WO2015141647A1 - Plaque en alliage d'aluminium pour élément structurel - Google Patents
Plaque en alliage d'aluminium pour élément structurel Download PDFInfo
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- WO2015141647A1 WO2015141647A1 PCT/JP2015/057774 JP2015057774W WO2015141647A1 WO 2015141647 A1 WO2015141647 A1 WO 2015141647A1 JP 2015057774 W JP2015057774 W JP 2015057774W WO 2015141647 A1 WO2015141647 A1 WO 2015141647A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/053—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with zinc as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
- C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/10—Alloys based on aluminium with zinc as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/047—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with magnesium as the next major constituent
Definitions
- the present invention relates to a high-strength aluminum alloy plate for a structural material that has improved workability and excellent corrosion resistance.
- the aluminum alloy plate of the present invention is a rolled plate, which is a plate obtained by subjecting a plate produced by rolling to aging at room temperature for 2 weeks or more after solution treatment and quenching treatment, before forming into a structural material and artificial This refers to the plate before age hardening.
- the structure of the plate aged at room temperature in the present invention refers to the structure of the plate after aging at room temperature for 2 weeks or more after the solution treatment and quenching treatment.
- the composition and tempering (solution treatment and quenching) of the JIS to AA6000 series aluminum alloy plates which are used in the above-mentioned automobile panels, are excellent in formability, strength, corrosion resistance, low alloy composition and recyclability. Control of the treatment, and further, the artificial age hardening treatment, is far from achieving the high strength.
- the 7000 series aluminum alloy which is an Al—Zn—Mg series aluminum alloy
- SCC stress corrosion cracking
- composition control of 7000 series aluminum alloy extruded material excellent in both strength and SCC resistance and structure control of precipitates have been conventionally proposed.
- conventional structure control such as composition control and precipitates in a 7000 series aluminum alloy plate according to the small practical use of the plate.
- Patent Document 1 the molten metal is cold-rolled after rapid solidification, and further, crystal precipitates in the crystal grains of the 7000 series aluminum alloy plate after artificial age hardening treatment are measured by a 400 times optical microscope.
- the size (converted to equivalent circle equivalent diameter) is 3.0 ⁇ m or less, and the average area fraction is 4.5% or less to improve strength and elongation.
- Patent Documents 2 and 3 in order to increase the strength and SCC resistance of a 7000 series plate for a structural material, the ingot is repeatedly rolled in a warm working region after forging, and the structure Is fine. This is because, by making the structure finer, a large tilt grain boundary having an orientation difference of 20 ° or more, which causes a potential difference between the grain boundary and the grain boundary, which causes a decrease in SCC resistance, is suppressed. This is to obtain a texture having a small angle grain boundary of 25 ° or more.
- such warm rolling is repeated because the conventional hot rolling and cold rolling methods cannot obtain a texture in which such a low-angle grain boundary is 25% or more. ing. Therefore, since the process is greatly different from the conventional method, it is difficult to say that it is a practical method for producing a plate.
- the extruded material is completely different from the rolled plate in its manufacturing process such as a hot working process, and the resulting structure of crystal grains and precipitates is, for example, a fibrous form in which the crystal grains are elongated in the extrusion direction.
- the crystal grains are basically different from a rolled plate having equiaxed grains.
- the object of the present invention is to provide an automobile member having both strength and formability and excellent corrosion resistance even after aging at room temperature as a rolled plate produced by the conventional method. It is to provide a 7000 series aluminum alloy plate for structural materials.
- the gist of the aluminum alloy sheet for structural material of the present invention is, in mass%, Zn: 3.0 to 6.0%, Mg: 2.5 to 4.5%, Cu: 0.00.
- the Zn content [Zn] and the Mg content [Mg] satisfy [Zn] ⁇ ⁇ 0.3 [Mg] +4.5, and the balance Is an Al—Zn—Mg-based aluminum alloy plate having a composition composed of Al and inevitable impurities, and is observed with a transmission electron microscope of 60000 times in a structure in which this plate is aged at room temperature after solution treatment and quenching treatment.
- the average composition ratio (Zn / Mg) of Zn and Mg in the grain boundary precipitates is 0.5 to 3.0, and a plate aged at room temperature after the solution treatment and quenching treatment, (I) Two-stage artificial aging treatment in which the first-stage heat treatment temperature is in the range of 70 to 100 ° C. for 2 hours or more, and the second-stage heat treatment temperature is in the range of 100 to 170 ° C. for 5 hours or more. Or (II) Particles observed with a transmission electron microscope at 60000 times in the structure of the plate after one of the one-stage artificial aging treatments for 12 to 36 hours at a heat treatment temperature of 100 to 150 ° C.
- the average composition ratio (Zn / Mg) of Zn and Mg in the inner precipitate is in the range of 1.5 to 3.5.
- the present inventors reduced the Zn content for improving the corrosion resistance, while using a 7000 series aluminum alloy plate having a composition in which the Mg content was increased to ensure strength and formability, the grains of the plate structure aged at room temperature. Focusing on the precipitates in the boundaries and grains, the effect of the composition of these precipitates on the properties was analyzed.
- the present invention can improve the balance between strength and ductility (formability) and BH properties, even for a 7000 series aluminum alloy plate with a reduced Zn content.
- a structural 7000 series aluminum alloy plate having both strength and formability hereinafter also referred to as formability or workability
- excellent corrosion resistance such as SCC resistance
- the measurement of the structure by the TEM is not a state of a plate that has not been aged at room temperature immediately after the tempering treatment, but as a guideline. This is a plate after aging at room temperature (room temperature standing) for more than a week, and is performed on the plate before forming into a structural material and before artificial age hardening treatment.
