 20-40 ℃/h, preserving the heat at 530-560 ℃ for 4-24h, and discharging; (3) hot rolling: performing multi-pass rolling to achieve the target thickness, and controlling the rolling temperature of the plate blank under a certain pass to be 500-565 ℃ when the thickness of the plate blank under the certain pass is more than 100mm during the multi-pass rolling; (4) solution heat treatment; (5) stretching treatment; and (6) aging treatment.
Description
Technical Field
The invention relates to an aluminum alloy and a manufacturing method thereof, in particular to a 6-series aluminum alloy and a manufacturing method thereof.
Background
It is known that during the production of aluminum alloys, a dense layer of Al is formed on the surface of the aluminum alloy by hard anodizing 2 O 3 Film of such Al 2 O 3 The thickness of the film is generally between 25 and 150 mu m, and the film has stronger corrosion resistance, abrasion resistance and insulation effects and can effectively improve the surface performance of the aluminum alloy material.
In the field of semiconductor and tool die processing, the hard anodizing method is commonly adopted for aluminum alloy thick plate tools to obtain Al with uniform color 2 O 3 And (3) a membrane. At present, the 6-series anodized aluminum alloy thick plate can obtain uniform oxide films on the upper surface and the lower surface after hard oxidation, but the oxide film on the cross section of the 6-series anodized aluminum alloy thick plate often has the phenomenon that the edge part is inconsistent with the center part, and the strip defect in the thickness cross section direction is easy to occur.
The difference between the core structure and the thickness edge structure of the conventional 6-series aluminum alloy is large, and Mg in a matrix 2 The uneven distribution of Si and AlFeSi phases may cause uneven anodic oxide film on the thickness section of the 6-series aluminum alloy thick plate, and the structural difference may occur at the center position, thereby inducing a band defect.
At present, in the prior art, the method for improving the structure difference of the 6 series aluminum alloy is generally as follows: improving the homogeneity of the as-cast structure (such as adopting electromagnetic casting), adopting a strong deformation process, adopting a homogenization heat treatment and the like. However, none of the above-mentioned technical means can effectively alleviate or eliminate the defect of the 6-series aluminum alloy.
Publication No. CN106591646AThe publication date is 2017, 4 and 26, and Chinese patent document named as 6061 aluminum alloy discloses 6061 aluminum alloy which contains 0.3-0.35% of Fe0.08-0.12% of Mn0.08. The color of the hard oxide is blacker by increasing the content of Fe, and meanwhile, in order to eliminate the adverse effect of Fe, the content of Mn is increased to form Al 6 Mn, in which part of Fe is dissolved, weakens the adverse effect of Fe in the aluminum alloy. By adopting the technical scheme, the hard oxidation surface of the product can be changed into grey black from golden yellow.
Chinese patent publication No. CN106694547B, published as 26.3.2019, entitled "hot rolling process of hard aluminum alloy for anodic oxidation", discloses a hot rolling process of hard aluminum alloy for anodic oxidation, which comprises the steps of: homogenizing and preserving heat at 490 ℃ for 8h, and then performing initial rolling at 440-460 ℃ by adopting an equal reduction distribution principle after homogenization; when the hot rolling is carried out to 370-390 ℃, the first rolling is carried out under the small reduction with the reduction rate of 7%, and then the first rolling is carried out under the overpressure with the reduction rate of 45%; then, continuously adopting the equal reduction distribution principle to roll, and controlling the rolling temperature to be 250-270 ℃. In the technical scheme, the production mode that a single-stand hot rolling mill is adopted to replace a plurality of stands is optimized.
Chinese patent publication No. CN101792877A, publication No. 2010, 8 months and 4 days, entitled "an aluminum alloy for semiconductor device and method for producing the same", discloses an aluminum alloy for semiconductor device, which comprises the following components in parts by weight: 1.00 to 1.20 percent of Mg, 0.58 to 0.75 percent of Si, 1.6 to 1.73 percent of Mg/Si, 0.10 to 0.15 percent of Cu, 0.04 to 0.20 percent of Cr, 0.10 to 0.40 percent of Mn, 0.015 to 0.02 percent of Ti, less than or equal to 0.3 percent of Fe and the balance of Al. The invention improves the structure uniformity of the aluminum alloy material for the semiconductor equipment by optimizing and controlling the alloy elements, and the second phase is completely distributed in the crystal and has the size not more than 5 microns. The alloy can obtain a base material after forging processing, the oxide film of the base material after anodic oxidation is uniform and consistent, the quality is good, and the defects of pinholes and the like do not exist.
