JP5860371B2 - Aluminum alloy automotive parts - Google Patents

Description

  The present invention relates to a high-strength aluminum alloy automobile member.

  In recent years, due to consideration for the global environment, social demands for reducing the weight of automobile bodies are increasing. In order to meet such demands, panels (outer panels such as hoods, doors, and roofs, inner panels), bumper fountains (bumper R / F), door beams, and other reinforcing materials are partly made of steel, etc. Instead of the steel material, an aluminum alloy material is applied.

  However, in order to reduce the weight of the automobile body, it is necessary to expand the application of the aluminum alloy material to automobile structural members such as frames and pillars that contribute particularly to weight reduction among the automobile members. However, these automobile structural members need to have higher strength than the automobile panel, such as the required 0.2% proof stress is 350 MPa or more. In this respect, in the JIS to AA 6000 series aluminum alloy plates, which are used in the above-mentioned automobile panels and have excellent formability, strength, corrosion resistance, low alloy composition and recyclability, composition and tempering (solution treatment and Even if the quenching process and further the artificial age hardening process) are controlled, there is a great limit to the increase in the strength.

Therefore, it is necessary to use a JIS or AA 7000 series aluminum alloy plate used as the reinforcing material requiring the same high strength for such a high-strength automobile structural member. However, a 7000 series aluminum alloy, which is an Al—Zn—Mg series aluminum alloy, is an alloy that achieves high strength by distributing precipitates MgZn ₂ composed of Zn and Mg at a high density. Therefore, there is a risk of causing stress corrosion cracking (hereinafter referred to as SCC), and in order to prevent this, it is unavoidable that it is over-aged and used at a proof stress of about 300 MPa. The characteristics of are fading.

  For this reason, various composition control of the 7000 series aluminum alloy excellent in both strength and SCC resistance and structure control of precipitates have been conventionally proposed.

As a typical example of composition control, for example, in Patent Document 1, Mg added in excess of Zn and Mg content (stoichiometry ratio of MgZn ₂ ) of a 7000 series aluminum alloy extruded material that forms MgZn ₂ without excess or deficiency. but by utilizing the fact that contributes to high strength by adding Mg to excess over stoichiometric ratio of MgZn _2, to suppress the MgZn ₂ amount, without reducing the SCC resistance, and high strength Yes.

As a representative example of the structure control of precipitates and the like, for example, in Patent Document 2, a 7000-series aluminum alloy extruded material after artificial age hardening treatment is used for a precipitate having a particle diameter of 1 to 15 nm in crystal grains. As a result of observation by (TEM), it is made to exist at a density of 1000 to 10000 / μm ² to reduce the potential difference between the inside of the grain and the grain boundary, thereby improving the SCC resistance.

  In addition to this, although not all can be exemplified, examples of composition control to improve both the strength and SCC resistance of 7000 series aluminum alloy extruded materials and examples of structure control such as precipitates are many practical applications in extruded materials. There are many in proportion to On the other hand, there are very few examples of 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.

  For example, in Patent Document 3, in a structural material made of a clad plate in which 7000 series aluminum alloy plates are welded together, the diameter of an aging precipitate after artificial age hardening treatment is 50 mm (angstrom) or less in order to improve strength. It has been proposed that a certain amount exists as a spherical shape. However, there is no disclosure about the SCC resistance performance, and there is no corrosion resistance data in the examples.

  Further, Patent Document 4 discloses that the crystal precipitates in the crystal grains of the 7000 series aluminum alloy plate after the artificial age hardening treatment are measured with a 400 times optical microscope to obtain a size (equivalent to an equivalent circle diameter in area). Conversion) is 3.0 μm or less, and the average area fraction is 4.5% or less to improve strength and elongation. However, there is no disclosure about the SCC resistance performance, and there is no corrosion resistance data in the examples.

JP 2011-144396 A JP 2010-275611 A JP-A-9-125184 JP 2009-144190 A

  As described above, various proposals have been made for extruded materials such as composition control of a 7000 series aluminum alloy excellent in both strength and SCC resistance and structure control of precipitates. However, as for the 7000 series aluminum alloy rolled sheet such as a hot-rolled sheet or a cold-rolled sheet (the hot-rolled sheet is further cold-rolled), there is no actual proposal except for the purpose of improving the strength.

  And, 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. For this reason, proposals such as composition control in the extruded material and structure control of precipitates can be applied to 7000 series aluminum alloy rolled sheets and also to automobile members made of these 7000 series aluminum alloy rolled sheets. It is unclear whether it is effective for improving both strength and SCC resistance. In other words, unless it is actually confirmed, it does not leave the expected range.