- the aluminum alloy plate referred to in the present invention is a plate produced by rolling, and the ingot is hot-rolled after soaking, further cold-rolled into a cold-rolled plate, and further subjected to solution treatment and quenching treatment, etc.
- the aluminum alloy plate referred to in the present invention defines the room temperature aged structure of the 7000 series aluminum alloy plate produced as described above, and is formed into a structural material for use as a material aluminum alloy plate. is there. For this reason, it refers to a plate after the plate manufactured as described above is aged at room temperature (room temperature standing), and before being formed into a structural material as an application and before artificial age hardening treatment.
- artificial age hardening is also simply referred to as artificial ageing
- artificial age hardening is simply referred to as artificial ageing.
- Al alloy composition (Aluminum alloy composition) First, the chemical component composition of the aluminum alloy sheet of the present invention will be described below, including reasons for limiting each element. In addition,% display of content of each element means the mass% altogether.
- the chemical composition of the aluminum alloy sheet of the present invention combines strength and formability, which are required characteristics for structural materials such as automobile members intended in the present invention, as a rolled sheet produced by a conventional method. It is a prerequisite for satisfying corrosion resistance.
- the Al-Zn-Mg-Cu-based 7000 series aluminum alloy composition in the present invention is a composition in which the Mg content is increased in order to secure strength while suppressing the Zn content in order to improve the corrosion resistance. .
- the chemical composition of the aluminum alloy sheet of the present invention is, by mass, Zn: 3.0 to 6.0%, Mg: 2.5 to 4.5%, Cu: 0.05 to 0.5. %, And the Zn content [Zn] and the Mg content [Mg] satisfy [Zn] ⁇ ⁇ 0.3 [Mg] +4.5, with the balance being Al and inevitable It shall consist of impurities.
- Zr 0.05 to 0.3%
- Mn 0.1 to 1.5%
- Cr 0.05 to 0.3%
- Sc 0.05
- One type or two or more types of up to 0.3% may be selectively included.
- one or two of Ag: 0.01 to 0.2% and Sn: 0.001 to 0.1% may be selectively included. .
- Zn 3.0-6.0% Zn, which is an essential alloy element, together with Mg, forms clusters during aging of the manufactured tempered plate at room temperature to improve work hardening characteristics and improve the workability of the structural material.
- an aging precipitate is formed to improve the strength during the artificial aging treatment after the forming process to the structural material. If the Zn content is less than 3.0%, the strength after the artificial aging treatment is insufficient. However, if the Zn content increases and exceeds 6.0%, the grain boundary precipitate MgZn 2 increases and intergranular corrosion tends to occur, and the corrosion resistance deteriorates. Therefore, the Zn content is suppressed to be relatively small. For this reason, the lower limit of the Zn content is 3.0%, preferably 3.4%. Further, the upper limit is 6.0%, preferably 4.6%.
- Mg 2.5-4.5% Mg, which is an essential alloy element, together with Zn, forms clusters during room temperature aging of the prepared tempered plate to improve work hardening characteristics and improve formability.
- an aging precipitate is formed during the artificial aging treatment after the forming process to the structural material, thereby improving the strength.
- the Mg content in order to suppress the Zn content relatively low, conversely, the Mg content is made relatively large in order to improve moldability and strength. If the Mg content is less than 2.5% by mass, the strength is insufficient and the work hardening characteristics are deteriorated. However, if it exceeds 4.5 mass%, the rollability of the plate is lowered, and the SCC sensitivity is enhanced. Therefore, the Mg content is in the range of 2.5 to 4.5%.
- the Zn content is suppressed to be relatively low, and the Mg content is relatively increased. To do.
- the Zn content [Zn] (mass%) and the Mg content [Mg] (mass%) are preferably balanced expressions of [Zn] ⁇ ⁇ 0.3 [Mg] +4.5, preferably Satisfies the balance equation of [Zn] ⁇ ⁇ 0.5 [Mg] +5.75.
- the 0.2% proof stress of the structural material after artificial aging treatment is set to 380 MPa or more in combination with a preferable manufacturing method described later. Is possible. Further, preferably, by satisfying [Zn] ⁇ ⁇ 0.5 [Mg] +5.75, the 0.2% proof stress of the structural material after artificial aging treatment is 400 MPa in combination with a preferable manufacturing method described later. This is possible.
- the contents of Zn and Mg are [Zn] ⁇ 0.3 [Mg] +4.5, the contents of Zn and Mg are within the specified range when the Zn content is suppressed relatively low. Even in this case, or by a preferable manufacturing method to be described later, there is a possibility that the 0.2% proof stress of the structural material after the artificial aging treatment cannot be 350 MPa or more. Further, when the Zn content and the Mg content are [Zn] ⁇ 0.5 [Mg] +5.75, the 0.2% proof stress of the structural material after the artificial aging treatment cannot be set to 400 MPa or more. There is sex.
- Cu 0.05 to 0.5%
- Cu has the effect of suppressing the SCC sensitivity of the Al—Zn—Mg alloy and improving the SCC resistance. It also improves general corrosion resistance.
- the Cu content is less than 0.05%, the effect of improving SCC resistance and general corrosion resistance is small.
- the lower limit of the Cu content is 0.05%, preferably 0.10%.
- the upper limit is 0.5%, preferably 0.4%.