With reference to the above prior patent documents, and in combination with various current improvement schemes, it is easy to find that researchers in the field mainly control the content of Fe as an impurity element and adopt processes such as homogenization or strong deformation to achieve the effect of reducing or breaking the AlFeSi phase and improve the anodic oxidation requirement of the aluminum alloy for the aluminum alloy with the anodic oxidation requirement. However, the design method cannot effectively solve the strip-shaped appearance defect of the middle part of the thickness section of the aluminum alloy.
Based on the defects and shortcomings in the prior art, the invention aims to obtain a novel 6-series aluminum alloy for hard anodic oxidation and a manufacturing method thereof, wherein the novel 6-series aluminum alloy adopts reasonable chemical component proportion and is matched with optimized homogenization and hot rolling processes to effectively improve Mg 2 The distribution of the Si phase and the AlFeSi phase ensures that the surface of the aluminum alloy after the hard anodic oxidation presents a uniform and consistent oxide film layer, the section of the aluminum alloy in the thickness direction has no strip defect, and the problem that the section part of the 6-series aluminum alloy thick plate in the prior art has appearance defect after the hard oxidation can be effectively solved.
Disclosure of Invention
One of the purposes of the invention is to provide a 6-series aluminum alloy for hard anodic oxidation, which can effectively improve Mg by adopting reasonable chemical component proportion and matching with optimized homogenization and hot rolling process 2 The distribution of the Si phase and the AlFeSi phase ensures that the surface of the aluminum alloy after the hard anodic oxidation presents a uniform and consistent oxide film layer, the section of the aluminum alloy in the thickness direction has no strip defect, and the problem that the section part of the 6-series aluminum alloy thick plate in the prior art has appearance defect after the hard oxidation can be effectively solved.
In order to achieve the purpose, the invention provides a 6-series aluminum alloy for hard anodizing, which contains Al and inevitable impurities, and further contains the following chemical elements in percentage by mass:
Si：0.45-0.6％，Cu：0.1-0.2％，Mn：0.06-0.12％，Mg：0.74-1.0％，Cr：0.05-0.15％，Zr：0.07-0.14％，0＜Ti≤0.15％，Fe≤0.25％。
further, in the 6-series aluminum alloy of the invention, the mass percentages of the chemical elements are as follows: si:0.45-0.6%, cu:0.1-0.2%, mn:0.06-0.12%, mg:0.74-1.0%, cr:0.05 to 0.15%, zr:0.07-0.14 percent, more than 0 percent and less than or equal to 0.15 percent of Ti, and less than or equal to 0.25 percent of Fe; the balance being Al and unavoidable impurities.
In the 6-series aluminum alloy of the present invention, the design principle of each chemical element is as follows:
si, mg: in the 6 series aluminum alloy, mg and Si are main strengthening elements, and the combination of Mg and Si can form nano-scale Mg in dispersion distribution in the 6 series aluminum alloy 2 Si phase, and thus may play a major strengthening role.
It should be noted that, in general, while the mass percentage of a single chemical element is controlled, the weight ratio of Mg to Si may be further preferably controlled. When the Mg/Si weight ratio is controlled to be 1.73, the Mg element and the Si element can be formed just completely as Mg 2 Si; when the Mg/Si ratio is higher than 1.73, excess Mg is formed; when Mg/Si is less than 1.73, excess Si is formed. The presence of excess Mg reduces Mg 2 Since the solid solubility of Si in Al lowers the strength of the aluminum alloy, the present invention adopts a design method of a composition containing excess Si in order to secure the strength of the aluminum alloy. When the Si content is too much, the oxidizing property is reduced by the existence of simple substance Si, so that the content of the excessive Si needs to be controlled, and the design scheme that the Mg/Si content is slightly lower than 1.73 is adopted. Therefore, in the 6-series aluminum alloy, the mass percentage of the Si element is controlled to be 0.45-0.6%, and the mass percentage of the Mg element is controlled to be 0.74-1.0%.
In some preferred embodiments, while the mass percentage of the single chemical element is controlled, the mass percentage of the Mg and Si elements can be further controlled to satisfy: mg/Si =1.65 to 1.68.
Cu: in the 6-series aluminum alloy, the Cu element can promote Mg and Si elements in the 6-series aluminum alloy to form atom clusters in the aging process, promote the subsequent atom clusters to grow into GP zones (solute atom accumulation zones in desolventizing reaction) and beta' phases with certain strengthening effects, and therefore the mechanical property of the aluminum alloy is improved. However, it should be noted that the content of Cu is not so high that the increase of Cu content increases the corrosion performance such as intergranular corrosion, and therefore, the content of Cu must be strictly controlled. Based on this, in the 6-series aluminum alloy of the present invention, the mass percentage content of the Cu element is controlled to be 0.1 to 0.2%.