  Therefore, there is still no effective means for the structure control technology excellent in both strength and SCC resistance of an automobile member made of a 7000 series aluminum alloy rolled plate, and there are many unclear points and room for clarification. Currently.

  In view of the problems described above, an object of the present invention is to provide an automobile member that is composed of a rolled 7000 series aluminum alloy sheet and has both strength and stress corrosion cracking resistance.

To this end, the gist of the present invention an aluminum alloy automotive member is an aluminum alloy automotive member thickness is 1 to 3 mm, in mass%, Zn: 3.0 to 8.0 % Mg: includes 0.5 to 4.0%, and the balance of the set formed of Al and unavoidable impurities, as a woven set after artificial aging curing was measured at a magnification 300,000 × transmission electron microscopy The number density of precipitates having a size of 2.0 to 20 nm in the crystal grains has an average structure of 2.0 × 10 ⁴ pieces / μm ³ or more, and 0.2% proof stress is 350 MPa or more. .

  The aluminum alloy rolled sheet referred to in the present invention is a hot-rolled sheet that has been hot-rolled or a cold-rolled sheet that has been cold-rolled, and is a material aluminum alloy that has undergone tempering such as solution treatment and quenching. Say the board. And this invention is a motor vehicle member after such a raw material aluminum alloy rolled sheet is processed into a motor vehicle member, is further assembled as a motor vehicle member, and the artificial age hardening process was performed.

  Therefore, in the present invention, the composition, structure and strength as an automobile member which is the final use state are defined, not the state of the raw aluminum alloy rolled plate. That is, the composition, structure, and strength are defined after the rolled aluminum alloy sheet is assembled as an automobile member and subjected to artificial age hardening as an automobile body. The artificial age hardening treatment referred to in the present invention refers to an age hardening treatment by artificial heating, and is clearly distinguished from natural age hardening at room temperature or the like (hereinafter simply referred to as artificial age treatment or age treatment). Also called).

  In the present invention, nano-sized fine precipitates of such an aluminum alloy automobile member, which can be measured by the high-power transmission electron microscope, are present in the crystal grains at a certain fixed number density. Let In addition, this control can also suppress the precipitation of precipitates existing at grain boundaries and coarse precipitates existing within crystal grains.

  As a result, the present invention can achieve an increase in strength such that the 0.2% proof stress of an aluminum alloy automobile member is 350 MPa or more, and despite this high strength, the SCC resistance is reduced. Can be suppressed.

Hereinafter, embodiments of the present invention will be specifically described for each requirement.
First, the chemical composition of the automobile member of the present invention or the material aluminum alloy rolled sheet 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 rolled sheet of the present invention is determined as an Al—Zn—Mg—Cu based 7000 series aluminum alloy in order to guarantee the properties such as strength and SCC resistance of the automobile member intended in the present invention. The From this point of view, the chemical composition of the rolled aluminum alloy sheet of the present invention is, in mass%, Zn: 3.0-8.0%, Mg: 0.5-4.0%, the balance being Al and inevitable It shall consist of impurities. This composition may further optionally include one or two of Cu: 0.05 to 0.6% and Ag: 0.01 to 0.15%, in addition to or in addition to this. Separately, one or more of Mn: 0.05 to 0.3%, Cr: 0.03 to 0.2%, and Zr: 0.03 to 0.3% may be selectively included.

Zn: 3.0-8.0%:
Zn, which is an essential alloy element, improves the strength together with Mg by forming fine precipitates, which are intermetallic compounds of Mg and Zn, defined in the present invention during the artificial age hardening treatment. If the Zn content is less than 3.0%, the strength is insufficient, and if it exceeds 8.0%, the grain boundary precipitate MgZn ₂ increases and the SCC sensitivity becomes sharp. Therefore, the Zn content is in the range of 3.0 to 8.0%. In order to prevent the Zn content from increasing and the SCC sensitivity from becoming sharp, it is desirable to add Cu or Ag described later. Preferably it is 4.0 to 7.0%.

Mg: 0.5-4.0%
Mg, which is an essential alloying element, together with Zn, forms fine precipitates that are intermetallic compounds of Mg and Zn as defined in the present invention during artificial age hardening, thereby improving strength and elongation. If the Mg content is less than 0.5%, the strength is insufficient, and if it exceeds 4.0%, the rollability of the plate is lowered and the SCC sensitivity becomes sharp. Therefore, the Mg content is in the range of 0.5 to 4.0%, preferably 3.0% or less.