- Zr 0.05 to 0.3%
- Mn 0.1 to 1.5%
- Cr 0.05 to 0.3%
- Sc 0.05 to 0.3% Since the transition elements of Zr, Mn, Cr, and Sc contribute to improvement in strength by refining the crystal grains of the ingot and the final product, they are selectively contained when necessary. When any one or two or more of these are contained, if the content of Zr, Mn, Cr, or Sc is less than the lower limit, the content is insufficient and the strength is lowered. On the other hand, when the contents of Zr, Mn, Cr, and Sc exceed the respective upper limits, the elongation decreases because coarse crystals are formed.
- the content in the case of containing these is 0.05%, preferably 0.08% for the lower limit of Zr, and 0.3%, preferably 0.2% for the upper limit.
- the lower limit of Mn is 0.1%, preferably 0.2%, and the upper limit is 1.5%, preferably 1.0%.
- the lower limit of Cr is 0.05%, preferably 0.1%, and the upper limit is 0.3%, preferably 0.2%.
- the lower limit of Sc is 0.05%, preferably 0.1%, and the upper limit is 0.3%, preferably 0.2%.
- Ag and Sn have the effect of finely precipitating aging precipitates that contribute to strength improvement by artificial aging treatment after forming into a structural material and promoting high strength. Let When one or both of these are contained, if the Sn content is less than 0.001% and the Ag content is less than 0.01%, the strength improvement effect is small. On the other hand, when there is too much Sn and Ag content, various characteristics, such as rolling property and weldability, will be reduced. In addition, the strength improvement effect is saturated, and Ag is only expensive. Therefore, Ag: 0.01 to 0.2% and Sn: 0.001 to 0.1% are set.
- Ti and B are impurities as a rolled plate, but also have the effect of refining the crystal grains of the ingot, so the upper limit of Ti is 0.2%, preferably 0.1%, and the upper limit of B is 0.05%, preferably 0.03%.
- Fe and Si are allowed to be contained without affecting the characteristics of the aluminum alloy rolled sheet according to the present invention as long as Fe: 0.5% or less and Si: 0.5% or less.
- the 7000 series aluminum alloy sheet structure of the present invention is defined by a cold-rolled sheet after tempering and aging at room temperature for 2 weeks or more. For this reason, after this cold-rolled sheet is made into a structure (tempered T4) aged at room temperature for 2 weeks or more after solution treatment and quenching treatment, this structure is observed with a transmission electron microscope of 60000 times.
- the average composition ratio (Zn / Mg) of Zn and Mg of the grain boundary precipitate (room temperature aging precipitate) is defined.
- a plate which has been aged at room temperature for 2 weeks or more after the solution treatment and quenching treatment is further subjected to (I) a heat treatment temperature of the second stage for 2 hours or more in the range of the first stage heat treatment temperature of 70 to 100 ° C.
- One-step artificial aging treatment for 12 to 36 hours at a heat treatment temperature range of 100 to 150 ° C. is performed, and this structure is observed with a transmission electron microscope of 60000 times.
- the average composition ratio (Zn / Mg) of Zn and Mg in the intragranular precipitate is defined.
- composition of grain boundary precipitates in the present invention, the average composition of Zn and Mg of grain boundary precipitates (room temperature aging precipitates) observed with a transmission electron microscope of 60000 times the texture of the tempered T4 plate
- the ratio (Zn / Mg) is in the range of 0.5 to 3.0.
- the Zn content in the grain boundary precipitate (room temperature aging precipitate) ( While reducing the Zn composition ratio), it is possible to relatively increase Mg.
- the amount of Zn consumed (unnecessarily) as this grain boundary precipitate can be reduced, and the amount of Zn solid solution in the matrix can be increased and secured.
- the amount of Zn required for the formation of aging precipitates during the subsequent artificial aging treatment can be maximized, and the balance between strength and formability and BH properties can be maximized.
- the structure of the structure by TEM is measured immediately after the tempering treatment such as solution hardening treatment in the state of the plate not aging at room temperature Roughly, as a guide, it is a plate after aging (room temperature standing) for 2 weeks or more, which is performed on the plate before forming the structure material and before the artificial aging treatment.
- the change with time in the composition ratio of the grain boundary precipitates is negligibly small even by the subsequent room temperature aging.
- composition of intragranular precipitate in order to guarantee the BH property of the manufactured cold-rolled sheet simultaneously with the grain boundary precipitate, it is applied to the plate after aging for 2 weeks or more at room temperature.
- the composition of the artificial aging precipitate is defined as the structure after the artificial aging treatment under specific conditions.
- the plate of the tempered T4 is (I) Two-stage artificial aging treatment in which the first-stage heat treatment temperature is in the range of 70 to 100 ° C. for 2 hours or more, and the second-stage heat treatment temperature is in the range of 100 to 170 ° C. for 5 hours or more. Or (II) One-step artificial aging treatment for 12 to 36 hours at a heat treatment temperature range of 100 to 150 ° C.
- the Zn content in the intragranular precipitate as the artificial aging precipitate is reduced. be able to.
- the Zn content (Zn composition ratio) in the intragranular precipitate can be reduced, and the amount of Zn necessary for the formation of the artificial aging precipitate (amount) can be reduced. Less is enough.
- the amount of aging precipitates contributing to strengthening during the artificial aging treatment can be maximized, and the balance between strength and formability and BH properties can be maximized.
- This intragranular precipitate has an increased composition ratio over time due to room temperature aging after the production of the plate (after tempering), so the average composition ratio (Zn) of Zn and Mg in the intragranular precipitate / Mg) for reproducibility, the same plate (the plate aged at room temperature after the tempering treatment) from which the grain boundary precipitates were measured was subjected to the artificial age hardening treatment under the specific conditions. Do as. Note that the number density of the intragranular precipitates and the average composition ratio of Zn and Mg (Zn / Mg) are naturally affected by this artificial aging treatment condition.
- the intragranular precipitate in the prior art has a high Zn content. There is no great difference from the composition. For this reason, when the Zn content as the alloy composition is lowered, the content of Zn in the intragranular precipitate (Zn composition ratio) is large, so it is necessary to form an aging precipitate (amount) during artificial aging treatment. As a result, the amount of Zn increases, and more Zn is consumed to form intragranular precipitates. For this reason, with an alloy composition having a smaller Zn content, the amount of aging precipitates contributing to strengthening during the artificial aging treatment is reduced, and the balance between strength and formability and BH properties are lowered.
- the average composition ratio (Zn / Mg) of Zn and Mg in the intragranular precipitate is less than the lower limit of 1.5 and deviates from the specified range, the Zn content itself as the composition of the plate is insufficient. This means that the intragranular precipitates, which are artificial aging precipitates, are reduced, the BH property is lowered, and the meaning itself of making a 7000 series aluminum alloy is lost.
- a structural 7000 series aluminum alloy plate with a reduced Zn content Even with a 7000 series aluminum alloy plate with a reduced Zn content, the balance between strength and ductility (formability) can be improved by the above grain boundary and grain precipitates.
- a structural 7000 series aluminum alloy having both 0.2% proof stress (BH property) of 380 MPa or more, preferably 400 MPa or more, and press forming workability, and excellent corrosion resistance such as SCC resistance. can provide a board.
- the grain boundary precipitates observed with a 60000 times TEM are lined up on the crystal grain boundaries. Observed amorphous precipitates, which can be observed with the TEM, and with TEM-EDX, the average composition ratio of Zn and Mg can be quantitatively analyzed.
- the equivalent circle diameter is as large as about 10 to 200 nm. This is a precipitate.
- the equivalent circle diameter is the diameter of a circle having the same area as an indeterminate compound, and has been widely used as a method for measuring or defining the size of a compound accurately and reproducibly. .
- the intragranular precipitates observed with a 60000-fold TEM are indeterminate precipitates scattered in the crystal grains, which can be observed with the TEM, and with TEM-EDX, the Zn and Mg
- the equivalent circle diameter is a precipitate having a size of about 1 to 50 nm that can be quantitatively analyzed.
- TEM-EDX is an X-ray spectrometer that is normally attached to the TEM used in the present invention, and is well known as an analyzer using energy dispersive X-ray spectroscopy (Energy Dispersive X-ray Spectroscopy). It is called EDX.
- This X-ray spectrometer is widely used for identification and quantitative analysis of the composition of a compound (precipitate) observed by TEM. Also in the present invention, this X-ray spectrometer is used to calculate the average composition ratio of Zn and Mg of the grain boundaries observed by the TEM and the respective precipitates in the grains.
- the average composition ratio of Zn and Mg of the grain boundaries to be defined and the precipitates in the grains is determined at arbitrary points and 10 points in the 1/4 thickness direction from the surface of the test plate to be measured. This means that 10 samples are collected and the measurement results are averaged. More specifically, with respect to a cross section perpendicular to the plate thickness direction of the test plate, a TEM (transmission electron) of 60000 times the plane parallel to the plate surface passing through an arbitrary point from the surface to 1 ⁇ 4 part in the plate thickness direction. Measure using a microscope.
- a sample is prepared by mechanically polishing a plate cross-section sample surface sampled 10 pieces from the above-mentioned site, cutting off about 0.25 mm from the plate surface by mechanical polishing, and further performing buffing to adjust the surface.
- the grain boundary to be measured in the visual field and each precipitate in the grain are specified by an automatic analyzer, and the average composition ratio of Zn and Mg in these precipitates Is measured and the average value is calculated.
- the measurement site is the sample polishing surface, and the measurement area per sample is 240 ⁇ m ⁇ 180 ⁇ m.
- the 7000 series aluminum alloy plate can be manufactured by a manufacturing method according to a normal manufacturing process. That is, an aluminum alloy hot-rolled sheet having a thickness of 1.5 to 5.0 mm is manufactured through normal manufacturing processes such as casting (DC casting or continuous casting), homogenization heat treatment, and hot rolling. The Subsequently, it is cold-rolled to obtain a cold-rolled sheet having a thickness of 3 mm or less. At this time, intermediate annealing may be selectively performed once or twice in the middle of cold rolling.
- an ordinary molten casting method such as a continuous casting method or a semi-continuous casting method (DC casting method) is appropriately selected for the aluminum alloy melt adjusted within the above-mentioned 7000-based component composition range. Cast.
- homogenization heat treatment Next, the cast aluminum alloy ingot is subjected to a homogenization heat treatment prior to hot rolling.
- the purpose of this homogenization heat treatment (soaking) is to homogenize the structure, that is, eliminate segregation in crystal grains in the ingot structure.
- the structure of the plate to be produced is defined as an average composition ratio of Zn and Mg of the precipitates in the grain boundaries and the grains observed by the TEM, and after the molding processability to the structural material. It is necessary to improve both the strength after artificial aging treatment. For this reason, it is preferable to perform the soaking process in two or two soaking steps.
- the plate structure after aging at room temperature after the tempering treatment is defined as an average composition ratio range of Zn and Mg of grain precipitates and precipitates in the grains defined in the present invention. It becomes difficult to be inside.
- Two-stage soaking means cooling after the first soaking, but it is not cooled to 200 ° C. or lower, and after stopping the cooling at a higher temperature, after maintaining at that temperature, Hot rolling is started after reheating to a high temperature.
- the two-time soaking is once cooled to a temperature of 200 ° C. or less including room temperature, reheated and maintained at that temperature for a certain period of time. Start.