Mn: in the 6 series aluminum alloy of the invention, mn element can be matched with matrix Al to form Al in the homogenizing or heating process 6 Mn，Al 6 Mn has a nano-scale size, and can pin dislocation in the subsequent thermal deformation and heat treatment processes, so that the growth of crystal grains is hindered, and recrystallization is inhibited, thereby effectively improving the strength of the aluminum alloy. However, it should be noted that the content of Mn element in the steel is not so high that when the content of Mn element in the steel is too high, a coarse Mn-containing phase is precipitated during solidification, which deteriorates the toughness of the aluminum alloy. Based on the above, in the 6-series aluminum alloy, the mass percentage of Mn element is controlled between 0.06 and 0.12 percent.
Cr: in the 6-series aluminum alloy of the present invention, the action of Cr is substantially the same as that of Mn, and Al is the main component of Cr in aluminum 7 Cr、Al 12 Cr and other compounds exist in a form, which can effectively hinder nucleation and growth of recrystallization and improve the strength of the aluminum alloy; however, it should be noted that Al 7 The hard oxidation of Cr can be directly dissolved in the electrolyte, so that the mass percent of Cr element in the 6-series aluminum alloy is controlled to be 0.05-0.15%.
Zr: in the 6 series aluminum alloy of the invention, zr element can be matched with Al element to form Al during the homogenization and heating process 3 Zr, al formed 3 Zr can be coherent with the matrix, the size of the Zr is nano-scale and is far smaller than the dispersed phase formed by Mn and Cr elements, and the Zr is dispersed and distributed with fine Al 3 The Zr has better effect of inhibiting recrystallization; however, it should be noted that the content of Zr element in the steel should not be too high, and too high content of Zr may cause peritectic reaction in the aluminum melt, which may easily cause too high viscosity of the aluminum melt. Based on the above, in the 6-series aluminum alloy of the invention, the mass percentage content of Zr element is controlled between 0.07 and 0.14 percent.
Of course, in some preferred embodiments, in order to obtain better implementation effect, in the 6-series aluminum alloy of the invention, the mass percentage content of the Zr element can be further preferably controlled to be between 0.09 and 0.12%.
Ti: in the 6-series aluminum alloy, ti is a grain refining element, so that the columnar crystal structure of the cast ingot can be reduced, and the effect of refining cast grains is achieved; meanwhile, ti element, mn element and Cr element are added in a combined manner, so that the recrystallization temperature can be obviously improved. Based on the above, in the 6-series aluminum alloy, the mass percentage content of Ti element is controlled to be more than 0 and less than or equal to 0.15 percent.
Fe: in the 6-series aluminum alloy, fe is an impurity element, the elongation of the aluminum alloy is reduced when the content of the Fe element in the alloy is high, and Fe can easily form Al together with Mn and Si 12 (Fe,Mn) 3 The Si compound is easily dissolved in anodic polarization to form defects. Therefore, in the 6-series aluminum alloy, the content of the Fe element must be strictly controlled, and the mass percentage of the Fe element is controlled to be less than or equal to 0.25 percent.
Further, in the 6-series aluminum alloy according to the present invention, it satisfies Mg/Si: 1.65-1.68.
In the above technical scheme, while the mass percentage of a single chemical element is controlled, the mass percentage of the elements Mg and Si can be further preferably controlled to satisfy Mg/Si: 1.65-1.68. Wherein, each chemical element in the Mg/Si formula respectively represents the mass percentage content of the corresponding element.
Furthermore, in the 6-series aluminum alloy, the mass percentage content of single impurity elements in the inevitable impurities is less than or equal to 0.05 percent, and the total content of the single impurity elements is less than or equal to 0.15 percent.
Further, in the 6-series aluminum alloy of the invention, the mass percentage of Zr is as follows: 0.09-0.12 percent.
Further, in the 6-series aluminum alloy according to the present invention, the microstructure thereof contains nano-sized Mg dispersed therein 2 A Si phase.
Further, in the 6-series aluminum alloy according to the present invention, the AlFeSi phase is an α (AlFeSi) phase.
Further, in the 6-series aluminum alloy according to the present invention, after anodic oxidation is performed by hard oxidation, a section in the thickness direction does not have a band defect.
Accordingly, another object of the present invention is to provide a method for producing the above-mentioned 6-series aluminum alloy of the present invention, which is simple to produce, and the obtained 6-series aluminum alloy sheet has no strip defects in the cross section in the thickness direction after being anodized by a hard oxidation process.