One or two of Cu: 0.05 to 0.6% and Ag: 0.01 to 0.15%:
Cu and Ag have the effect of improving the SCC resistance of the Al—Zn—Mg alloy. When one or both of these are contained, the effect of improving SCC resistance is small when the Cu content is less than 0.05% and the Ag content is less than 0.01%. On the other hand, if the Cu content exceeds 0.6%, various properties such as rollability and weldability are reduced. Moreover, even if it contains Ag content exceeding 0.15%, the effect will be saturated and it will become expensive. Therefore, the Cu content is 0.05 to 0.6%, preferably 0.4% or less, and the Ag content is 0.01 to 0.15%.

One or more of Mn: 0.05 to 0.3%, Cr: 0.03 to 0.2%, Zr: 0.03 to 0.3%:
Mn, Cr and Zr contribute to strength improvement by refining the crystal grains of the ingot. When any one, two or three of these are contained, if the content of Mn, Cr, or Zr is less than the lower limit, the content is insufficient, recrystallization is promoted, and SCC resistance is improved. descend. On the other hand, when the contents of Mn, Cr, and Zr exceed the respective upper limits, a coarse crystallized product is formed, resulting in a decrease in elongation. Therefore, the ranges are Mn: 0.05 to 0.3%, Cr: 0.03 to 0.2%, and Zr: 0.03 to 0.3%.

Ti, B:
Ti and B are impurities in the rolled plate, but have the effect of refining the crystal grains of the aluminum alloy ingot, so that each content in the range specified by the JIS standard is allowed as a 7000 series alloy. The upper limit of Ti is 0.2%, preferably 0.1%, and the upper limit of B is 0.05% or less, preferably 0.03%.

Other elements:
In addition to these elements, other elements such as Fe and Si are inevitable impurities. As a melting raw material, in addition to pure aluminum ingots, the inclusion of these impurity elements due to the use of aluminum alloy scrap is assumed (allowed), and each content within the range specified by the JIS standard of 7000 series alloys is allowed. . For example, if Fe: 0.5% or less and Si: 0.5% or less, inclusion is permitted without affecting the characteristics of the aluminum alloy rolled sheet according to the present invention.

(Organization)
In the present invention, the number density of precipitates having a size of 2.0 to 20 nm measured with a transmission electron microscope having a magnification of 300,000 times is used as the structure after the artificial age hardening treatment is performed on the 7000 series aluminum alloy structure of the automobile member. Is defined as a structure having an average of 2.0 × 10 ⁴ pieces / μm ³ in the crystal grains. This precipitate is an intermetallic compound of Mg and Zn (composition is MgZn ₂ or the like) that is generated in crystal grains during the artificial age hardening treatment or the like, and according to the composition, Cu, It is a finely dispersed phase containing a contained element such as Zr. In addition, the size of the precipitate referred to in the present invention refers to the equivalent-circle diameter (average diameter) of the precipitate having an irregular shape.

  In this way, by allowing a precipitate having a fine size of 2.0 to 20 nm to exist in the crystal grains at a certain number of the number density specified above, the 0.2% proof stress of the aluminum alloy automobile member is 350 MPa or more. A certain level of strength and elongation can be achieved. Further, by allowing the fine size precipitates to exist as defined above, it is possible to suppress the precipitation existing at the grain boundaries and the coarse precipitates existing within the crystal grains. Contributes to improved growth. And although it is such high intensity | strength, it has also led to being able to suppress a fall of SCC resistance.

If the number density of the precipitates having a size of 2.0 to 20 nm is less than 2.0 × 10 ⁴ / μm ³ on average in the crystal grains, high strength cannot be achieved. This is because the fine precipitates having a size of 2.0 to 20 nm that contribute to the increase in strength are insufficient. The upper limit of the number density of the precipitates having a size of 2.0 to 20 nm is limited by the production limit by controlling the composition and heat treatment, and the upper limit within the crystal grains is only about 10 ⁵ particles / μm ^{3 on} the average. Cannot be deposited inside.

  In the present invention, not the material aluminum alloy rolled sheet, but a structure as an automobile member after the rolled sheet is processed and further subjected to artificial age hardening. The nano-sized fine precipitates defined in the present invention greatly change depending on the heat treatment conditions, and after the solution treatment and quenching treatment of the aluminum alloy rolled sheet of the material, and also greatly depending on the subsequent artificial aging treatment conditions. is there.