- a Zn compound or a transition element compound is finely dispersed to finely affect the compound that affects the moldability to the structural material.
- solid solution of Zn, Mg, and Cu is promoted.
- the average composition ratio of Zn and Mg of the precipitates in the grain boundaries and grains observed by the TEM is obtained.
- the soaking temperature in the first stage or the first time is controlled to 400 to 450 ° C., preferably 400 to 440 ° C.
- the ingot is heated and held in this temperature range.
- the holding time of the first or first soaking may be about 1 to 8 hours.
- the second or second soaking temperature is controlled to 450 ° C. to the solidus temperature, preferably 470 ° C. to the solidus temperature.
- the solid solution of the compound can be promoted by heating and holding the ingot in this temperature range. If this soaking temperature is less than 450 ° C., sufficient dissolution of these elements cannot be obtained. On the other hand, if the solidus temperature is exceeded, partial melting occurs and the mechanical properties deteriorate, so the upper limit is made the solidus temperature or lower.
- the holding time during the second or second soaking may be about 1 to 8 hours.
- the hot rolling start temperature is selected from the range of 350 ° C. to the solidus temperature and hot rolled to obtain a hot rolled sheet having a thickness of about 2 to 7 mm. There is no need for annealing (roughening) of the hot-rolled sheet before cold rolling.
- Cold rolling In cold rolling, the hot-rolled sheet is rolled into a cold-rolled sheet (including a coil) having a desired final thickness of about 1 to 3 mm. Intermediate annealing may be performed between cold rolling passes.
- solution treatment After cold rolling, solution treatment is performed as a tempering. Thus, the average composition ratio of Zn and Mg in the grain boundary precipitates (room temperature aging precipitates) observed by the TEM is obtained.
- the solution treatment is not particularly limited and may be heating and cooling using a normal continuous heat treatment line. However, in order to obtain a sufficient solid solution amount of each element and refinement of crystal grains, the holding time is predetermined at a solution treatment temperature of 450 ° C. to a solidus temperature, preferably 480 to 550 ° C. After reaching the solution treatment temperature, it is carried out in the range of 2 to 3 seconds and 30 minutes or less.
- the average cooling (temperature decrease) rate after the solution treatment is 10 ° C./s or more in order to obtain an average composition ratio of Zn and Mg of the grain boundary precipitates (room temperature aging precipitates) observed by the TEM.
- the cooling rate is preferably as high as possible, preferably 30 ° C./s or higher, more preferably 40 ° C./s or higher.
- the average cooling (cooling) rate after solution treatment is slow, coarse grain boundary precipitates are formed, and as a result, the grain boundary precipitates (room temperature aging precipitates) Zn and Mg are observed. It is difficult to achieve an average composition ratio.
- forced cooling means such as air cooling such as a fan, water cooling means such as mist, spray, and immersion are selected or combined, or they are baked in hot water from room temperature to 100 ° C.
- the solution treatment is basically only one time, but when the room temperature age hardening has progressed too much, the solution treatment and the restoration treatment are made the above-mentioned preferable conditions in order to ensure the moldability to the automobile member. It may be applied again, and this excessive room temperature age hardening may be canceled once.
- the aluminum alloy plate of the present invention is molded into an automobile member as a material and assembled as an automobile member.
- artificial aging treatment is separately performed to obtain an automobile member or an automobile body.
- Artificial age hardening treatment The 7000 series aluminum alloy plate of the present invention is observed by the TEM by an artificial age hardening treatment (hereinafter also simply referred to as artificial aging treatment or aging treatment) after forming into a structural material.
- the average composition ratio of Zn and Mg in the aging precipitate) is set to 380 MPa or more, preferably 400 MPa or more at a desired strength and 0.2% proof stress as a structural material such as an automobile member.
- the time point at which this artificial aging treatment is performed is preferably after the forming processing of the material 7000 series aluminum alloy plate to the automobile member. This is because the 7000 series aluminum alloy plate after the artificial aging treatment has high strength but has low formability, and may not be formed depending on the complexity of the shape of the automobile member.
- the temperature and time conditions of this artificial aging treatment are determined within the range of general artificial aging conditions (T6, T7) from the desired strength, the strength of the 7000 series aluminum alloy plate of the material, or the progress of room temperature aging. Is done.
- T6, T7 general artificial aging conditions
- the aging treatment at 100 to 150 ° C. is performed for 12 to 36 hours (including the overaging region) in the case of one-stage aging treatment.
- the first-stage heat treatment temperature is in the range of 70 to 100 ° C. for 2 hours or longer
- the second-stage heat treatment temperature is in the range of 100 to 170 ° C. for five hours or longer (overaging region). Select from).
- the strength after BH is used as the structural material, particularly as the average composition ratio of Zn and Mg in the intragranular precipitate (artificial aging precipitate) observed by the TEM.
- This condition means that the heating rate during the artificial aging treatment in the one-stage artificial aging process or the heating rate during the first artificial aging treatment in the two-stage artificial aging treatment is 30 ° C./min or less. It is to carry out at the slowest possible heating rate.
- the second stage temperature rise rate does not affect the strength after BH, and an efficient temperature rise rate of 30 ° C./min or more is selected.
- the second stage reheating can be performed after holding at the first stage heating temperature, after cooling to room temperature and then reheating, or by continuously reheating from the held temperature. There is no difference in the impact on either.
- the conditions of the artificial age hardening treatment in the average composition ratio (Zn / Mg) of Zn and Mg of the intragranular precipitates defined as preferable conditions in the present invention are 90 ° C. at a temperature rising rate of 30 ° C./min. It is set as a two-stage specific condition of heating to 140 ° C. at a heating rate of 30 ° C./min and holding for 8 hours. This is for the purpose of correlating the average composition ratio of Zn and Mg of intragranular precipitates produced in the actual artificial aging treatment after forming the material 7000 series aluminum alloy plate into an automobile member. It is.
- the conditions of the actual artificial aging treatment after forming the material 7000 series aluminum alloy plate on the automobile member are variously different.
- each heating rate is set to 30 ° C./min or less
- the artificial aging treatment conditions are within the above preferred range, the strength
- the temperature increase rate of 30 ° C./min under the condition of artificial age hardening in the average composition ratio (Zn / Mg) of the intragranular precipitates defined in the present invention is 380 MPa, which is necessary for the structural material.
- the average composition ratio (Zn / Mg) of Zn and Mg of the precipitates in the grain boundaries and grains within the plate is as shown in Tables 2 and 3 together with the component composition shown in Table 1
- the average cooling rate after the solution treatment of the cold rolled sheet was variously controlled.
- a 7000 series aluminum alloy molten metal having each component composition shown in Table 1 below was DC cast to obtain an ingot of 45 mm thickness ⁇ 220 mm width ⁇ 145 mm length.
- the ingot was subjected to two-stage soaking or twice soaking under the conditions shown in Table 2.
- the second stage soaking is cooled to 250 ° C., once the cooling is stopped at that temperature, reheated and held at the second stage soaking temperature, and cooled to the hot rolling start temperature.
- the hot rolling was started.
- the second soaking was once cooled to room temperature, reheated and held at the second soaking temperature, cooled to the hot rolling start temperature, and then started hot rolling.
- the soaking process of only one time in Table 2 does not perform the second reheating after cooling once, and keeps the soaking temperature and time as usual, and then cools to the hot rolling start temperature and performs hot rolling. Started.
- hot rolling was performed at a starting temperature shown in Table 2 to produce a hot rolled sheet having a thickness of 5 mm.
- This hot-rolled sheet was cold-rolled to 2 mmt without subjecting it to any roughening treatment.
- the cold-rolled sheet is subjected to a solution treatment at 500 ° C. for 1 minute in common with each example, and after this solution treatment, the method of forced air cooling is changed, and the average cooling rate is changed to various temperatures to cool to room temperature.
- a tempered material was obtained.
- the aluminum alloy plate after solution treatment was sampled from a plate aged at room temperature for 2 weeks in common with each example, and an average composition ratio of Zn and Mg of the precipitates at the grain boundaries was collected. Measurement of (Zn / Mg), measurement of work hardening index n value, mechanical properties such as strength and elongation were investigated as follows.
- the artificial age-hardening treatment after forming the automobile member was simulated, and the aluminum alloy sheet after room temperature aging for the above two weeks was treated as T6 treatment, and further the first stage temperature increase rate shown in Tables 2 and 3 Then, after holding at the aging temperature for 3 hours, the artificial age hardening treatment is performed in two stages in which it is continuously reheated from the held temperature, heated to 140 ° C. at a heating rate of 30 ° C./min and held for 8 hours. Went.
- Invention Example 18 in Table 2 was performed under the condition that the first stage was heated to 90 ° C. at a temperature increase rate of 30 ° C./min and held for 3 hours, and then the second stage was 30 ° C. / The heating rate was 1 minute, and the heating was performed up to 130 ° C. and held for 12 hours.
- Inventive example 19 in Table 2 was an artificial aging treatment with only one stage, and the temperature elevation rate was 30 ° C./min. The temperature was raised to 120 ° C. and maintained for 24 hours.
- a plate-shaped test piece is taken from the central part of the aluminum alloy plate after the artificial age hardening treatment, and the average composition ratio (Zn / Mg) of Zn and Mg of each precipitate in the grains, mechanical properties and corrosion resistance are also obtained.
- the investigation was conducted as follows. These results are shown in Tables 2 and 3, respectively.
- the work hardening index n value was measured by performing a room temperature tensile test in the direction perpendicular to the rolling direction, using the plate-like test piece after the artificial age hardening treatment as a JIS No. 5 tensile test piece (distance between gauge points 50 mm). Then, the true stress and true strain are calculated from the end point of yield elongation, plotted on a logarithmic scale with the horizontal axis being strain and the vertical axis being stress, and the gradient of the straight line represented by the measurement point is 10% or 15% of nominal strain. The n value (10 to 15%) was calculated from the two points.
- a current having a current density of 1 mA / cm 2 was allowed to flow for 24 hours in a state immersed in an aqueous sodium chloride solution (5% by mass), and then the sample was pulled up, and then the cross section of the test piece was cut and polished.
- the magnification was x100, and a corrosion depth of 200 ⁇ m or less was evaluated as “ ⁇ ” as minor corrosion. Moreover, the case where it exceeded 200 micrometers was evaluated as "x" as big corrosion.
- Invention Examples 1 to 19 are within the composition range of the aluminum alloy of the present invention, and are manufactured within the range of the preferable manufacturing conditions described above.
- (Zn / Mg) is in the range of 0.5 to 3.0.
- the average composition ratio (Zn / Mg) with Mg is in the range of 1.5 to 3.5, which satisfies the structure provision of the present invention.
- Comparative Examples 20 to 32 in Table 3 have an alloy composition of 17 to 29 as shown in Table 1, which is outside the scope of the present invention.
- the alloy compositions are numbers 17 and 18 in Table 1, and [Zn] and [Mg] are within the specified ranges, respectively, but are balanced expressions of Zn and Mg. Both [Zn] ⁇ ⁇ 0.3 [Mg] +4.5 and [Zn] ⁇ ⁇ 0.5 [Mg] +5.75 are not satisfied. For this reason, although it is manufactured within preferable manufacturing conditions, the composition ratio of precipitates is not satisfied, and the work hardening index n value (10 to 15%) after room temperature aging is 0.21 to 0.22 level. Even if the 0.2% yield strength after the age hardening treatment is high, it is too low at about 329 MPa, and it does not have both moldability and strength.
- the alloy compositions are 19 to 21 with the numbers in Table 1, and Mg is too small beyond the lower limit. For this reason, even if the balance formula of Zn and Mg is satisfied and manufactured within the preferable manufacturing conditions, the composition ratio Zn / Mg of the intragranular precipitate is outside the lower limit, and the work hardening index n after aging at room temperature. Although the value is 0.21 level, even if the 0.2% proof stress after the artificial age hardening treatment is high, it is too low at about 353 MPa, and it does not have both moldability and strength.
- Comparative Examples 25 to 28 have an alloy composition of 22 to 25 as shown in Table 1, and Mg is too much outside the upper limit. For this reason, even if the balance formula of Zn and Mg is satisfied and manufactured within the preferable manufacturing conditions, the composition ratio Zn / Mg of the intragranular precipitate is outside the lower limit, and the work hardening index n after aging at room temperature. Although the value (10-15%) is 0.22 to 0.23 level, even if the 0.2% proof stress after artificial age hardening is high, it is too low at around 369 MPa, and it does not have both moldability and strength. .
- Comparative Examples 29 and 30 have alloy compositions of numbers 26 and 27 in Table 1, and Zn is too much outside the upper limit. For this reason, even if the balance formula of Zn and Mg is satisfied and manufactured within the preferable manufacturing conditions, the composition ratio Zn / Mg of the intragranular precipitate is outside the lower limit, and the work hardening index n after aging at room temperature. Although the value (10-15%) is 0.22 to 0.23 level, even if the 0.2% yield strength after artificial age hardening is high, it is too low at around 362 MPa, and it does not have both moldability and strength. . Moreover, corrosion resistance is also inferior.
- Comparative Example 31 has an alloy composition of 28 as shown in Table 1, and Cu is out of the lower limit. For this reason, the balance formula of Zn and Mg is satisfied, manufactured within preferable manufacturing conditions, satisfies the precipitate composition ratio, and has a work hardening index n value (10 to 15%) after aging at room temperature of 0.23. In terms of level, the 0.2% proof stress after the artificial age hardening treatment is also at the 448 MPa level, and it has both moldability and strength. However, it is fatally inferior in corrosion resistance.
- Comparative Example 32 has an alloy composition of 29 in Table 1 and Cu is out of the upper limit. For this reason, the balance formula of Zn and Mg is satisfied, and it is manufactured within preferable manufacturing conditions and satisfies the precipitate composition ratio, but the work hardening index n value (10 to 15%) after aging at room temperature is 0.00. It is as low as 209, and the 0.2% proof stress after artificial age hardening is at the level of 456 MPa, but it does not have both moldability and strength.
- Comparative Examples 33 to 37 in Table 3 are manufactured out of the preferable manufacturing condition range, although the invention example aluminum alloy of Alloy No. 1 in Table 1 is used.
- the first soaking temperature is too low.
- Comparative Example 34 the second soaking temperature is too low.
- Comparative Example 35 the average cooling rate after the solution treatment is too slow.
- Comparative Examples 36 and 37 are only one-time heat treatment.
- the comparative example in which these soaking conditions deviate from the preferred range does not satisfy the compositional ratio Zn / Mg of grain boundary precipitates or the composition ratio Zn / Mg of intragranular precipitates, and work hardening after aging at room temperature.
- the index n value (10 to 15%) is less than 0.22 and the ductility and molding processability to structural materials are inferior, or the 0.2% proof stress after artificial age hardening is less than 340 MPa. It does not have both workability and strength.
- the present invention can provide a 7000 series aluminum alloy plate for automobile members having strength, formability, and corrosion resistance even after aging at room temperature. Therefore, the present invention is also suitable for automobile structural materials such as frames and pillars that contribute to weight reduction of the vehicle body, and structural materials for other uses.
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Abstract
Selon l'invention, une plaque en alliage d'aluminium de séries 7000 d'une composition spécifique manufacturée par un procédé usuel conserve une dureté élevée, un équilibre entre les teneurs en Mg et Zn, tout en régulant la teneur en Zn. Cette plaque présente une résistance à la corrosion, un aptitude au moulage et une résistance élevée nécessaires à un élément structurel, grâce à la régulation du rapport de composition moyen entre Zn et Mg dans un précipité de joint de grain, lorsque la plaque manufacturée est vieillie à température ambiante, et grâce à la régulation du rapport de composition moyen entre Zn et Mg dans un précipité intragranulaire de la plaque après qu'un ultérieur traitement de durcissement et de vieillissement artificiel soit mis en oeuvre.
Priority Applications (2)
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US15/126,421 US20170081749A1 (en) | 2014-03-17 | 2015-03-16 | Aluminum alloy sheet for structural components |
CN201580011346.4A CN106062226A (zh) | 2014-03-17 | 2015-03-16 | 结构材料用铝合金板 |
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JP2014-053702 | 2014-03-17 | ||
JP2014053702A JP2015175045A (ja) | 2014-03-17 | 2014-03-17 | 構造材用アルミニウム合金板 |
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WO2015141647A1 true WO2015141647A1 (fr) | 2015-09-24 |
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PCT/JP2015/057774 WO2015141647A1 (fr) | 2014-03-17 | 2015-03-16 | Plaque en alliage d'aluminium pour élément structurel |
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US (1) | US20170081749A1 (fr) |
JP (1) | JP2015175045A (fr) |
CN (1) | CN106062226A (fr) |
WO (1) | WO2015141647A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3239313A3 (fr) * | 2016-04-04 | 2019-08-14 | Korea Automotive Technology Institute | Alliage d'aluminium corroyé |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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JP6880989B2 (ja) * | 2017-04-26 | 2021-06-02 | 日立金属株式会社 | 吸着構造体ユニット及びそれらの製造方法 |
CN106929720B (zh) * | 2017-05-02 | 2019-03-22 | 常州市亿和合金熔铸有限公司 | 一种高强度易再结晶变形铝合金及其制备方法 |
EP3848476A1 (fr) * | 2020-01-07 | 2021-07-14 | AMAG rolling GmbH | Tôle ou bande en alliage d'aluminium durcissable, pièce de véhicule fabriquée à partir de celle-ci, utilisation et procédé de fabrication de tôle ou de bande |
MX2023003128A (es) * | 2020-09-17 | 2023-03-22 | Novelis Inc | Aleaciones de aluminio de la serie 7xxx de alta resistencia y sensibles al bajo enfriamiento y metodos de fabricacion. |
CN113981342B (zh) * | 2021-09-03 | 2022-09-06 | 福建祥鑫新材料科技有限公司 | 一种提高7系铝合金抗应力腐蚀性能的热处理方法 |
CN115261683B (zh) * | 2022-04-04 | 2024-04-09 | 中国第一汽车股份有限公司 | 一种免水淬的高强韧铸造Al-Si合金及其制备方法 |
EP4332260A1 (fr) | 2022-09-05 | 2024-03-06 | AMAG rolling GmbH | Alliage d'aluminium durcissable, bande ou feuille d'alliage d'aluminium à partir de cet alliage, procédé de fabrication de cette bande ou feuille d'alliage d'aluminium durcissable et son utilisation dans un formage superplastique |
CN115161524B (zh) * | 2022-09-08 | 2022-11-29 | 北京科技大学 | 一种抗应力腐蚀高强铝合金及其制备方法 |
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JPH01127642A (ja) * | 1987-11-10 | 1989-05-19 | Kobe Steel Ltd | 絞り成形用熱処理型高強度アルミニウム合金板及びその製造法 |
JP2009221566A (ja) * | 2008-03-18 | 2009-10-01 | Kobe Steel Ltd | 耐水素脆化特性に優れた高圧ガス容器用アルミニウム合金材 |
JP2010159489A (ja) * | 2008-12-09 | 2010-07-22 | Sumitomo Light Metal Ind Ltd | 7000系アルミニウム合金材の成形加工方法及び該7000系アルミニウム合金材の成形加工方法により成形される成形加工品 |
WO2014142199A1 (fr) * | 2013-03-14 | 2014-09-18 | 株式会社神戸製鋼所 | Plaque en alliage d'aluminium destinée à un matériau de structure |
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US2631317A (en) * | 1949-02-18 | 1953-03-17 | Gourielli Inc | Perfume applicator |
US4060411A (en) * | 1975-02-26 | 1977-11-29 | Mamiya Koki Kabushiki Kaisha | Precipitation-hardenable, nitrided aluminum alloys and nitrided mother alloys therefor |
JPH03122247A (ja) * | 1989-10-06 | 1991-05-24 | Furukawa Alum Co Ltd | 耐応力腐食割れ性に優れた溶接用高力アルミニウム合金 |
CN101621006B (zh) * | 2008-07-03 | 2011-01-12 | 中芯国际集成电路制造(上海)有限公司 | 利用锗预非晶处理来形成p-型轻度掺杂的漏极区的方法 |
FR2976967B1 (fr) * | 2011-06-22 | 2015-05-01 | Total Sa | Fluides traceurs a effet memoire pour l'etude d'un gisement petrolier |
CN102876942A (zh) * | 2012-09-04 | 2013-01-16 | 昆山市源丰铝业有限公司 | 车用铝合金板 |
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2014
- 2014-03-17 JP JP2014053702A patent/JP2015175045A/ja not_active Ceased
-
2015
- 2015-03-16 CN CN201580011346.4A patent/CN106062226A/zh active Pending
- 2015-03-16 US US15/126,421 patent/US20170081749A1/en not_active Abandoned
- 2015-03-16 WO PCT/JP2015/057774 patent/WO2015141647A1/fr active Application Filing
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JPH01127642A (ja) * | 1987-11-10 | 1989-05-19 | Kobe Steel Ltd | 絞り成形用熱処理型高強度アルミニウム合金板及びその製造法 |
JP2009221566A (ja) * | 2008-03-18 | 2009-10-01 | Kobe Steel Ltd | 耐水素脆化特性に優れた高圧ガス容器用アルミニウム合金材 |
JP2010159489A (ja) * | 2008-12-09 | 2010-07-22 | Sumitomo Light Metal Ind Ltd | 7000系アルミニウム合金材の成形加工方法及び該7000系アルミニウム合金材の成形加工方法により成形される成形加工品 |
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Publication number | Priority date | Publication date | Assignee | Title |
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EP3239313A3 (fr) * | 2016-04-04 | 2019-08-14 | Korea Automotive Technology Institute | Alliage d'aluminium corroyé |
EP3680356A1 (fr) * | 2016-04-04 | 2020-07-15 | Korea Automotive Technology Institute | Alliage d'aluminium corroyé |
Also Published As
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US20170081749A1 (en) | 2017-03-23 |
JP2015175045A (ja) | 2015-10-05 |
CN106062226A (zh) | 2016-10-26 |
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