In order to achieve the above object, the present invention provides the above 6-series aluminum alloy production method, comprising:
(1) Smelting and casting to obtain an aluminum alloy ingot;
(2) Heating: controlling the heating speed to be 20-40 ℃/h, preserving the heat at 530-560 ℃ for 4-24h, and discharging;
(3) Hot rolling: performing multi-pass rolling to achieve the target thickness, and controlling the rolling temperature of the plate blank under a certain pass to be 500-565 ℃ when the thickness of the plate blank under the certain pass is more than 100mm during the multi-pass rolling;
(4) Solution heat treatment;
(5) Stretching treatment;
(6) And (5) aging treatment.
In the invention, the inventor can effectively improve Mg by reasonably designing alloy elements and matching with an optimized manufacturing process 2 The distribution of Si phase and AlFeSi phase makes the surface of the prepared 6 series aluminum alloy plate after hard anodic oxidation present a uniform oxidation film layer, and the section in the thickness direction has no strip defect.
In the step (1) of the above-mentioned manufacturing method of the present invention, the smelting operation may be performed by using a smelting furnace, and after the chemical composition meets the design requirements of the present invention, the aluminum alloy slab may be melted and alloyed in the smelting furnace, and then cast into an aluminum alloy slab ingot by way of semi-continuous casting.
After the head and the tail of the prepared aluminum alloy flat ingot are sawed and the surface of the aluminum alloy flat ingot is milled, the aluminum alloy flat ingot can be placed in a heating furnace for heating treatment and then taken out of the furnace, in the step (2) of the manufacturing method of the invention,the invention optimally sets the heating treatment process, controls the metal heating speed to be 20-40 ℃/h, and takes out the furnace after the temperature is controlled to be kept for 4-24h at 530-560 ℃. Wherein the temperature is controlled to be increased at 20-40 ℃/h to ensure that the Mn, cr and Zr phases form a nano-grade Mn, cr and Al-containing phase 3 Zr phase, which can inhibit the crystal grains from growing in the subsequent hot rolling and solution treatment, and ensure the structural consistency of the edge part and the center part of the section of the 6-series aluminum alloy plate in the thickness direction.
In addition, the heating operation in the step (2) of the present invention is controlled to satisfy the parameters of the above-mentioned heat treatment process, and it is also possible to ensure that Mg is present 2 The Si phase is dissolved in the heating process to eliminate coarse Mg 2 Si phase influences the hard anodic oxidation effect; the morphology of an AlFeSi phase can be effectively changed, so that a beta (AlFeSi) phase is converted into an alpha (AlFeSi) phase, and the uniformity of an oxide film is improved; in addition, this heating process can also provide sufficient workability for the hot rolling process in the subsequent step (3).
Accordingly, in step (3) of the above-described manufacturing method of the present invention, the slab after tapping in step (2) needs to be hot rolled, and then multiple passes of rolling are performed to achieve a target thickness. Wherein, in the multi-pass rolling, when the thickness of the plate blank in a certain pass is more than 100mm, the rolling temperature of the plate blank in the pass is controlled to be 500-565 ℃, so as to reduce the occurrence of coarse Mg in the conventional hot rolling process 2 Si is separated out; particularly, the method can well inhibit coarse Mg precipitation at the core part position of the thick plate 2 Si phase, avoiding the occurrence of stripe defects in the core.
Further, in the manufacturing method of the present invention, in the step (4), the heating is performed to 525 to 545 ℃, the heat preservation is performed for 30 to 90min, and the water quenching cooling treatment is performed immediately after the heat preservation is finished.
Further, in the production method of the present invention, in the step (5), the stretching amount is controlled to be 1 to 3%.
Furthermore, in the manufacturing method of the invention, in the step (6), single-stage aging treatment is carried out at 170-190 ℃, the temperature is kept for 8-14 h, and natural cooling is carried out after the temperature is kept.
Compared with the prior art, the 6-series aluminum alloy for hard anodic oxidation and the manufacturing method thereof have the following advantages and beneficial effects:
in the 6-series aluminum alloy, reasonable chemical component design is adopted, a manufacturing process is optimized in a matching manner, mn, cr and Zr elements in steel are regulated, and Mn, cr and Zr-rich compounds are used as inhibitors for grain growth, so that the consistency of the core and surface structures of the thick plate after hot rolling process and solution treatment of the aluminum alloy can be effectively ensured. Meanwhile, the 6-series aluminum alloy thick plate can be effectively prepared by adopting the manufacturing process disclosed by the invention, and the thick Mg can be reduced by utilizing an optimized process design 2 The aggregation degree of the Si phase in the core of the plate reduces the oxidation defect of the hard anode in a strip shape.
In conclusion, the invention can effectively improve Mg in the 6 series aluminum alloy by controlling the chemical element components, heating, hot rolling, solid solution, aging and stretching processes 2 The distribution of the Si phase and the AlFeSi phase ensures that the section of the obtained 6-series aluminum alloy plate in the thickness direction has no strip defects after the 6-series aluminum alloy plate is subjected to anodic oxidation by adopting a hard oxidation process.
Drawings
Fig. 1 is a cross-sectional oxide film morphology in the thickness direction of the comparative aluminum alloy of comparative example 1 after being anodized by a hard oxidation process.
FIG. 2 is a cross-sectional oxide film morphology of the 6-series aluminum alloy of example 2 in the thickness direction after anodization using a hard oxidation process.
Detailed Description
The 6-series aluminum alloy for hard anodizing and the manufacturing method thereof according to the present invention will be further explained and explained with reference to the drawings and specific examples, but the explanation and explanation do not unduly limit the technical solution of the present invention.
Examples 1 to 6 and comparative examples 1 to 2
The 6-series aluminum alloys of examples 1 to 6 and the comparative 6-series aluminum alloys of comparative examples 1 to 2 were each produced by the following procedure:
(1) The aluminum alloy slab ingot is cast in a semi-continuous casting manner after being melted and alloyed by using a melting furnace according to chemical components shown in the following table 1.
(2) And (3) sawing the head, the tail and the face of the prepared aluminum alloy slab ingot, then placing the aluminum alloy slab ingot in a heating furnace for heating, controlling the heating rate to be 20-40 ℃/h, preserving heat for 4-24h at 530-560 ℃, and then discharging the aluminum alloy slab ingot from the furnace.
(3) And (3) hot rolling after discharging, performing multi-pass rolling to achieve a target thickness, and controlling the rolling temperature of the slab at a certain pass to be 500-565 ℃ when the thickness of the slab at the certain pass is more than 100mm in the multi-pass rolling.
(4) Solution heat treatment: heating the prepared aluminum alloy plate to 525-545 ℃ in a solution heat treatment furnace, preserving heat for 30-90min, and immediately carrying out water quenching cooling treatment after heat preservation.
(5) And (3) stretching treatment: and (3) stretching the aluminum alloy plate by a stretcher, wherein the stretching amount is controlled to be 1-3%.
(6) Aging treatment: single-stage aging treatment is carried out at 170-190 ℃, the temperature is kept for 8-14 h, and the aluminum alloy thick plate is obtained after natural cooling after the temperature is kept.
In the present invention, the chemical composition design and related processes of the 6-series aluminum alloys of examples 1-6 meet the design specifications of the present invention. Accordingly, the comparative steels of comparative examples 1-2 were prepared by the above-mentioned process flow, but the chemical composition designs of comparative examples 1-2 or related processes had parameters that did not meet the design specifications of the present invention, and the chemical composition designs can be found in table 1 below.
Table 1 shows the mass percentage ratios of the respective chemical elements of the 6-series aluminum alloys of examples 1 to 6 and the comparative 6-series aluminum alloys of comparative examples 1 to 2.
TABLE 1 (balance Al and unavoidable impurities other than Fe)
Note: in the above table, each chemical element in the Mg/Si formula represents the mass percentage of the corresponding element.
The specific manufacturing process operations for the 6-series aluminum alloys of examples 1-6 are as follows:
example 1
The chemical components shown in the table 1 are mixed, melted and alloyed, and then cast into ingots; sawing and milling the cast ingot, then placing the cast ingot in a heating furnace for heat treatment, controlling the heating rate to be 30 ℃/h, keeping the temperature for 4h at the heating temperature of 560 ℃, and then finishing heating and discharging; then discharging the steel plate out of the furnace and hot rolling the steel plate into a plate with the thickness of 12mm, wherein in the multi-pass rolling process, the thickness of the plate blank in the 1 st to 18 th passes is more than 100mm, and the rolling temperature in the 1 st to 18 th passes is 550 ℃, 552 ℃, 556 ℃, 557 ℃, 558 ℃, 559 ℃, 560 ℃, 565 ℃, 555 ℃, 565 ℃, 560 ℃ and 555 ℃ in sequence; after hot rolling, placing the hot rolled plate at 530 ℃ for heat preservation for 30min, and immediately performing water quenching cooling treatment after heat preservation; then, stretching treatment is carried out, and the stretching amount is controlled to be 1.9%; finally, single-stage aging treatment is carried out at 170 ℃, heat preservation is carried out for 10 hours, and after natural cooling, the 6 series aluminum alloy thick plate of the embodiment 1 can be obtained.
Example 2
The chemical components shown in the table 1 are mixed, melted and alloyed, and then cast into ingots; sawing and milling the cast ingot, placing the cast ingot in a heating furnace for heat treatment, controlling the heating speed to be 30 ℃/h, preserving the heat for 20h at the heating temperature of 540 ℃, and then finishing heating and discharging; then discharging and hot rolling the steel plate into a plate with the thickness of 40mm, wherein in the multi-pass rolling process, the thickness of the plate blank in the 1 st to 14 th passes is more than 100mm, and the rolling temperature in the 1 st to 14 th passes is 535 ℃, 542 ℃, 546 ℃, 552 ℃, 542 ℃, 545 ℃, 540 ℃, 548 ℃ and 550 ℃ in sequence; after hot rolling, placing the hot rolled plate at 535 ℃ for heat preservation for 60min, and immediately carrying out water quenching cooling treatment after heat preservation; then, stretching treatment is carried out, and the stretching amount is controlled to be 2.0%; finally, single-stage aging treatment is carried out at 175 ℃, heat preservation is carried out for 10 hours, and after natural cooling, the 6-series aluminum alloy thick plate of the embodiment 2 can be obtained.
Example 3
The chemical components shown in the table 1 are mixed, melted and alloyed, and then cast into ingots; sawing and milling the cast ingot, placing the cast ingot in a heating furnace for heat treatment, controlling the heating speed to be 40 ℃/h, preserving the heat for 4h at the heating temperature of 530 ℃, and then finishing heating and discharging; then discharging and hot rolling to form a plate with the thickness of 30mm, wherein in the multi-pass rolling process, the thickness of the plate blank of the 1 st to 16 th passes is more than 100mm, and the rolling temperature of the 1 st to 16 th passes is 520 ℃, 525 ℃, 528 ℃, 530 ℃, 535 ℃, 536 ℃, 532 ℃, 533 ℃, 535 ℃, 540 ℃, 535 ℃, 538 ℃ and 535 ℃; after hot rolling is finished, placing the hot rolled plate at 545 ℃ for heat preservation for 45min, and immediately performing water quenching cooling treatment after heat preservation is finished; then, stretching treatment is carried out, and the stretching amount is controlled to be 2.0%; finally, single-stage aging treatment is carried out at 175 ℃, heat preservation is carried out for 10 hours, and after natural cooling, the 6-series aluminum alloy thick plate of the embodiment 3 can be obtained.
Example 4
The chemical components shown in the table 1 are mixed, melted and alloyed, and then cast into ingots; sawing and milling the cast ingot, placing the cast ingot in a heating furnace for heat treatment, controlling the heating speed to be 20 ℃/h, preserving the heat for 24h at the heating temperature of 530 ℃, and then finishing heating and discharging; then discharging and hot rolling the steel plate into a plate with the thickness of 50mm, wherein in the multi-pass rolling process, the thickness of the plate blank of the 1 st to 14 th passes is more than 100mm, and the rolling temperatures of the 1 st to 14 th passes are 505 ℃, 508 ℃, 500 ℃, 505 ℃, 503 ℃, 508 ℃, 510 ℃, 520 ℃, 525 ℃, 530 ℃, 525 ℃ and 525 ℃ in sequence; after hot rolling is finished, placing the hot rolled plate at 535 ℃ and preserving heat for 60min, and immediately carrying out water quenching and cooling treatment after heat preservation is finished; then, stretching treatment is carried out, and the stretching amount is controlled to be 2.0%; finally, single-stage aging treatment is carried out at 170 ℃, heat preservation is carried out for 14h, and after natural cooling, the 6 series aluminum alloy thick plate of the embodiment 4 can be obtained.
Example 5
Proportioning the raw materials according to the chemical components shown in the table 1, melting, alloying and casting to form an ingot; sawing and milling the cast ingot, placing the cast ingot in a heating furnace for heat treatment, controlling the heating speed to be 35 ℃/h, preserving the heat for 8h at the heating temperature of 550 ℃, and then finishing heating and discharging; then discharging and hot rolling the steel plate into a plate with the thickness of 80mm, wherein in the multi-pass rolling process, the thickness of the plate blank in the 1 st to 12 th passes is more than 100mm, and the rolling temperature in the 1 st to 12 th passes is 510 ℃, 518 ℃, 520 ℃, 525 ℃, 533 ℃, 538 ℃, 540 ℃, 550 ℃, 540 ℃ and 535 ℃; after hot rolling, placing the hot rolled plate at 530 ℃ for heat preservation for 60min, and immediately performing water quenching cooling treatment after heat preservation; then, stretching treatment is carried out, and the stretching amount is controlled to be 3.0%; finally, single-stage aging treatment is carried out at 180 ℃, heat preservation is carried out for 12 hours, and after natural cooling, the 6 series aluminum alloy thick plate of the embodiment 5 can be obtained.
Example 6
The chemical components shown in the table 1 are mixed, melted and alloyed, and then cast into ingots; sawing and milling the cast ingot, placing the cast ingot in a heating furnace for heat treatment, controlling the heating speed to be 25 ℃/h, preserving the heat for 16h at the heating temperature of 535 ℃, and then finishing heating and discharging; then discharging and hot rolling the steel plate into a plate with the thickness of 110mm, wherein in the multi-pass rolling process, the thickness of the plate blank of the 1 st to 12 th passes is more than 100mm, and the rolling temperature of the 1 st to 12 th passes is 520 ℃, 525 ℃, 533 ℃, 535 ℃, 530 ℃, 525 ℃, 520 ℃ and 525 ℃ in sequence; after hot rolling is finished, placing the hot rolled plate at 525 ℃ for heat preservation for 90min, and immediately performing water quenching cooling treatment after heat preservation is finished; then, stretching treatment is carried out, and the stretching amount is controlled to be 1.0%; finally, single-stage aging treatment is carried out at 190 ℃, the temperature is kept for 8h, and after natural cooling, the 6-series aluminum alloy thick plate of the embodiment 6 can be obtained.
Comparative example 1
The chemical components shown in the table 1 are mixed, melted and alloyed, and then cast into ingots; sawing and milling the cast ingot, then placing the cast ingot in a heating furnace for heat treatment, controlling the heating rate to be 30 ℃/h, keeping the temperature for 4h at the heating temperature of 560 ℃, and then finishing heating and discharging; then discharging and hot rolling into a plate with the thickness of 40 mm; after hot rolling, placing the hot rolled plate at 530 ℃ for heat preservation for 30min, and immediately performing water quenching cooling treatment after heat preservation; then, stretching treatment is carried out, and the stretching amount is controlled to be 1.9%; finally, single-stage aging treatment is carried out at 170 ℃, heat preservation is carried out for 10 hours, and after natural cooling, the comparative 6 series aluminum alloy thick plate of the comparative example 1 can be obtained.
Comparative example 2
Proportioning the raw materials according to the chemical components shown in the table 1, melting, alloying and casting to form an ingot; sawing and milling the cast ingot, placing the cast ingot in a heating furnace for heat treatment, controlling the heating speed to be 30 ℃/h, preserving the heat for 4h at the heating temperature of 500 ℃, and then finishing heating and discharging; then discharging and hot rolling into a plate with the thickness of 30 mm; after hot rolling, placing the hot rolled plate at 530 ℃ for heat preservation for 30min, and immediately performing water quenching cooling treatment after heat preservation; then, stretching treatment is carried out, and the stretching amount is controlled to be 1.9%; finally, single-stage aging treatment is carried out at 170 ℃, heat preservation is carried out for 10h, and after natural cooling, the comparative 6 series aluminum alloy thick plate of the comparative example 2 can be obtained.
Table 2 lists specific process parameters of the 6-series aluminum alloys of examples 1-6 and the comparative 6-series aluminum alloys of comparative examples 1-2 in the above-described process steps.
Table 2.
Accordingly, the obtained finished 6-series aluminum alloy thick plates of examples 1 to 6 were sampled, respectively, and the finished comparative 6-series aluminum alloy thick plates of examples 1 to 2 were sampled to obtain corresponding samples, and the samples of the aluminum alloy thick plates of each example and comparative example were observed to analyze the microstructures thereof. As can be seen from the observation and analysis, in the 6-series aluminum alloy thick plates of examples 1 to 6, the microstructure thereof contained Mg in a dispersed distribution on a nanometer scale 2 And the Si phase, and the AlFeSi phase is judged to be an alpha (AlFeSi) phase through SEM morphology and XRD.
Accordingly, after the observation and analysis, the samples of the aluminum alloy thick plates of examples 1 to 6 and comparative examples 1 to 2 were further taken, and the samples of each example and comparative example were anodized according to the same hard oxidation process, and the presence or absence of a band defect in the section in the thickness direction was observed, and the results are shown in the following table 3.
And (3) hard oxidation process: the current density is controlled to be 3.5Adm3 +/-0.35A/dm 3 under the conditions of 0 +/-5 ℃ and 160-180 g/L of sulfuric acid solution, and the method is carried out according to the GB/T19822.
Table 3 shows the cross-sectional states in the thickness direction of the 6-series aluminum alloy thick plates of examples 1 to 6 and the 6-series aluminum alloy thick plates of comparative examples 1 to 2 after being anodized by hard oxidation.
Table 3.
As can be seen from table 3, the 6-series aluminum alloy thick plates of examples 1 to 6 have no strip defects in the cross section in the thickness direction after being anodized by a hard oxidation process; the comparative 6 series aluminum alloy thick plates of comparative examples 1-2 all had obvious strip defects in the cross section in the thickness direction after being anodized by a hard oxidation process.
This shows that the thick 6-series aluminum alloy plates of examples 1 to 6 obtained by the 6-series aluminum alloy for hard anodizing and the manufacturing method of the present invention can solve the problem of the band defect on the surface of the thickness section and can obtain a uniform hard oxide film.
Fig. 1 is a cross-sectional oxide film morphology in the thickness direction of comparative example 1, which is a comparative example 6 aluminum alloy after being anodized by a hard oxidation process.
FIG. 2 is a cross-sectional oxide film morphology of the 6-series aluminum alloy of example 2 in the thickness direction after anodization using a hard oxidation process.
As shown in fig. 1 and 2, in the present invention, the 6-series aluminum alloy of example 2 shown in fig. 2 has no band defect in a cross section in the thickness direction after being anodized by a hard oxidation process; in contrast, the aluminum alloy of comparative example 6 shown in fig. 1, which was the aluminum alloy of comparative example 1, had a significant band defect in the cross section in the thickness direction after being anodized by hard oxidation.
In conclusion, the invention can effectively improve Mg by adopting reasonable chemical component proportion and matching with optimized homogenization and hot rolling processes 2 The distribution of Si phase and AlFeSi phase makes the surface of the hard anodized aluminum alloy present a uniform oxide film layer, which can effectively solve the appearance defect of the cross section of the 6-series aluminum alloy thick plate in the prior art after hard oxidationTo a problem of (a).
It should be noted that the combination of the features in the present application is not limited to the combination described in the claims of the present application or the combination described in the specific examples, and all the features described in the present application may be freely combined or combined in any manner unless contradicted by each other.
It should also be noted that the above-mentioned embodiments are only specific embodiments of the present invention. It is apparent that the present invention is not limited to the above embodiments and similar changes or modifications thereto which can be directly or easily inferred from the disclosure of the present invention by those skilled in the art are intended to be within the scope of the present invention.
Claims (12)
1. A6-series aluminum alloy for hard anodizing, which contains Al and inevitable impurities and is characterized by further containing the following chemical elements in percentage by mass:
Si：0.45-0.6％，Cu：0.1-0.2％，Mn：0.06-0.12％，Mg：0.74-1.0％，Cr：0.05-0.15％，Zr：0.07-0.14％，0＜Ti≤0.15％，Fe≤0.25％。
2. the 6-series aluminum alloy according to claim 1, wherein the aluminum alloy comprises the following chemical elements in percentage by mass:
si:0.45-0.6%, cu:0.1-0.2%, mn:0.06-0.12%, mg:0.74-1.0%, cr:0.05-0.15%, zr:0.07-0.14 percent of Ti, more than 0 and less than or equal to 0.15 percent of Ti, and less than or equal to 0.25 percent of Fe; the balance being Al and unavoidable impurities.
3. The 6-series aluminum alloy according to claim 1 or 2, which satisfies the following conditions: 1.65-1.68.
4. The 6-series aluminum alloy according to claim 1 or 2, wherein the mass percentage content of the individual impurity elements is 0.05% or less and the total content is 0.15% or less among the inevitable impurities.
5. The 6-series aluminum alloy according to claim 1 or 2, wherein the mass percentage of Zr is: 0.09-0.12 percent.
6. The series 6 aluminum alloy according to claim 1 or 2, wherein the microstructure contains a dispersion of nano-sized Mg 2 A Si phase.
7. The 6-series aluminum alloy according to claim 1 or 2, wherein the AlFeSi phase is an α (AlFeSi) phase.
8. The series 6 aluminum alloy according to claim 1 or 2, wherein a cross section in a thickness direction thereof is free from a band defect after the anodizing by the hard oxidation process.
9. The method for producing a 6-series aluminum alloy according to any one of claims 1 to 8, comprising the steps of:
(1) Smelting and casting to obtain an aluminum alloy ingot;
(2) Heating: controlling the heating speed to be 20-40 ℃/h, preserving the heat at 530-560 ℃ for 4-24h, and discharging;
(3) Hot rolling: performing multi-pass rolling to reach a target thickness, and controlling the rolling temperature of the plate blank under a certain pass to be 500-565 ℃ when the thickness of the plate blank under the certain pass is more than 100mm during the multi-pass rolling;
(4) Solution heat treatment;
(5) Stretching treatment;
(6) And (5) aging treatment.
10. The method of claim 9, wherein in the step (4), the mixture is heated to 525 to 545 ℃ and is kept at the temperature for 30 to 90 minutes, and water quenching and cooling treatment are performed immediately after the temperature is kept.
11. The production method according to claim 9, wherein in the step (5), the stretching amount is controlled to be 1 to 3%.
12. The method of claim 9, wherein in step (6), the single-stage aging treatment is performed at 170-190 ℃, the temperature is maintained for 8-14 h, and the product is naturally cooled after the temperature maintenance is finished.
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