  The number density of the precipitates having a size of 2.0 to 20 nm of the present invention is too fine to be observed or measured with an optical microscope of about 400 times used in the above-mentioned conventional technology, and the prescribed magnification is 300000 times. It can be observed with a high-power transmission electron microscope.

(Production method)
The manufacturing method of the 7000 series aluminum alloy rolled sheet in the present invention will be specifically described below.

  In this invention, it can manufacture with the manufacturing method by the normal manufacturing process of a 7000 series aluminum alloy rolled sheet. 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 At this stage, a product plate may be used. Further, it is further cold-rolled while selectively performing intermediate annealing once or twice before cold rolling or in the middle of cold rolling to obtain a cold plate having a thickness of 3 mm or less. It is good also as a product board of a rolled sheet.

(Dissolution, casting cooling rate)
First, in the melting and casting process, 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 homogenization heat treatment conditions are suitably selected from a range of homogenization time of 2 hours or more, preferably at a temperature of about 400 to 550 ° C.

(Hot rolling)
In the hot rolling, the hot rolling itself becomes difficult because burning occurs under conditions where the hot rolling start temperature exceeds the solidus temperature. On the other hand, when the hot rolling start temperature is less than 350 ° C., the load during hot rolling becomes too high, and the hot rolling itself becomes difficult. Therefore, 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. Annealing (roughening) of the hot-rolled sheet before cold rolling is not always necessary, but may be performed.

(Cold rolling)
In the cold rolling, the hot-rolled sheet is rolled to produce a cold-rolled sheet (including a coil) having a desired final sheet thickness of about 1 to 3 mm. Intermediate annealing may be performed between cold rolling passes.

(Solution and quenching)
After cold rolling, solution treatment and quenching are performed. The solution treatment quenching process may be a general heating or cooling method and is not particularly limited. However, in order to obtain a sufficient solid solution amount of each element or to refine crystal grains, it is desirable to set a solution treatment temperature of 450 to 550 ° C.

  In addition, from the viewpoint of suppressing the formation of coarse grain boundary precipitates that reduce strength and formability, the average cooling rate of the quenching treatment after the solution treatment is preferably 5 ° C./s or more. When this cooling rate is low, coarse grain boundary precipitates are generated during cooling, the amount of solid solution after solution treatment is reduced, and the amount of hardening in the subsequent aging treatment is reduced. In order to ensure this cooling rate, the quenching treatment is performed by selecting water cooling means and conditions such as air cooling such as a fan, mist, spray, and immersion, respectively.

Artificial age hardening treatment:
The conditions of the artificial age-hardening treatment of the raw material plate manufactured as described above, for example, after being formed into an automobile material, are selected so as to have the strength and elongation required for the automobile material. For example, in the case of one-stage aging treatment, aging treatment at 100 to 150 ° C. is performed for 12 to 36 hours (including an overaging region). In the two-stage process, the first-stage heat treatment temperature is in the range of 70 to 100 ° C. for 2 hours or longer, and the second-stage heat treatment temperature is in the range of 100 to 170 ° C. for five hours or longer (over-aged region). Select from).

  7000 series aluminum alloy cold-rolled sheets of each component composition shown in Table 1 below are manufactured, and this tempered cold-rolled sheet is simulated to be applied to a particularly high-strength automobile structure material among automobile members. The structure and mechanical properties of this plate after age hardening were measured and evaluated. These results are shown in Table 2 below.

  Specifically, in common with each example, 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 hot rolling after homogenization heat treatment at 470 ° C. for 4 hours to produce a hot rolled sheet having a thickness of 5.0 mm. This hot-rolled sheet was cold-rolled without being roughened (annealed) and without intermediate annealing between passes, and was commonly used as a cold-rolled sheet having a thickness of 2.0 mm. The cold-rolled sheet was water-cooled after solution treatment at 500 ° C. for 30 seconds in common with each example. Finally, an artificial age hardening treatment simulating an automobile structural material was performed under the conditions shown in Table 2.

  Test pieces were collected from the aluminum alloy plate after the artificial age hardening treatment thus obtained, and the number density and mechanical properties of the fine precipitates in the crystal grains were examined as follows. These results are shown in Table 2, respectively.

(Mechanical properties)
In each example, a room temperature tensile test in the direction perpendicular to the rolling direction of a plate-shaped test piece obtained by cutting the center part of each obtained aluminum alloy plate was performed, and tensile strength (MPa), 0.2% proof stress (MPa) The total elongation (%) was measured. The room temperature tensile test was performed at a room temperature of 20 ° C. based on JIS2241 (1980). The tensile speed was 5 mm / min, and the test was performed at a constant speed until the test piece broke.

(Fine precipitate)
In each example, a thin film sample was prepared from the cross section of the central portion of the plate-shaped test piece, and a portion having a film thickness of 0.1 μm was observed at a accelerating voltage of 200 kV using a transmission electron microscope with a magnification of 300,000 times. The average number density (pieces / μm ³ ) of precipitates having a size of 2.0 to 20 nm was measured. This observation was performed on five test pieces, and the number density of the precipitates having a size of 2.0 to 20 nm in the crystal grains was obtained and averaged (referred to as average number density). Here, as described above, the size of the precipitate was measured in terms of the diameter of a circle having an equivalent area.

SCC resistance:
In order to evaluate the SCC resistance of the aluminum alloy sheet after the artificial age hardening treatment, a stress corrosion cracking test by a chromic acid acceleration method was performed. A plate-shaped test piece was cut out from the tempered cold-rolled plate, subjected to a 4% strain load in the direction perpendicular to the rolling direction after heat treatment at 400 ° C., and subjected to age hardening treatment shown in Table 2, followed by 90 ° C. It was immersed in the test solution for a maximum of 10 hours, and SCC was visually observed. The stress load was determined by generating a tensile stress on the outer surface of the test piece by tightening the bolts and nuts of the jig, and the load strain was measured with a strain gauge adhered to the outer surface. A test solution was prepared by adding 36 g of chromium oxide, 30 g of potassium dichromate and 3 g of sodium chloride (per liter) to distilled water. The case where no SCC occurred was evaluated as ◯, and the case where SCC occurred within 10 hours was evaluated as x.

As is clear from Tables 1 and 2, each invention example is within the composition range of the aluminum alloy of the present invention, and the number density of precipitates having a size of 2.0 to 20 nm as the structure after the artificial age hardening treatment is performed. It has a structure which is 2.0 × 10 ⁴ pieces / μm ³ or more on average. As a result, the 0.2% yield strength after the artificial aging treatment is 350 MPa or more, preferably 400 MPa or more, and the SCC resistance is also excellent. The total elongation is also preferably 13.0% or more.

  On the other hand, each comparative example is outside the scope of the present invention as shown in Table 1. In Comparative Example 6, Zn falls outside the lower limit. In Comparative Example 7, Mg deviates from the lower limit. Although these comparative examples are manufactured by a preferable manufacturing method, the number density of precipitates having a size of 2.0 to 20 nm is small and the strength is low. In Comparative Example 8, since Cu exceeded the upper limit, a large crack occurred during hot rolling, and the production was interrupted. In Comparative Example 9, Zr deviates from the upper limit. For this reason, coarse crystals are formed and the elongation is extremely low.

  Further, Comparative Example 10 shows a case where the alloy composition is within the range of the present invention as shown in Table 1, but is not strengthened because the heating time of the artificial age hardening treatment is too short.

  The above results support the critical significance of the requirements of the present invention for the aluminum alloy sheet of the present invention to have both high strength, high ductility and SCC resistance.

  As described above, the present invention can provide an automobile member having both strength and stress corrosion cracking resistance, which is made of a 7000 series aluminum alloy rolled sheet. Therefore, it is suitable for an automobile member that uses an aluminum alloy to reduce the weight of the vehicle body, and particularly for a high-strength automobile structure member such as a frame or a pillar.

Claims (3)

A aluminum alloy automotive member thickness is 1 to 3 mm, in mass% Zn: 3.0 to 8.0% Mg: includes 0.5 to 4.0%, the balance being Al and an aluminum alloy composition consisting of unavoidable impurities, as after artificial aging curing organization, precipitation the number density of the size of 2.0~20nm in the crystal grains as measured at a magnification 300,000 × transmission electron microscope at an average An automobile member having a structure of 2.0 × 10 ⁴ pieces / μm ³ or more and 0.2% proof stress of 350 MPa or more.   The automobile member according to claim 1, wherein the aluminum alloy further includes one or two of Cu: 0.05 to 0.6% and Ag: 0.01 to 0.15% by mass%.   The aluminum alloy is one or more of Mn: 0.05 to 0.3%, Cr: 0.03 to 0.2%, and Zr: 0.03 to 0.3% in mass%. The automobile member according to claim 1, comprising: