CN103282526B - Magnesium alloy materials - Google Patents
Magnesium alloy materials Download PDFInfo
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- CN103282526B CN103282526B CN201180063110.7A CN201180063110A CN103282526B CN 103282526 B CN103282526 B CN 103282526B CN 201180063110 A CN201180063110 A CN 201180063110A CN 103282526 B CN103282526 B CN 103282526B
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/06—Alloys based on magnesium with a rare earth metal 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
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metal Rolling (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Forging (AREA)
Abstract
The present invention provides the magnesium alloy materials of excellent corrosion resistance. A kind of magnesium alloy materials, it is made up of the magnesium alloy of the Al containing 7.3 mass %��16 mass %, when the content of Al overall for this magnesium alloy materials is set to x mass %, the content of Al is more than 0.8x mass % and 1.2x mass % area below is 50 more than area %, the region that the content of Al is more than 1.4x mass % is 17.5 below area %, and the content being created substantially absent Al is 4.2 mass % area below. In this magnesium alloy materials, the deviation of Al concentration is little, and the few region of the content of Al is few, thereby, it is possible to be effectively prevented the aggravation of the generation of the corrosion of locality, this corrosion. Therefore, compared with the die-casting material identical with overall Al content, the excellent corrosion resistance of this magnesium alloy materials. This magnesium alloy materials can enumerate sheet material, the coiled material obtained by the sheet material winding of long size, formed products.
Description
Technical field
The present invention relates to various components such as being suitable to the housing of electric/electronic device class, automotive part and the raw-material magnesium alloy materials of these components. Particularly relate to the magnesium alloy materials of excellent corrosion resistance.
Background technology
Constituent material containing various components such as the housing in the Portable power pneumoelectric subset class such as mobile phone, subnotebook PC used for magnesium alloy of various addition element and automobile components in magnesium.
The main flow of the component being made up of magnesium alloy is die-casting material and thixotropic injection moulding material (the AZ91 alloy of ASTM standard). In recent years, using the component plate being made up of the wrought magnesium alloy being representative with the AZ31 alloy of ASTM standard being implemented punch process and obtain always. Patent documentation 1 proposes the magnesium alloy plate that alloy is constituted and punch process is excellent worked as by the AZ91 alloy phase with ASTM standard.
Owing to magnesium is active metal, therefore, the surface to above-mentioned component or as its raw-material magnesium alloy plate is implemented the anti-corrosion treatment such as anodized, chemical conversion treatment and is improved corrosion resistance.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2007-098470 publication
Summary of the invention
Invent problem to be solved
The magnesium alloy containing Al such as above-mentioned AZ31 alloy and AZ91 alloy has the content tendency that corrosion resistance is more excellent more at most of Al. Such as, the excellent corrosion resistance of AZ91 alloy in the magnesium alloy. But, even the component being made up of AZ91 alloy (mainly die-casting material and thixotropic injection moulding material), it is also desirable to carry out above-mentioned anti-corrosion treatment. It reason for this is that, even the die-casting material etc. being made up of AZ91 alloy, if carry out corrosion testing described later when not implementing anti-corrosion treatment, then also can produce the corrosion of locality. Therefore, for magnesium alloy materials, it is desirable to improve corrosion resistance further.
Therefore, it is an object of the invention to provide the magnesium alloy materials of excellent corrosion resistance.
As it has been described above, the content of Al is more many more can improve corrosion resistance. Therefore, the present inventor, with the magnesium alloy of the Al containing more than 7.3 mass % for object, makes various forms of magnesium alloy materials and have studied corrosion resistance. As a result, even if all the content of the Al of magnesium alloy materials is identical, also can make because form is different corrosion resistance have excellent have bad. In order to illustrate its reason, first, the tissue of each form has been carried out research as a result, in the magnesium alloy materials of corrosion-resistant, there is thick precipitate (based on the addition element in alloy. Representational is containing at least one intermetallic compound in Al and Mg), in the magnesium alloy materials of excellent corrosion resistance, fine precipitate exists dispersedly, or is created substantially absent precipitate.
At this, the addition element such as the Al in magnesium alloy mainly goes out at least one state in thing and solid solution exist with precipitate (representational precipitate is for intermetallic compound), crystalline substance. When Al is for precipitate etc., precipitate and composition are few away from the Al quantitative change of the parent phase of the magnesium alloy in region about itself.
There is the tissue of above-mentioned coarse precipitates and can be described as the tissue that the big region of higher than surrounding and this high Al Concentration portion the Area comparison of Al concentration (mainly by precipitate and the region that formed about) exists locally. In other words, it may be said that be the relatively low region of Al concentration locally and a large amount of tissue existed. Furthermore, it is believed that be susceptible to corrosion at the regional that above-mentioned Al concentration is low, the corrosion of the locality such as pitting produces or aggravation.
On the other hand, the tissue that fine precipitate exists equably can be described as the tissue that Al concentration tiny area that is higher than surrounding and that be made up of exists equably this high Al Concentration portion. In other words, it may be said that the tissue that the precipitate being fine exists dispersedly and the Al major part that remains in parent phase is uniformly dispersed. The tissue being created substantially absent precipitate can be described as the tissue being substantially made up of, exist a little or be completely absent very fine precipitate the parent phase being uniformly dispersed Al. Think and make by making Al be uniformly dispersed the corrosion of locality as above be not susceptible to or aggravate that there is the excellent corrosion resistance of the magnesium alloy materials of this tissue.
When Al concentration being analyzed from thick region as above to tiny area, it may be preferred to utilize EPMA (ElectronProbeMicroAnalyzer, electron beam microscopic analyzer). Therefore, utilize EPMA device that above-mentioned various forms of magnesium alloy materials are carried out Al concentration analysis, result obtains following opinion: shown in embodiment as be described hereinafter, for the magnesium alloy materials of excellent corrosion resistance, when the content of the Al that this alloy material is overall is set to x mass %, the region of x mass % �� �� accounts for half, is created substantially absent the position that the content of Al is considerably less, and the position much more very content of Al is also fewer. That is, the present inventor obtains following opinion: the parameters such as the area occupation ratio of use Al concentration, it is possible to specify excellent corrosion resistance quantitatively. Additionally, it is believed that this quantitatively specifies that how all available the existence form regardless of Al is.
The present invention, based on above-mentioned opinion, carrys out the magnesium alloy materials of regulation excellent corrosion resistance by Al concentration and area occupation ratio thereof.
The present invention relates to a kind of magnesium alloy materials, it is made up of the magnesium alloy containing more than 7.3 mass % and the Al of below 16 mass %. This magnesium alloy materials, when the content of the Al that above-mentioned magnesium alloy materials is overall is set to x mass %, meets following (1)��(3).
(1) content of Al is 50 more than area % for (x �� 0.8) more than quality % and (x �� 1.2) quality % area below,
(2) content of Al is the region of (x �� 1.4) more than quality % is 17.5 below area %,
(3) content being created substantially absent Al is 4.2 mass % area below.
As mentioned above, in the magnesium alloy materials of the present invention, it is created substantially absent the region of the corrosion-resistant that content is below 4.2 mass % of Al, and, the region (region of 0.8x mass %��1.2x mass %) that Al concentration is high accounts for more than half, and the region that Al concentration is very high (region of more than 1.4x mass %) is few. That is, the magnesium alloy materials of the present invention is created substantially absent the region that Al concentration is low, thereby, it is possible to be effectively prevented the corrosion of locality. Additionally, in the magnesium alloy materials of the present invention, the region that Al concentration is very high is few or is created substantially absent and (representational is, precipitate containing Al etc. is fine and its total amount is few (according to form, it is created substantially absent)), thus, in magnesium alloy parent phase itself, Al is also fully and disperse widely and exist. So, the magnesium alloy materials of the present invention is formed in the equally high state of its at least whole face side region Al concentration. According to this composition, the excellent corrosion resistance of the magnesium alloy materials of the present invention.
A mode as the present invention, it is possible to enumerate the mode that region is 5 below area % that content is (x �� 1.4) more than quality % that content is (x �� 0.8) more than quality % and (x �� 1.2) quality % area below is 70 more than area % and Al of Al.
According to aforesaid way, more than the region (region of 0.8x mass %��1.2x mass %) that Al concentration is high accounts for 7 one-tenth, and the region that Al concentration is very high (region of more than 1.4x mass %) is 5 below area %, it is 3 below area % according to form, considerably less, therefore, Al more uniformly exists, and corrosion resistance is more excellent.
A mode as the present invention, it is possible to enumerate the mode that the content of Al is (x �� 0.9) more than quality % and (x �� 1.2) quality % area below is 50 more than area %.
According to aforesaid way, the region (region of 0.9x mass %��1.2x mass %) that Al concentration is higher accounts for more than half, and the region of excellent corrosion resistance is many, and therefore, corrosion resistance is more excellent.
A mode as the present invention, it is possible to be set forth in above-mentioned magnesium alloy materials face side region cross section in, the area that adds up to containing at least one intermetallic compound in Al and Mg be the mode of 3 below area %.
In aforesaid way, at least whole face side region, the intermetallic compound containing Al, Mg is very fine and its total amount is few or is completely absent, therefore, and excellent corrosion resistance. It addition, in particularly considerably less at the intermetallic compound containing Al or the mode that is completely absent, the Al concentration of parent phase is equally high state, therefore, excellent corrosion resistance.
A mode as the present invention, it is possible to enumerate the mode that above-mentioned magnesium alloy materials is sheet material.
Aforesaid way can be preferred for implementing the raw material of the plastic working material of the plastic working such as punch process, forging processing, bending machining. Particularly, by the condition of plastic working being set as specified conditions described later, obtained plastic working material also are able to maintain the Al CONCENTRATION DISTRIBUTION same with above-mentioned sheet material, excellent corrosion resistance.
A mode as the present invention, it is possible to enumerating above-mentioned magnesium alloy materials is the mode that the sheet material of long size winds the coiled material obtained.
Above-mentioned coiled material is made up of the sheet material of excellent corrosion resistance, therefore, by this coiled material is used for implementing the raw material of the plastic working material of the plastic working such as punch process, forging processing, bending machining, it is possible to contribute to the batch production of plastic working material. Particularly, by the condition of plastic working being set as specified conditions described later, obtained plastic working material also are able to maintain the Al CONCENTRATION DISTRIBUTION same with above-mentioned coiled material, excellent corrosion resistance. Or, by stamping-out suitable after above-mentioned coiled material is carried out uncoiling or cutting, it is possible to manufacture the sheet material of intended shape, it is possible to contribute to the batch production of this sheet material. Obtained sheet material substantially maintains the Al CONCENTRATION DISTRIBUTION of this coiled material, therefore excellent corrosion resistance. Certainly, obtained sheet material can directly utilize, it is also possible to for the raw material of above-mentioned plastic working material.
A mode as the present invention, it is possible to enumerating this magnesium alloy materials is the mode that sheet material is implemented the plastic working material that plastic working obtains.
As described later, the magnesium alloy materials of the present invention can adopt various forms. Particularly, the plastic working material (formed products) of intended shape it is configured to by being as shown in aforesaid way, it is possible to be preferred for various member of formation and housing etc. When the material that above-mentioned sheet material obtains for implementing solution treatment (particularly final solution treatment) as described later, draftability is excellent, therefore, this form sheet material being implemented the plastic working such as punch process or forging and obtain is compared with die-casting material and thixotropic injection moulding material, except excellent corrosion resistance, toughness is also excellent. Or, when the material that above-mentioned sheet material obtains for implementing the plastic working (time processing) such as calendering or further time processing material is implemented final solution treatment and obtains material when, when the processing such as calendering, the internal flaw such as space (hole) reduces or is substantially eliminated, toughness is thus made to improve, or make crystal grain miniaturization by calendering etc., thus make intensity improve. This form sheet material being implemented the plastic working such as punch process or forging (secondary operations) and obtain is compared with die-casting material and thixotropic injection moulding material, and except excellent corrosion resistance, the mechanical property such as toughness and intensity is also excellent.
Invention effect
The excellent corrosion resistance of the magnesium alloy materials of the present invention.
Accompanying drawing explanation
Fig. 1 is the composition mapping graph picture of the FE-EPMA of magnesium alloy materials, Fig. 1 (A) is sample No.1: coiled material (does not carry out final solid solution), Fig. 1 (B) is sample No.2: coiled material (carries out final solid solution), Fig. 1 (C) is sample No.3: sheet material (rapid heating and cooling material), Fig. 1 (D) is sample No.100: die-casting material.
Fig. 2 indicates that the block diagram of the Al concentration of magnesium alloy materials and the relation of area occupation ratio (%), Fig. 2 (A) is sample No.1: coiled material (does not carry out final solid solution), Fig. 2 (B) is sample No.2: coiled material (carries out final solid solution), Fig. 2 (C) is sample No.3: sheet material (rapid heating and cooling material), Fig. 2 (D) is sample No.100: die-casting material.
Fig. 3 is the microphotograph (5000 times) of magnesium alloy materials, Fig. 3 (A) is sample No.1: coiled material (does not carry out final solid solution), Fig. 3 (B) is sample No.2: coiled material (carries out final solid solution), Fig. 3 (C) is sample No.3: sheet material (rapid heating and cooling material), Fig. 3 (D) is sample No.100: die-casting material.
Fig. 4 indicates that the figure of the Al concentration (quality %) of the ICP ICP Atomic Emission Spectrophotometer of the different magnesium alloy materials of Al content and the relation of the X-ray intensity of EPMA.
Detailed description of the invention
Below, the present invention is illustrated in more detail.
[magnesium alloy materials]
(composition)
The magnesium alloy of the various compositions (remainder: Mg and impurity, more than Mg:50 mass %) that the magnesium alloy constituting the magnesium alloy materials of the present invention can be set forth in Mg containing addition element. Particularly, the present invention is set as the high concentration alloy of addition element containing more than 7.3 mass %, wherein, is set as in addition element at least containing the Mg-Al system alloy of Al. The content of Al is more many, and corrosion resistance is more excellent, and there is the tendency that the mechanical property such as intensity, hardness is also excellent. Therefore, the content of Al is the high concentration alloy poor alloy phase ratio with Al of more than 7.3 mass % as representative of the present invention, and corrosion resistance, mechanical property are excellent. But, when the content of Al is more than 16 mass %, can cause that plastic working reduces, therefore, the upper limit is set as 16 mass %. When the content of Al is below 12 mass %, plastic working is more excellent, it is thus preferred to, it is particularly preferred to below 11 mass %, more preferably 8.3 mass %��9.5 mass %.
Addition element beyond Al can enumerate more than one elements selected from Zn, Mn, Si, Be, Ca, Sr, Y, Cu, Ag, Sn, Li, Zr, Ce, Ni, Au and rare earth element (except Y, Ce). During containing these elements, the content of each element can enumerate more than 0.01 mass % and below 10 mass %, it is preferable that more than 0.1 mass % and below 5 mass %. Additionally, containing when adding up to more than 0.001 mass %, Si, Ca, Sn, Y, Ce in above-mentioned addition element of preferably adding up to more than 0.1 mass % and below 5 mass % and at least one element in rare earth element (except Y, Ce), thermostability, anti-flammability are excellent. When containing rare earth element, it adds up to content to be preferably more than 0.1 mass %, and particularly, when containing Y, its content is preferably more than 0.5 mass %. Impurity can enumerate such as Fe etc.
The composition more specifically of Mg-Al system alloy can be enumerated such as: the AZ system alloy (Mg-Al-Zn alloy of ASTM standard, Zn:0.2 mass %��1.5 mass %), AM system alloy (Mg-Al-Mn system alloy, Mn:0.15 mass %��0.5 mass %), Mg-Al-RE (rare earth element) is alloy, AX system alloy (Mg-Al-Ca system alloy, Ca:0.2 mass %��6.0 mass %), AS system alloy (Mg-Al-Si system alloy, Si:0.2 mass %��6.0 mass %), AJ system alloy (Mg-Al-Sr system alloy, Sr:0.2 mass %��7.0 mass %) etc. particularly, containing the Mg-Al system alloy of the Al of 8.3 mass %��9.5 mass %, the Zn of 0.5 mass %��1.5 mass %, the corrosion resistance of representational AZ91 alloy, mechanical property are excellent, it is thus preferred to.
In the present invention, the content (hereinafter referred to as Al ensemble average amount) of the Al that magnesium alloy materials is overall: x mass % is unrelated with the existence of the Al in magnesium alloy materials (mainly precipitate, crystalline substance go out at least one in thing and solid solution), refers to the total amount of the Al contained in magnesium alloy materials. Representatively property ground example, the mensuration of this total amount can preferably by ICP ICP Atomic Emission Spectrophotometer method (InductivelyCoupledPlasmaAtomicEmissionSpectroscopy:ICP-A ES).
(Al concentration and area occupation ratio (area ratio))
The maximum of the magnesium alloy materials of the present invention is characterised by Al CONCENTRATION DISTRIBUTION. Specifically, when the surface of this alloy material is carried out Al concentration analysis, the region that the content of (1) Al is Al ensemble average amount (x mass %) �� 20% accounts for more than half (wherein, 7.3��x��16). The region that region is corrosion-resistant lower than 0.8x mass % (minimum 5.84 mass %), for the region more than 1.2x mass % (maximum 19.2 mass %), the corrosion resistance in this region itself is high, but, it is present in this region owing to Al concentrates, therefore easily there is the region of corrosion-resistant comparatively speaking. On the other hand, the region of 0.8x mass %��1.2x mass % is (following, this region is called center compositing area) the difference of Al concentration little, by making the region of this Al even concentration be 50 more than area %, not easily there is the big position of the difference of Al concentration, the i.e. region lower than 0.8x mass % as above and the region more than 1.2x mass %. Therefore, for the magnesium alloy materials of the present invention, the region of corrosion-resistant is few or is created substantially absent, and the face side region of at least this alloy material it is made up of the region that Al concentration is higher, thus, it is not likely to produce the corrosion of locality, excellent corrosion resistance. As it has been described above, the area occupation ratio of center compositing area is more high, the region of Al even concentration is more big, it is easy to make Al concentration reach uniformly. That is, Al CONCENTRATION DISTRIBUTION width easily narrows. Therefore, the area occupation ratio of center compositing area is preferably 55 more than area %, it is particularly preferred to be 70 more than area %, more preferably 90 more than area %, it is particularly preferred to 95 more than area %. It addition, the higher region of Al concentration, the specifically region of 0.9x mass %��1.2x mass % be 30 more than area %, more preferably 50 more than area % time, Al concentration is high, and the region of this high concentration exists equably, thus makes corrosion resistance more excellent. The details of the assay method of Al concentration and the assay method of area occupation ratio is as described later.
Any part of arbitrary section pair cross-section that the mensuration of Al concentration can take magnesium alloy materials carries out, but is the surface of this alloy material with corroding maximally related region. Therefore, in the magnesium alloy materials of the present invention, at least its surface meets the Al CONCENTRATION DISTRIBUTION of above-mentioned regulation. Except magnesium alloy materials inside (such as, through-thickness exceedes the region of the 1/4 of thickness from surface) the Al CONCENTRATION DISTRIBUTION mode identical with the Al CONCENTRATION DISTRIBUTION on surface outside, in the present invention, it is allowed to the mode that internal Al CONCENTRATION DISTRIBUTION is different from the Al CONCENTRATION DISTRIBUTION on surface.
It addition, in the magnesium alloy materials of the present invention, the content of (2) Al is the region few (wherein, 7.3��x��16) of Al ensemble average amount (x mass %) �� more than 140%. For the region of more than 1.4x mass % (maximum 22.4 mass %), the corrosion resistance in this region itself is high, but, it is present in this region owing to Al concentrates, therefore, it is easy to have that Al concentration is relatively low and the region of corrosion-resistant. On the other hand, in the magnesium alloy materials of the present invention, few to 17.5 below area % by the region (following, this region is called ultrahigh concentration region) making more than 1.4x mass %, not easily there is the region of corrosion-resistant, excellent corrosion resistance. The area occupation ratio in ultrahigh concentration region is more low, and the relatively low region of Al concentration is more few, it is possible to reduce the region of corrosion-resistant. That is, Al CONCENTRATION DISTRIBUTION width easily narrows. Thus, the area occupation ratio in ultrahigh concentration region is preferably 15 below area %, more preferably 14 below area %, it is particularly preferred to 5 below area %, especially more preferably 3 below area %, it is preferred that 1 below area %. It is preferred that ultrahigh concentration region is 0.15 below area %, it is generally desirable to, it is absent from ultrahigh concentration region.
It addition, in the magnesium alloy materials of the present invention, (3) are created substantially absent the region that the content of Al is 4.2 mass % area below (below this region being called low concentration region), i.e. corrosion-resistant described above. When there is the relatively large number of position of Al content, preferentially produce corrosion or corrosion aggravation at the relatively small number of position of Al content. On the other hand, in the magnesium alloy materials of the present invention, it is created substantially absent this low-down position of Al concentration, namely easily produces the position of corrosion and the position of corrosion easily aggravation, therefore, excellent corrosion resistance. It addition, be created substantially absent the mensuration referred to by EPMA not observe the position of below 4.2 mass %.
(tissue)
Tissue as excellent corrosion resistance, it is desirable to the region that Al concentration is very high is little and few, it is preferable that be created substantially absent. Therefore, expect to be created substantially absent with Al12Mg17, be called Al according to addition element2Ca��Al4Ca��Al3The corrosion resistance that the rich Al intermetallic compound such as Ni is the tissue of the rich Al precipitate of representative is the most excellent. But, if the area occupation ratio in above-mentioned ultrahigh concentration region meets specific scope and is created substantially absent low concentration region, then excellent corrosion resistance, therefore, in the present invention, in the scope meeting above-mentioned area occupation ratio, allow to exist rich Al precipitate as above-mentioned intermetallic compound. Particularly when there is rich Al intermetallic compound, for the little (mean diameter: less than 3.0 ��m of each intermetallic compound, preferably less than 0.5 ��m) and during homodisperse tissue (add up to area occupation ratio: less than 11%), Al concentration easily becomes uniform, it is thus preferred to. It addition, deposit equably in case at Al precipitate rich as above-mentioned intermetallic compound, it is possible to expect the function as the barrier to corrosion.
According to the addition element in alloy, except can forming above-mentioned rich Al intermetallic compound, it is also possible to form Mg2Si��Mg2Ca��Mg2Sn��Mg17Sr2Deng the intermetallic compound containing Mg. In at least its face side region of magnesium alloy materials, contain the intermetallic compound of Mg, Al as above when being 3 below area %, excellent corrosion resistance, it is thus preferred to. Therefore, in the present invention, the lower limit of above-mentioned intermetallic compound does not do special setting. In the present invention, measure the face side region of the area occupation ratio of above-mentioned intermetallic compound and be set as the through-thickness surface from magnesium alloy materials until the region of 100 ��m. When the thickness of magnesium alloy materials is less than 100 ��m, be set as through-thickness from surface until thickness 1/4 region. The assay method of the area ratio of above-mentioned intermetallic compound is as described later.
(form)
As the form of the magnesium alloy materials of the present invention, if according to manufacturing process is distinguished, then can enumerate: the deformable material (wherein, way carries out solution treatment in the mill) that rolled material, extruded material etc. are implemented deformation processing and obtained; Correction material deformable material being implemented correction process and obtain; Heat treatment material deformable material being implemented the heat treatment to remove for the purpose of strain etc. and obtain; The solid solution material various forms such as die-casting material, thixotropic injection moulding material, deformable material, correction material, founding materials (material such as, obtained by double roller continuous casting method) being implemented final solution treatment and obtain; Solid solution material is implemented the deformation processing such as calendering, extrusion and obtains (after solid solution) deformable material; Implement to correct to solid solution material and obtain (after solid solution) correction material; Solid solution material is implemented the deformation processing such as calendering and above-mentioned heat treatment successively and obtains (after solid solution) heat treatment material; The grinding-material that deformable material, correction material, heat treatment material, solid solution material are implemented grinding and obtained. Furthermore it is possible to the rapidoprint enumerated the sheet material to any one form in deformable material, correction material, heat treatment material, solid solution material, grinding-material to implement the plastic workings such as drawing, bending, forging, punch process and the machining such as cutting, stamping-out and obtain.
In above-mentioned deformable material, particularly, for rolled material, crystal grain miniaturization is made by rolling, to be such as average crystallite particle diameter be less than 10 ��m, be the micro organization of less than 5 ��m further, or the internal flaw such as space (hole) is few or little or the tissue (with respect to material composition by calculating the solid density material obtained, the density of actual measurement is the tissue of more than 99%) that is created substantially absent. Having the high tissue of this micro organization, above-mentioned density can as representing it is an index of rolled material. As it has been described above, rolled material is few or little by internal flaw, be preferably created substantially absent internal flaw, the mechanical property such as hot strength, draftability, rigidity is excellent, therefore, it is possible to be suitable for the raw material of structural material and structural material.
Correct and such as can utilize smoothing roll processing etc. Utilize the smoothing roll correction material that obtains of processing to import shear band according to the degree correcting processing, thus, carry out microscope and observe, even if being formed sometimes, the tissue being also difficult to observe by clear and definite grain boundary. In this situation, it is obtained in that monochromatic light X-ray diffraction peak, therefore be even noncrystalline neither tissue, it is possible to obtain monochromatic light X-ray diffraction peak, not it is observed that the tissue of grain boundary can as representing it is an index of the correction material utilizing smoothing roll processing to obtain. Correction material, produce when plastic workings such as punch process to recrystallize in particular with the correction material that obtains of smoothing roll processing, there is the tendency that plastic working is excellent. When the degree corrected is low, outward appearance, tissue, engineering properties are sometimes similar with above-mentioned rolled material.
For solid solution material, owing to implementing the solution treatment for generating supersaturated solid solution, therefore, the addition element such as Al mainly exists with solid solution thereof, not easily there is Al12Mg17��Al(MnFe)��Al2Ca��Al4Ca��Al3The precipitates such as the intermetallic compound containing Al such as Ni, even if it is also little and few for existing. Therefore, the existence ratio of the intermetallic compound containing Al can be an index of solid solution material less as expression. Specifically, it is possible to be set forth in magnesium alloy materials face side region (representational be through-thickness from surface until the region of 100 ��m) cross section in the ratio adding up to area containing at least one intermetallic compound in Al and Mg be less than 3%, be further less than 1% material as solid solution material. In addition, for solid solution material, under implementing the heat treated situation of 400 DEG C �� more than 30 hours, there is the tendency (wherein, test film adopts surface to carry out the material of grinding) that hardness after this heat treatment is difficult to reduce or draftability does not substantially change. It is taken as that, it is possible to the intensity of variation of the mechanical property before and after this heat treatment is used as the index of solid solution material.
As it has been described above, solid solution material is by generally forming supersaturated solid solution at it and make Al be prone to exist equably. Specifically, when the solid solution material implementing final solution treatment and obtain, there is center compositing area to be 90 more than area %, ultrahigh concentration region be 3 below area %, be the Al CONCENTRATION DISTRIBUTION of 1 below area % further. Therefore, the corrosion resistance of solid solution material is more excellent. It addition, in solid solution material, become the defects such as coarse precipitates as the starting point of crackle (representational is intermetallic compound) when being created substantially absent plastic working, thus, plastic working is also excellent. Therefore, this solid solution material can be suitable as the raw material of plastic working material.
The surface of grinding-material has carried out smoothing and has made surface characteristic excellent. Therefore, surface roughness little (such as, being calculated as less than 20 ��m using maximum height Rz) or it can be seen that grinding marks is as representing it is an index of grinding-material.
Heat treatment material also depends on heat treatment condition, and to be the ratio shared by the particle of less than 0.1 ��m be it is postulated that such as (1) does not observe shear band, (2) crystallization particle diameter in cross section in the inside of magnesium alloy materials 5 below area % can as representing it is an index of heat treatment material.
When above-mentioned rapidoprint is plastic working material, by utilizing the form that the magnesium alloy materials of the present invention is sheet material as raw material and to implement plastic working under given conditions, it be 50 more than area %, ultrahigh concentration region is 17.5 below area %, the Al CONCENTRATION DISTRIBUTION being created substantially absent low concentration region that this plastic working material also has center compositing area, excellent corrosion resistance. That is, this plastic working material is able to maintain that above-mentioned raw-material Al CONCENTRATION DISTRIBUTION. Above-mentioned machined material also substantially is able to maintain above-mentioned raw-material Al CONCENTRATION DISTRIBUTION.
On the other hand, if distinguish the form of the magnesium alloy materials of the present invention by shape, then can enumerate: sheet material (substantially utilizes the parallel table back side being made up of plane and the side that connects between the above-mentioned table back side to constitute and the uniform shape of distance (=thickness) essence on the whole between the table back side, during vertical view, representational is rectangle, in addition, the various flat shapes such as desirable circle, ellipse, polygon); The coiled material sheet material of long size wound and obtain; Various obform bodies except above-mentioned sheet material. Sheet material can by carry out cutting or stamping-out etc. and obtain the various flat shapes such as variously-shaped, such as circle, ellipse, polygon, the form possessing through hole (also including hole big as window) at one part. In addition, sheet material includes having reeded form by using profiled roller etc. in a part as described later, has the form etc. of rib (protuberance) in a part and have the form of the different part of thickness. The arbitrary 3D shape body that obform body can be enumerated such as can pass through casting die, thixotropic injection moulding method shapes maybe can pass through the 3D shape body that the plastic workings such as punch process shape. Above-mentioned 3D shape body can be enumerated such as: the part at sheet material integrally has the projections such as rib or groove and the different shape of local thickness, the cross section of housing etc. for various equipment] casing of shape or] framework of shape, have the polygonal better simply shape of column geometric ratio such as bottom tube-like body and spheroid, ellipsoid, triangle column. It addition, obform body can set that the form for having through hole (also including hole big as window) at one part. This shape with concaveconvex shape or through hole easily can shape by utilizing casting die etc. Can also utilize and blank etc. be implemented machining, grinding etc. and shapes and schedule to last the raw material hoping shape. In addition, obform body can enumerate the form etc. with the plastic working portion only a part being implemented the plastic workings such as punch process and formed.
As mentioned above, the magnesium alloy materials of the present invention can take variously-shaped, but when being coiled material, except can being suitable as the raw material of the plastic working material implementing the plastic workings such as punch process, additionally it is possible to contribute to the batch production of this plastic working material. When the magnesium alloy materials of the present invention is coiled material, form can be enumerated more specifically: calendering coiled material, casting coiled material or solid solution coiled material calendering coiled material implemented final solution treatment and obtains. These coiled materials can be enumerated such as: thickness be below 10mm, further for below 5mm, width be more than 100mm, further for more than 200mm, be in particular more than 250mm, length is more than 30m, further for more than 50m, the coiled material being in particular more than 100m. This long material and wide size material are suitable as the raw material of plastic working material as mentioned above. Particularly, rolled material and rolled material is implemented final solution treatment and the material that obtains compared with above-mentioned founding materials, it is possible to make the thinner form of thickness or the longer form of length. Be below 2mm for example, it is possible to make thickness, be in particular below 1.5mm, be in particular the thin-walled material of below 1mm, length be more than 50m, further for more than 100m, be in particular the long material of more than 200m. Thickness is the raw material that the thin-walled material of below 2mm can be suitable as the plastic working material of slim, light weight. But, thickness is preferably more than 0.1mm, 0.3mm��1.2mm and easily utilizes.
The excellent corrosion resistance of the magnesium alloy materials of the present invention, therefore, is not carried out the anti-corrosion treatment such as chemical conversion treatment or anodized even from corrosive environment, it is possible to expect to use fully. In this situation, except can cutting down the productivity ratio of the operation of anti-corrosion treatment, raising magnesium alloy materials, additionally it is possible to reduce garbage, therefore, can expect to reduce carrying capacity of environment. Certainly, the form that the magnesium alloy materials of the present invention can be made the form implementing the anti-corrosion treatment such as chemical conversion treatment and anodized, namely possess corrosion-resistant coating. When surface possesses corrosion-resistant coating, even if carrying out high-precision cross-section, it is also possible to make the substrate surface being made up of magnesium alloy expose mensuration Al concentration by utilizing grinding or cutting etc. to remove corrosion-resistant coating. If making except possessing corrosion-resistant coating, being also equipped with the form of coating layer etc., then can improve corrosion resistance further or improve commodity value by imparting of painted, pattern etc. Corrosion-resistant coating and coating layer are applied to desired position.
[manufacture method]
When manufacturing the magnesium alloy materials of the present invention, it is necessary to implement solution treatment at least one times in the period before obtaining end article. Particularly when adopt include the manufacture method of hot calender operation, it is possible to use except including solid solution operation, also in refrigerating work procedure after final hot calender by until making the rate of cooling that raw material reaches specified temp control the manufacture method at particular range. Or, it is possible to use no matter all in final solid solution operation, the rate of cooling of specific range of temperatures is controlled the manufacture method at particular range with or without hot calender operation. Such as, as the manufacture method of the magnesium alloy materials of the present invention, it is possible to enumerate: possess the form (manufacture method 1-1��1-5) of calendering procedure, do not possess the form (manufacture method 2) of calendering procedure. Additionally, in each manufacture method being described below, it is possible to eliminate at least one operation obtaining having in the scope of the magnesium alloy materials of the present invention of the specific Al CONCENTRATION DISTRIBUTION of the condition meeting above-mentioned (1)��(3) or change the order of each operation.
(manufacture method 1-1)
When the magnesium alloy materials of the present invention is set as rolled material, for instance, it is possible to manufacture by having the manufacture method of following preparatory process, middle solid solution operation and calendering procedure.
Preparatory process: prepare the operation of the founding materials being made up of the magnesium alloy containing more than 7.3 mass % and the Al of below 16 mass % and being manufactured by continuous metal cast process.
Middle solid solution operation: the solution treatment above-mentioned founding materials implemented to keep temperature to be more than following minimum maintenance temperature, retention time be more than 1 hour and less than 25 hours manufactures the operation of centre solid solution material.
Than the temperature of low 10 DEG C of the temperature of Al solid solution in Mg (solidus temperature) in the double equilibrium diagram (quality %) of minimum maintenance temperature: Mg-Al.
Calendering procedure: above-mentioned middle solid solution material is implemented the hot calender of more than 1 passage and manufactures the operation of rolled material.
Particularly in the manufacturing process after middle solid solution operation, within being set as keeping the total ascent time of processing object and raw material (representational is rolled material) more than 150 DEG C and within the scope of 300 DEG C of temperature below 12 hours, further, in the way of being not heated to the temperature more than 300 DEG C, above-mentioned raw-material thermal history is controlled.
Further, in calendering procedure, after implementing final hot calender, the average cooling rate in from raw-material temperature when beginning to cool down to the period that this raw-material temperature reaches less than 100 DEG C is set as more than 0.8 DEG C/min.
In above-mentioned minimum maintenance temperature: in the double equilibrium diagram (quality %) of Mg-Al, representational than solidus temperature the temperature of low 10 DEG C (manufacture method 1-2 described later is too) as follows. Al ensemble average amount in magnesium alloy: when x mass % is more than 5 mass % and below 13 mass %, solidus temperature is 283 DEG C��437 DEG C, solidus temperature rises along with the increase of Al ensemble average amount, and therefore, above-mentioned minimum maintenance temperature represents with following expression of first degree.
(minimum maintenance temperature)=20 �� x+ (182-10)=20x+172
On the other hand, when Al ensemble average amount is more than 13 mass % and below 16 mass %, above-mentioned minimum maintenance temperature is set as (437-10) DEG C=427 DEG C.
In manufacture method 1-1, particularly after middle solution treatment, it is preferable that in the operation before end article, the raw-material total ascent time will be kept to shorten to less than 12 hours in 150 DEG C��300 DEG C temperature ranges. 150 DEG C��300 DEG C temperature ranges are Al12Mg17Deng the temperature range that rich Al intermetallic compound easily grows. By by set as above for the retention time of this temperature range for the comparatively short time, particularly can suppress the growth of above-mentioned intermetallic compound such that it is able to suppress the area occupation ratio increasing or reducing intermetallic compound of ultrahigh concentration region and low concentration region. And, in the way of substantially not producing the diffusion of Al after final hot calender, in refrigerating work procedure at least when reaching to regulate the state of cooling to reach above-mentioned specific rate of cooling before 100 DEG C, the growth of above-mentioned intermetallic compound can be suppressed such that it is able to suppress the increase of ultrahigh concentration region and low concentration region. All the more fast rate of cooling, more can suppress the increase of ultrahigh concentration region and low concentration region, it is thus preferred to. Even if it addition, be not heated to more than 300 DEG C, it is possible to suppress the growth of above-mentioned intermetallic compound.
(manufacture method 1-2)
The magnesium alloy materials of the present invention is being set as through the solid solution material that calendering procedure obtains, it is possible to manufacture by such as possessing the manufacture method of following preparatory process, middle solid solution operation, calendering procedure and final solid solution operation.
Preparatory process: prepare the operation of the founding materials being made up of the magnesium alloy containing more than 7.3 mass % and the Al of below 16 mass % and being manufactured by continuous metal cast process.
Middle solid solution operation: the solution treatment above-mentioned founding materials implemented to keep temperature to be more than following minimum maintenance temperature, retention time be more than 1 hour and less than 25 hours manufactures the operation of centre solid solution material.
Than the temperature of low 10 DEG C of the temperature of Al solid solution in Mg (solidus temperature) in the double equilibrium diagram (quality %) of minimum maintenance temperature: Mg-Al
Calendering procedure: above-mentioned middle solid solution material is implemented the hot calender of more than 1 passage and manufactures the operation of rolled material.
Final solid solution operation: above-mentioned rolled material implements to keep temperature to be more than above-mentioned minimum maintenance temperature, retention time be the operation of the final solution treatment of more than 1 hour and less than 40 hours.
Particularly, in final solid solution operation, the rate of cooling in 330 DEG C��380 DEG C temperature ranges meets the following conditions.
By the through-thickness surface from above-mentioned rolled material until when the region of 10 ��m is set to surface region, surface region being cooled down with the rate of cooling of more than 1 DEG C/min.
By implementing final solution treatment as mentioned above after calendering further, the precipitate solid solutions such as the rich Al intermetallic compound that calendering procedure is previously created can be made such that it is able to effectively suppress increasing or the area occupation ratio of reduction intermetallic compound of ultrahigh concentration region low concentration region. In the calendering procedure of above-mentioned manufacture method 1-2, it is also possible in the same manner as above-mentioned manufacture method 1-1, the rate of cooling after final hot calender is set as specific scope. Additionally, in this manufacture method 1-2, after final solid solution operation, obtain end article before, shorten the total ascent time kept more than 150 DEG C and within the scope of 300 DEG C of temperature below as far as possible, and in time controlling raw-material thermal history in the way of being not heated to the temperature more than 300 DEG C, it is able to maintain that the Al CONCENTRATION DISTRIBUTION of the solid solution material obtained through final solid solution operation, it is thus preferred to.
(manufacture method 1-3)
Can implement to eliminate the finished heat treatment for the purpose of strain to by the above-mentioned manufacture method 1-1 rolled material manufactured. Namely, the magnesium alloy materials of the present invention is being set as through the heat treatment material that calendering procedure obtains, it is possible to by except the preparatory process except possessing manufacture method 1-1, middle solid solution operation, calendering procedure, the manufacture method that is also equipped with finished heat treatment operation described later manufactures.
(manufacture method 1-4)
Or, it is possible to the rolled material manufactured by manufacture method 1-1,1-2, solid solution material by improve implement for the purpose of glacing flatness etc. to correct (representational is heat straightening) or by improves implement for the purpose of surface characteristic (removing the lubricant etc. used in oxide layer and surface defect, calendering etc.) etc. to clean, grinding. Particularly, when the magnesium alloy materials of the present invention being set as correction material or grinding-material, it is possible to by except possessing preparatory process, middle solid solution operation, calendering procedure (manufacture method 1-1 or the operation of regulation in 1-2), final solid solution operation (only the operation of regulation in manufacture method 1-2), the manufacture method of at least one operation being also equipped with in correction process described later and grinding step manufactures.
(form of the product of manufacture method 1-1��1-4)
Above-mentioned possess preparatory process, middle solid solution operation, calendering procedure manufacture method, be also equipped with being selected from this manufacture method in the manufacture method of at least one operation of final solid solution operation, finished heat treatment operation, correction process, grinding step and matting, the sheet material that can obtain predetermined length (thinks the sheet material (such as, below length 5m, particularly below 1m) of short size being difficult to wind. Hereinafter referred to as sheet material) or the sheet material of long size.
Above-mentioned sheet material such as make by founding materials being cut into predetermined length in preparatory process predetermined length founding materials (cast sheet) and using this founding materials as raw material through after operation and obtain. Or, make casting coiled material by winding the founding materials of long size in preparatory process, also make coiled material in each operation and be finally cut into predetermined length, it is also possible to obtain sheet material. On the other hand, when not carrying out above-mentioned cutting, the sheet material of long size can be obtained, by the sheet material of this long size is wound, obtain the magnesium alloy materials of the present invention of web form. When making coiled material, in each operation after preparatory process, it is commonly performed unreeling and winding of coiled material. It addition, in this situation, the raw material provided to each operation is that long material or wide size material are wound the coiled material obtained, therefore, once substantial amounts of raw material moved or heat, thus carrying out the process of each operation continuously, therefore, the productivity ratio of magnesium alloy materials is excellent. The magnesium alloy materials of the present invention can be made as the raw material of each operation by any one using in sheet material, coiled material.
(manufacture method 1-5)
Or, when any one sheet material in above-mentioned rolled material, solid solution material, heat treatment material, correction material, grinding-material and cleaning material being implemented plastic working and the magnesium alloy materials of the present invention is made plastic working material, it is possible to manufacture by making above-mentioned each manufacture method be also equipped with following plastic working operation.
Plastic working operation: when being less than 8 hours (preferably less than 0.5 hour) keeping temperature to be less than 350 DEG C (preferably less than 300 DEG C), retention time, obtained sheet material is preheated and the operation of sheet material enforcement plastic working to this heated condition.
Below, each operation of manufacture method 1-1��1-5 is illustrated in more detail.
" preparatory process "
Above-mentioned founding materials is preferably by continuous metal cast process. Continuous metal cast process not only can stably obtain the founding materials of greater homogeneity along its length, and can solidify by chilling, therefore, oxide and segregation etc. can not only be reduced, and the generation of the thick crystallization precipitate more than 10 ��m of the starting point of crackle can be become when can suppress to roll etc., thus rolled, founding materials that the plastic working such as extrusion is excellent. Particularly, double roller continuous casting method easily forms the tabular founding materials of reduced in segregation. The sectional area of founding materials and thickness, width and length are not particularly limited, but easily produce segregation time blocked up, it is therefore preferable that thickness is below 10mm, and more preferably below 7mm, it is particularly preferred to for below 5mm. Additionally, using length be more than 30m, further for more than 50m, the founding materials being in particular the long size of more than 100m or width be more than 100mm, further for more than 250mm, the wide size being in particular more than 600mm founding materials as the raw material of rolled material time, it is possible to make the calendering plate of long size or the calendering plate of wide size. Founding materials can make the casting coiled material of wound into rolls, it is also possible to makes the casting sheet material being cut into predetermined length, suitably selects according to desired form. When wound into rolls, when the internal diameter of casting coiled material is little, when the state to be heated to more than 150 DEG C before being about to founding materials is wound is wound, will not crack and be wound, it is possible to easily make casting coiled material.
" middle solid solution operation "
Make composition homogenize by solution treatment in the middle of above-mentioned founding materials is implemented and make the element solid solutions such as Al, it is possible to reducing the existence of coarse precipitates, it is possible to make the raw material that the plastic workings such as calendering, extrusion are excellent. As the maintenance temperature of middle solution treatment, representational maintenance temperature can enumerate more than 350 DEG C and less than 450 DEG C, can enumerate more than 380 DEG C especially, can enumerate more than 390 DEG C and less than 420 DEG C further. Retention time can enumerate more than 1 hour and less than 25 hours, can enumerate more than 10 hours and less than 25 hours especially. The content of the preferred Al retention time more at most is more long. Additionally, in the refrigerating work procedure started from above-mentioned maintenance temperature, water-cooled or air blast etc. is utilized to force cooling etc. to accelerate rate of cooling (preferably more than 1 DEG C/min in the same manner as when final solution treatment described later, more preferably more than 50 DEG C/min) time, growth and the precipitation of precipitate can be suppressed, it is thus preferred to. Particularly when utilizing casting sheet material, it is easy to control rate of cooling.
Although solution treatment in the middle of can directly above-mentioned founding materials being implemented but it also may implement the little calendering of reduction ratio (reduction ratio: 15%/1 passage of about 1%/1 passage��about) between in force before solution treatment or carry out surfacing.
" calendering procedure "
When magnesium alloy is implemented calendering, when raw-material temperature is set as room temperature, it is difficult to improve reduction ratio and cause that production efficiency reduces, therefore, if it is considered that productivity ratio, be then preferably performed the hot calender of at least 1 passage. By being heated improving the plastic workings such as calendering to raw material (rolled material of middle solid solution material or calendering midway), more improve raw-material temperature, more can improve plastic working, but raw-material temperature rising can make the precipitate coarsenings such as the intermetallic compound containing Al, cause that ultrahigh concentration region and low concentration region increase, or cause that because of coarse precipitates plastic working reduces. Therefore, raw-material temperature is preferably less than 300 DEG C, it is particularly preferred to be more than 150 DEG C and less than 280 DEG C. Raw-material heating can preheat operation by setting and utilize the heaters such as atmosphere heating furnace to carry out. Heating furnace can use the suitable heating furnace that can hold raw material (sheet material or coiled material).
Particularly, when casting sheet material being implemented calendering and make rolled material (sheet material) and obtained rolled material is made the magnesium alloy materials of the present invention with above-mentioned specific Al CONCENTRATION DISTRIBUTION, it is preferable that shorten the retention time of the above-mentioned maintenance temperature preheating operation. At this, as mentioned above, mainly raw material is maintained at specific temperature range in time shortening calendering as far as possible: when being controlled (within being preferably 12 hours) in the way of the time of 150 DEG C��300 DEG C, can effectively suppress the growth of precipitate (particularly rich Al intermetallic compound), it is possible to prevent the increase of the area occupation ratio of ultrahigh concentration region and low concentration region, intermetallic compound. For the coiled material that long material or wide size material winding are obtained, by the heating of coiled material entirety to uniform temperature time, there is coiled material at least some of in preheating, be held in time of above-mentioned specific temperature range elongated tendency. Particularly, in order to long material and wide size material are also made small-sized coiled material, closely winding to reduce when the gap of turn-to-turn by raw material, it is necessary to extend to a certain extent for coiled material entirety being carried out the time that uniformly heating is required. Accordingly, it is possible to the time being held in above-mentioned specific temperature range elongated region can be there is. In order to suppress the growth of precipitate at whole coiled material, it is desirable to regulate the size of coiled material in the way of preheating time is also included within the above-mentioned total ascent time or shorten preheating time. As the method being used for shortening preheating time, it is possible to enumerate and such as arrange, before next-door neighbour's calender device, the method that heated in-line device (the representational heater being to utilize radiant heat, electrified regulation, sensing heating etc.) implements quickly heating. By adopting on-line mode, additionally it is possible to after shortening heating, implement the time before calendering. Additionally, as the method being used for shortening raw material 150 DEG C��300 DEG C times kept, method can be listed below: after passing through from calender device (representational for stack), rolled material be impregnated in coolant, lubricant is medium carries out chilling (preferred rate of cooling: more than 1 DEG C/sec). When carrying out above-mentioned anxious heat and chilling, it is possible to effectively shorten in calendering procedure raw material 150 DEG C��300 DEG C times kept. Particularly, above-mentioned anxious heat and chilling can easily be implemented when the material that the raw material implementing calendering is the short sizes such as casting sheet material. In addition, such as, even when preparing multiple raw materials and being heated once by its stacking and to them, it is also possible to be used in the time that each raw material is heated to uniform temperature by arranging suitable gap between raw material comparatively short. The method also is able to be easily implemented with when the raw material implementing calendering is the short size materials such as casting sheet material. Such as, when making predetermined length and there is rolled material (sheet material) of specific Al CONCENTRATION DISTRIBUTION of the condition meeting above-mentioned (1)��(3), preferably in when implementing the hot calender of more than 1 passage, by calendering before preheat in the total retention time be set as more than 0.01 hour and less than 8 hours, it is particularly preferred to be set as more than 0.01 hour and less than 0.3 hour. By controlling pre-heating conditions like this, it is possible to obtain being created substantially absent the magnesium alloy materials that precipitate, Al CONCENTRATION DISTRIBUTION width are narrower, i.e. the magnesium alloy materials that corrosion resistance is more excellent.
The above-mentioned calendering including hot calender can carry out 1 passage and can also carry out multi-pass. By carrying out the calendering of multi-pass, can not only obtain the rolled material that thickness is thin, and the average crystallite particle diameter (such as, less than 10 ��m, it is preferable that less than 5 ��m) of the tissue constituting rolled material can be reduced or improve the plastic working of punch process etc. In order to obtain the rolled material of expectation thickness, it is possible to suitably select passage, the reduction ratio of each passage and total reduction. In addition it is also possible to utilize known rolling condition, for instance, not only raw material is heated, and stack is also carried out the suitable conditions such as heating.
Particularly, when making as rolled material (sheet material) or rolling coiled material and there is the material of specific Al CONCENTRATION DISTRIBUTION of the condition meeting above-mentioned (1)��(3), preferably in, in the refrigerating work procedure after the hot calender that enforcement is final, the average cooling rate in raw-material temperature when starting from cooling to the period that this raw-material temperature reaches at least 100 DEG C being set as more than 0.8 DEG C/min. After final hot calender, by raw material being quickly carried out cooling, it is possible to the growth that is effectively prevented in cooling precipitate, it is possible to the area occupation ratio being effectively prevented ultrahigh concentration region and low concentration region, intermetallic compound increases. Particularly when coiled material, easily keeping the state after heating as mentioned above for a long time, therefore, generation and the increase etc. that carry out rapidly cooling down suppressing ultrahigh concentration region and low concentration region after final hot calender are effective. Additionally, when implementing final solution treatment after calendering, it is not necessarily required to meet above-mentioned rate of cooling, but by until reducing the area occupation ratio of ultrahigh concentration region, low concentration region, intermetallic compound before final solution treatment, in the solid solution material finally given, also can expect the area occupation ratio being easily reduced ultrahigh concentration region, low concentration region, intermetallic compound. Above-mentioned average cooling rate can be enumerated such as: the raw-material temperature after measuring final hot calender, when beginning to cool down, setting and arrive time t (minute) 100 DEG C required from obtained mensuration temperature: Tmp (DEG C), the speed that will be represented by (Tmp-100)/t (DEG C/min) is as average cooling rate. Then, in the way of (Tmp-100)/t (DEG C/min) >=0.8 (DEG C/min), the state of cooling is regulated. Raw-material temperature measuring can use any one in the non-contact sensors such as contact type sensor, moisture recorder such as thermocouple. Prepare very thin thermocouple and be disposed at raw-material surface and be measured.
The faster the better for above-mentioned rate of cooling, it is preferable that more than 1 DEG C/sec, more preferably more than 5 DEG C/sec. In refrigerating work procedure, it is possible to use the arbitrary chiller of above-mentioned rate of cooling can be reached. Particularly, when utilizing pressure cooling, rate of cooling can be accelerated. Forced cooling device can utilize following various device: uses the device of the gas mediums such as fan (air cooling), air blast (injecting type air cooling); Use the device of the liquid mediums such as water-cooled; And use the device etc. of the solid dielectrics such as chill roll. Particularly, when utilizing the air coolings such as air blast, the effect such as deterioration of surface characteristic that the removal step that can obtain removing the liquid refrigerant being attached on raw material, the attachment that will not produce liquid refrigerant cause. On the other hand, when utilizing liquid refrigerant, it is easy to accelerate rate of cooling. When liquid refrigerant utilizes the cold-producing medium containing the abluent (such as, interfacial agent) etc. that can remove the middle lubricants used such as calendering, it is also carried out cleaning while cooling, it is thus preferred to. Forced cooling device can off-line arrangement, but when configuring with online mode, it is possible to significantly guarantee the contact area on raw material surface and cooling medium, therefore can improve cooling effectiveness. When coiled material, it is also possible to be formerly wound carrying out above-mentioned cooling afterwards after final hot calender. It addition, when coiled material, it is possible to above-mentioned cooling is carried out when winding, but when carrying out above-mentioned cooling when uncoiling, it is easy to accelerate rate of cooling. When being capable of above-mentioned rate of cooling, it is also possible to naturally let cool and do not use above-mentioned forced cooling device.
It addition, when carrying out the little calendering of reduction ratio during pressure-sizing is prolonged etc., it is possible to adopt cold working. In cold working, substantially it is not likely to produce the change of Al concentration, is substantially able to maintain that the distribution of the Al concentration before cold working.
When carrying out the calendering of multi-pass, it is possible to the retention time in above-mentioned 150 DEG C��300 DEG C temperature ranges includes carrying out between passage intermediate heat-treatment in the scope of above-mentioned total ascent time. Pass through intermediate heat-treatment, it is possible to remove, minimizing imports raw-material strain, residual stress, texture etc. due to the plastic working (being mainly calendering) before this heat treatment. By such operation, it is prevented that the crackle accidentally produced in the calendering after this heat treatment or strain, deformation, it is possible to roll more swimmingly. Preferably the raw-material maintenance temperature of this intermediate heat-treatment is also set to less than 300 DEG C. Keep temperature preferably more than 150 DEG C, it is particularly preferred to more than 250 DEG C and less than 280 DEG C. Retention time can enumerate such as about 0.5 hour��about 3 hours. It addition, in refrigerating work procedure after intermediate heat-treatment, by accelerating rate of cooling (preferably more than 1 DEG C/min, more preferably more than 50 DEG C/min), it is also possible to suppress the growth of precipitate, it is thus preferred to.
As it has been described above, the thickness of rolled material, width and length can suitably select. It addition, when above-mentioned calendering suitably utilizes lubricant, it is possible to reduce frictional resistance during calendering, it is prevented that raw-material sintering etc., thus calendering easy to implement. Additionally, utilize when the roller periphery reeded stack of tool (abnormity stack) is as stack, the rolled material with rib can be manufactured, when utilizing the stack (abnormity stack) in roller periphery with protuberance as stack, it is possible to manufacture and have reeded rolled material. Additionally, for obtained rolled material, it is possible to implement machining, grinding and form desired concaveconvex shape, stairstepping, or form protruding, through hole.
" final solution treatment "
By implementing final solution treatment after above-mentioned calendering, make precipitate solid solution again, it is possible to reduce ultrahigh concentration region and intermetallic compound fully and be created substantially absent low concentration region. When keeping temperature lower than above-mentioned minimum maintenance temperature or retention time less than 1 hour, it is impossible to generate supersaturated solid solution fully, it is difficult to realize the minimizing of ultrahigh concentration region and intermetallic compound fully. When keeping temperature too high (representational be above 450 DEG C) or retention time more than 40 hours, energy loss can be produced and make productivity ratio reduce when sometimes also can produce the sintering of parent phase or also be heated after being sufficiently formed solid solution condition, it is therefore preferable that temperature will be kept to be set as relatively low temperature. For example, it is possible to enumerate more than 390 DEG C and less than 420 DEG C, the retention time: more than 10 hours and less than 25 hours.
Then, when implementing final solution treatment, in the refrigerating work procedure started from above-mentioned maintenance temperature, rate of cooling is regulated in the mode that the rate of cooling in 330 DEG C��380 DEG C temperature ranges is more than 1 DEG C/min. At this, for the magnesium alloy containing substantial amounts of Al that content is more than 7.3 mass % of Al, it may be said that be easily generated Al 330 DEG C��380 DEG C temperature range contents12Mg17Deng precipitates such as rich Al intermetallic compounds. Therefore, it is desirable to pass through from this temperature range as quickly as possible. Therefore, when manufacturing the magnesium alloy materials that content is 7.3 mass % the invention above of Al, the time that the temperature range easily produced from precipitate is passed through is shortened by the rate of cooling accelerated as mentioned above in 330 DEG C��380 DEG C temperature ranges, suppress the precipitation of above-mentioned intermetallic compound, thus the increase of the ultrahigh concentration region suppressing the generation with this precipitate and coming and low concentration region. Rate of cooling is the bigger the better, it is preferable that more than 1 DEG C/min, it is preferred that more than 50 DEG C/min.
At least make to meet above-mentioned rate of cooling as the surface region of the rolled material processing object. As it has been described above, corrosion produces from the surface of magnesium alloy materials, aggravates. Therefore, the above-mentioned surface region of magnesium alloy materials has the state of excellent corrosion resistance, namely has the specific Al CONCENTRATION DISTRIBUTION of the condition meeting above-mentioned (1)��(3), therefore, at least cool down using above-mentioned rate of cooling as the surface region processing object. Specifically, it is possible to suitably with forcing cooling as above. Particularly, when utilizing fan or use the air cooling such as air blast of air-blast device of injection emitting mechanism etc. of cold wind, except can obtaining being difficult to the effects such as oxidation, cooling speckle are few, additionally it is possible to obtain liquid refrigerant removed as described above, suppress the attachment with liquid refrigerant and the effects such as the surface characteristic deterioration that comes. On the other hand, when utilizing liquid refrigerant, it is possible to use the spraying of the liquid refrigerant such as spray water or reducing liquid, watering, to the impregnating cooling means of liquid refrigerant. It addition, when implementing correct processing or implement the plastic working such as punch process after final solution treatment, it is possible to use lubricant applying, as liquid refrigerant, is cooled down on solid solution material or by solid solution material dipping by lubricant in the lubricant. When the middle lubricants used such as calendering are removed by expectation, as forcing cooling way, as set forth above, it is possible to utilize the liquid refrigerant containing abluent. The water-cooled using liquid refrigerant more can accelerate rate of cooling than air cooling. When coiled material, it is possible to be made directly cooling, but when cooling down when uncoiling, it is easy to accelerate rate of cooling. Although also depending on the thickness of the sheet material constituting coiled material, but when such as uncoiling, when utilizing injection emitting mechanism to cool down, it is possible to reach the rate of cooling of about 50 DEG C/min, when carrying out water-cooled, it is possible to reach the rate of cooling of about 400 DEG C/min. It is wound after being cooled near room temperature. It addition, the plastic working of the sheet material (including founding materials) obtained through final solid solution operation is also excellent, therefore, under the degree of the winding diameter industrially used, even if also being able to be sufficiently carried out winding near room temperature.
For above-mentioned rate of cooling, measure the raw-material surface temperature after final solid solution, in the way of making the rate of cooling in 330 DEG C��380 DEG C temperature ranges reach desired speed, set the time (minute), and regulate the state of cooling to reach desired speed. At this, due to the excellent heat conductivity of magnesium alloy, therefore, through-thickness is identical with the implication of the temperature of most surface until the temperature in the region (surface region) of 10 ��m from surface. Therefore, the rate of cooling in region, surface can measure the temperature of raw-material most surface and be set according to this mensuration temperature. In the mensuration of the temperature of raw-material most surface, it is possible to use any one in contact type sensor, the non-contact sensor such as above-mentioned thermocouple, moisture recorder.
" finished heat treatment "
When implementing finished heat treatment after calendering, it is preferable that maintenance temperature is set as less than 300 DEG C. Condition can be enumerated more specifically: keeping temperature is more than 100 DEG C and less than 300 DEG C, and the retention time is more than 5 minutes and less than 60 minutes. The time being preferably maintained within the scope of more than 150 DEG C and 300 DEG C of temperature below by the raw material (rolled material) in this finished heat treatment operation is also included within the above-mentioned total ascent time, it is preferable that the retention time was less than 30 minutes. By adopting such specified conditions, it is possible to the rolled material that strain when making the specific Al CONCENTRATION DISTRIBUTION with the condition meeting above-mentioned (1)��(3) and roll etc. reduce or are removed.
" rectification "
Rectification is implemented, it is possible to increase the flatness of sheet material by waiting after calendering or after final solution treatment. Can also implement to correct under room temperature or room temperature temperature below, but when carrying out heat straightening, it is possible to improve flatness further. When carrying out heat straightening, it is preferable that maintenance temperature is set as less than 300 DEG C. Condition can be enumerated more specifically: keeping temperature is more than 100 DEG C and less than 300 DEG C, it is preferable that 150 DEG C��280 DEG C. The time being preferably maintained within the scope of more than 150 DEG C and 300 DEG C of temperature below by the raw material (such as, rolled material) of this correction process was also included within the above-mentioned total ascent time. Heat straightening such as can suitably with possess can heating raw materials heating furnace and in order to the raw material seriality after heating is given bending (strain) and multiple rollers is opposed to be configured to the roll straightening device in jagged roller portion up and down. When using roll straightening device, even if the raw material of long size also is able to correct continuously. Additionally, heat straightening can utilize such as hot-press arrangement. After heat straightening, when average cooling rate in from raw-material temperature when beginning to cool down to the period that this raw-material temperature reaches less than 100 DEG C is set as more than 0.8 DEG C/min, it is also possible to effectively suppress the increase of the amount of the precipitate such as ultrahigh concentration region and the increase of low concentration region, intermetallic compound that the growth of precipitate causes. In order to realize this rate of cooling, as set forth above, it is possible to suitably utilize forced cooling device, it is also possible to naturally let cool. Particularly when starting to carry out heat straightening continuously from calendering, during rate of cooling controlled as described above, Al CONCENTRATION DISTRIBUTION can not only be made to become specific state, and, even if being not easy to when wound into rolls produce crimping, the sheet material that flatness is excellent can be obtained, it is thus preferred to.
" plastic working "
When the plastic workings such as punch process implemented by the sheet material that manner described above is made or coiled material, improve plastic working by the raw material such as sheet material, coiled material is heated. Raw-material temperature preferably less than 350 DEG C, more preferably less than 300 DEG C, it is particularly preferred to less than 280 DEG C. Particularly preferably more than 150 DEG C and less than 280 DEG C, more preferably more than 150 DEG C and less than 220 DEG C. When raw material being preheated to this temperature, by less than 8 hours will be set as the retention time as mentioned above, it is possible to suppress the growth of precipitate, it is effectively prevented the increase of the area occupation ratio of ultrahigh concentration region and the increase of low concentration region, intermetallic compound. As long as by raw material heating to carrying out the degree of desired plastic working, then the retention time is more short more preferred, more preferably less than 0.5 hour (less than 30 minutes), more preferably less than 0.3 hour further. Particularly, as it has been described above, sometimes longer than sheet material for the time needed for making coiled material entirety reach uniform temperature, therefore, can use the heater that such as can carry out instant heating or in heating furnace appropriately configured fan, wind deflector so that the retention time shorten. On the other hand, the time the itself during plastic working such as punch process also depends on shape, it is postulated that be as short as the approximate number second in punch process to few minutes, substantially without the unfavorable condition such as coarsening producing precipitate. By carrying out plastic working under this specific condition, it is possible to make the plastic working material of the specific Al CONCENTRATION DISTRIBUTION with the condition meeting above-mentioned (1)��(3).
Heat treatment is implemented, it is possible to remove the strain, the residual stress improve mechanical property that are imported by plastic working after above-mentioned plastic working. This heat treatment condition can be enumerated: keeping temperature is 100 DEG C��300 DEG C, and the retention time is about 5 minutes��about 60 minutes. But, in this heat treatment, it is desirable to the retention time in 150 DEG C��300 DEG C temperature ranges was also included within the above-mentioned total ascent time.
" raw material is maintained at the total ascent time of specific temperature range "
As mentioned above, in operation after middle solution treatment, before preferred end article (preheating before calendering (including intermediate heat-treatment), finished heat treatment, rectification, plastic working etc. each operation), it is preferable that raw material is maintained at the total ascent time in 150 DEG C��300 DEG C temperature ranges to be controlled to be short period of less than 12 hours. When carrying out final solution treatment, it is preferable that in the operation after final solution treatment, before end article, the total ascent time being maintained at by raw material in 150 DEG C��300 DEG C temperature ranges is set as less than 12 hours.
In order to guarantee enough heat time heating times in the plastic workings such as calendering, it is preferable that the total ascent time kept in above-mentioned 150 DEG C��300 DEG C temperature ranges is more than 0.01 hour. More preferably to make temperature range for more than 150 DEG C and less than 280 DEG C it is preferred that more than 150 DEG C and less than 220 DEG C, the total ascent time is less than 8 hours, is in particular the mode of less than 0.3 hour and controls the degree of finish of each passage in calendering procedure and the manufacturing condition such as total degree of finish, pre-warmed condition (pre-warmed method, time etc.), the condition (cooling means, time etc.) of refrigerating work procedure, linear velocity. It addition, the content of Al is more many, above-mentioned rich Al intermetallic compound more easily precipitates out, it is therefore preferable that the content always according to Al regulates the above-mentioned total ascent time.
As mentioned above, when carrying out final solution treatment after middle solution treatment, preferably in being not heated to more than 300 DEG C after final solution treatment, but, if such (preferably less than the 8 hours short time such as coarsening not producing precipitate, more preferably less than 1 hour), then allow for.
As mentioned above, as the manufacture method including calendering procedure, as manufacture method more specifically, it is possible to enumerate the operations such as such as casting �� middle solid solution (preferably in controlling rate of cooling in refrigerating work procedure) �� calendering �� intermediate heat-treatment (according to maintaining the temperature at control rate of cooling in refrigerating work procedure) �� calendering �� rectification, grinding, cleaning. According to this manufacture method, by implementing middle solution treatment before calendering, it is possible to make precipitate become fine/minimum, it is possible to the miniaturization that undertaken organizing by calendering afterwards, the improvement of mechanical property.
(manufacture method 2)
On the other hand, when the magnesium alloy materials of the present invention be by do not include form that the manufacture method of calendering procedure formed, representational for shaped by die casting etc. formed body (including obform body), it is possible to manufacture by such as possessing the manufacture method of following preparatory process and final solid solution operation.
Preparatory process: prepare choosing and freely contain the raw-material operation of one in the die-casting material of magnesium alloy composition of Al of more than 7.3 mass % and below 16 mass %, thixotropic injection moulding material and extruded material.
Final solid solution operation: above-mentioned raw material is implemented in the double equilibrium diagram (quality %) keeping temperature to be Mg-Al than more than the temperature of Al low 10 DEG C of temperature of solid solution in Mg (minimum maintenance temperature), the retention time is the operation of final solution treatment of more than 1 hour and less than 40 hours.
Particularly, the rate of cooling in 330 DEG C��380 DEG C temperature ranges meets the following conditions.
By through-thickness from above-mentioned raw-material surface until when the region of 10 ��m is set to surface region, surface region being cooled down with the rate of cooling of more than 1 DEG C/min.
In manufacture method 2, by the raw material prepared in above-mentioned preparatory process is implemented the final solution treatment same with above-mentioned manufacture method 1-2, it is possible to make the solid solution material with the specific Al CONCENTRATION DISTRIBUTION meeting above-mentioned (1)��(3) condition. Particularly, above-mentioned manufacture method 2 can be suitable for manufacturing the magnesium alloy materials of complicated 3D shape as above.
Die Casting Condition and thixotropic injection moulding condition can utilize known condition. Extruded material such as by preparing the blank that is made up of the magnesium alloy of the Al containing above-mentioned specified quantitative and can extrude manufacture under known condition.
" other operations "
By possess to the rolled material obtained by manufacture method 1,2, heat treatment material, correction material, solid solution material implement grind (preferred wet lapping) grinding step, it is possible to obtain the grinding-material (form of the magnesium alloy materials of the present invention) with the specific Al CONCENTRATION DISTRIBUTION of the condition meeting above-mentioned (1)��(3). Additionally, by being also equipped with the operation of the enforcement anti-corrosion treatment such as chemical conversion treatment, anodized in the either method of manufacture method 1,2 or being also equipped with being formed the operation of coating layer, it is possible to obtain the magnesium alloy materials of the base material possessing the specific Al CONCENTRATION DISTRIBUTION with the condition meeting above-mentioned (1)��(3) and the corrosion-resistant coating formed on the substrate or the present invention of coating layer. The material of corrosion-resistant coating or coating layer and formation condition can utilize known material and condition. During anti-corrosion treatment, it is preferable that implement the pretreatment such as defat, acid etching, scrubbing, surface modulation. When carrying out plastic working, after plastic working, form corrosion-resistant coating or during coating layer, it is possible to the damage of corrosion-resistant coating or coating layer when preventing plastic working.
Embodiment
Below, the embodiment more specifically of the present invention is illustrated.
[test example 1]
Making the magnesium alloy materials containing Al under various conditions, distribution and corrosion resistance to Al concentration are investigated.
In this experiment, prepare following sample No.1��5 made magnesium alloy materials and as compare commercially available die-casting material (AZ91 alloy, thickness 3mm, width 75mm, length 150mm sheet material). This die-casting material is implemented wet type belt-sanding same with the milled processed that sample No.1��5 described later are implemented when and makes abrasive sheet, using this abrasive sheet as sample No.100.
The manufacturing process of sample No.1��5 described below.
Sample No.1: coiled material (does not carry out final solid solution) after calendering
Casting �� middle solid solution �� calendering �� rectification �� grinding
Sample No.2: solid solution coiled material (carries out final solid solution) after calendering
Casting �� middle solid solution �� calendering �� final solid solution �� rectification �� grinding
Sample No.3: sheet material (rapid heating and cooling material) �� midway does not wind
�� middle solid solution �� calendering �� rectification �� grinding (is cut) in casting after casting
Sample No.4: solid solution material (die casting)
The preparation of die-casting material �� final solid solution
Sample No.5: solid solution material (extrusion)
The preparation of extruded material �� final solid solution
" sample No.1,2 "
Make by the cast sheet (thickness 4mm, width 300mm) with the magnesium alloy composition forming (Mg-8.75%Al-0.65%Zn (being all quality %)) worked as with AZ91 alloy phase and the long size obtained by double roller continuous casting method, first it is wound, makes casting coiled material. This casting coiled material is loaded batch kiln, implements the solution treatment (middle solution treatment) of 400 DEG C of (>=20 �� 8.75+172=347 DEG C) �� 24 hour. The middle solid solution coiled material obtained is carried out uncoiling, implements the calendering of multi-pass under the following conditions and wind, make the calendering coiled material of thickness 0.6mm, width 250mm, length 800m.
(rolling condition)
Reduction ratio: 5%/passage��40%/passage
Raw-material temperature: 200 DEG C��280 DEG C
Roll temperature: 100 DEG C��250 DEG C
At this, adopt and following constitute: the raw material frame of uncoiling is unreeled between drum and the winding drum being accommodated in another heating furnace what be accommodated in heating furnace, makes raw material move between two drums by the rotations of two drums. It addition, configuration stack, the raw material enforcement calendering to movement between this two drum. At this, for each passage, make to unreel drum and winding drum reverse rotation, the calendering carrying out multi-pass continuously by making to unreel and wind reverse. Then, for each passage, the raw material after winding in heating furnace is heated to said temperature, and makes the raw material of heated condition move between drum.
After raw material is implemented the hot calender of final passage, it is made directly winding and regulates raw-material temperature with above-mentioned heating furnace, then, the raw material of uncoiling being blowed the wind being adjusted to certain temperature, thus regulates rate of cooling. At this, with until raw-material temperature (200 DEG C��280 DEG C) reach the average cooling rate of 100 DEG C be No.1:2.0 DEG C/min of sample, No.2:1.7 DEG C/min of sample, reach the average cooling rate till room temperature (about 20 DEG C) from 100 DEG C be No.1:1.0 DEG C/min of sample, the mode of No.2:0.9 DEG C/min of sample regulates the temperature of above-mentioned wind and cools down. Then, the calendering plate returning to room temperature is wound and makes calendering coiled material.
By above-mentioned calendering coiled material uncoiling, utilize roll straightening device to implement heat straightening, make and correct coiled material (raw-material temperature: 250 DEG C), by this rectification coiled material uncoiling, wet type belt-sanding is implemented in the grinding abrasive band using #600, and the abrasive sheet obtained is wound, and makes and grinds coiled material. Using this grinding coiled material as sample No.1. For sample No.1, after above-mentioned middle solution treatment, obtain in the manufacturing process before final grinding coiled material, within being set as 12 hours the total ascent time that raw material keeps in 150 DEG C��300 DEG C temperature ranges, it is not performed for more than the heating of 300 DEG C.
On the other hand, above-mentioned calendering coiled material is loaded in batch furnace, implements the final solution treatment of 350 DEG C (>=(20 �� 8.75+172)=347) �� 1 hour, then, be cooled to room temperature (about 20 DEG C) by pressure cooling. The surface being cooled through the cylindrical shape utilizing the injection emitting mechanism coiled material to taking out from batch furnace blows cold wind and carries out. Particularly, the mode being 3 DEG C/min (>=1 DEG C/min) with the average cooling rate of the surface region (through-thickness is from the region till 10 ��m of surface) of in 380 DEG C��330 DEG C temperature ranges, to be constituted coiled material sheet material regulates the temperature of cold wind, air quantity, wind speed etc. At this, in the suitable position of coiled material, thermocouple is installed, carries out above-mentioned adjustment in the mode that the rate of cooling at the slowest position of cooling is 3 DEG C/min. It addition, at this, coiled material former state cools down but it also may cool down when by coiled material uncoiling.
The above-mentioned solid solution coiled material uncoiling that will obtain, operates in the same manner as sample No.1, implements heat straightening, wet type belt-sanding under identical condition. Using the grinding coiled material that obtains as sample No.2. Additionally, for sample No.2, after above-mentioned final solution treatment, obtain, in the final manufacturing process grinding coiled material, within being set as 12 hours the total ascent time that raw material keeps in 150 DEG C��300 DEG C temperature ranges, not being performed for more than the heating of 300 DEG C. The operation that sample No.2 is maintained in 150 DEG C��300 DEG C temperature ranges after final solution treatment, by raw material is substantially only heat straightening. At this, to passing through to roll thinning raw material enforcement heat straightening, therefore, it is possible to the retention time making said temperature scope is few minutes.
" sample No.3 "
Prepare multiple by the cast sheet constituting with sample No.1,2 same magnesium alloys formed and being obtained by double roller continuous casting method (thickness 5mm, width 300mm, length 500mm casting sheet material). After each cast sheet obtained is implemented the solution treatment (middle solution treatment) of 400 DEG C �� 24 hours, while carrying out the cutting for regulating length, with sample No.1,2 calenderings implementing multi-pass when same, make the calendering plate (sheet material) of thickness 0.6mm, width 300mm, length 2000mm. Before each passage of calendering, utilize and can the heater of instant heating preheat, raw material is heated to predetermined temperature. The total retention time in preheating is 3 hours. It addition, after raw material is implemented the hot calender of final passage, this raw material is placed on cooling steel plate (can by making thermal medium circulation carry out temperature controlled steel plate), thus regulates rate of cooling. At this so that until raw-material temperature (200 DEG C��280 DEG C) reach the average cooling rate of 100 DEG C be 60 DEG C/min, until raw-material temperature reaches, the mode that average cooling rate is 40 DEG C/min of room temperature (about 20 DEG C) regulates the temperature of cooling steel plate, the mounting time cools down. Operate to the calendering plate and the sample No.1 that make, in the same manner as 2, implement heat straightening, wet type belt-sanding under identical condition. Abrasive sheet (the sheet material that will obtain. Hereinafter sometimes referred to rapid heating and cooling material) as sample No.3. Sample No.3 is same with sample No.1, after above-mentioned middle solution treatment, obtain in the manufacturing process before final abrasive sheet, within being set as 12 hours the total ascent time that raw material keeps in 150 DEG C��300 DEG C temperature ranges, it is not performed for more than the heating of 300 DEG C.
" sample No.4 "
Prepare the commercially available die-casting material same with sample No.100 (AZ91 alloy (Al:8.75 mass %), thickness 3mm, width 75mm, length 150mm sheet material), after this die-casting material is implemented the final solution treatment of 380 DEG C (>=(20 �� 8.75+172)=347) �� 20 hours, by forcing cooling to be cooled to room temperature (about 20 DEG C). The surface of sheet material is blowed cold wind with sample No.2 likewise by use injection emitting mechanism and carries out by this cooling, so that the mode that rate of cooling is 50 DEG C/min (>=1 DEG C/min) of the surface region in 380 DEG C��330 DEG C temperature ranges regulates the temperature of cold wind, air quantity, wind speed etc. After above-mentioned pressure cooling, when less than 250 DEG C, implement the planarization (rectification) based on hot pressing processing, then, by with sample No.1,2 same method enforcement wet lappings. Using the abrasive sheet that obtains as sample No.4.
" sample No.5 "
Prepare the commercially available die-casting material same with sample No.100 is carried out re-melting casting after carry out extrusion processing and obtain raw material (AZ91 alloy, thickness 3mm, width 50mm, length 150mm sheet material), this extruded material is implemented the final solution treatment of 380 DEG C �� 20 hours, then, injection emitting mechanism is used, by forcing cooling to be cooled to room temperature (about 20 DEG C) in the same manner as sample No.4. After this pressure cooling, same with sample No.4 when, implement the rectification based on hot pressing processing and wet lapping, using the abrasive sheet that obtains as sample No.5. Sample No.5 is also so that the mode that rate of cooling is 50 DEG C/min (>=1 DEG C/min) of surface region in 380 DEG C��330 DEG C temperature ranges regulates the temperature of cold wind, air quantity, wind speed etc.
It addition, about the adjustment of the rate of cooling in the rate of cooling in the refrigerating work procedure after above-mentioned final hot calender, final solution treatment operation, if the related data being produced as follows in advance with reference to this related data, then can easily carry out above-mentioned adjustment. in order to utilize temperature sensor measurement thickness, length, the most surface of the cooling object such as multiple coiled materials that winding number is different or sheet material, or the temperature from 10 ��m of surface place is (such as, form groove at above-mentioned position and bury temperature sensor etc. in the cell underground) and temperature to cold wind, air quantity, when each parameter of the forced cooling devices such as wind speed suitably changes, measure the raw-material temperature when cooling from above-mentioned refrigerating work procedure starts and arrive the time 100 DEG C required, the time 330 DEG C required is arrived from 380 DEG C, obtain rate of cooling, make the related data of each parameter and rate of cooling. when cooling object is coiled material, it is possible to temperature sensor is arranged in the appropriate location of coiled material, make the related data that the rate of cooling at the position the slowest with cooling is relevant in advance.
The content (Al ensemble average amount) for measuring the overall Al of sample is cut: the entire amount test film of x mass % from sample No.1��5 of gained and comparative sample No.100, utilize this test film, by ICP ICP Atomic Emission Spectrophotometer, obtain Al ensemble average amount, as a result, any one sample is x=8.75 mass %.
Mapping test film is cut from sample No.1��5 of gained and comparative sample No.100, use FE (FieldEmission, field emission)-EPMA device (Jeol Ltd. JXA-8530F), carry out the element on the surface of each test film: the analysis of Al and mensuration. Condition determination described below.
(condition determination)
Accelerating potential: 15kV
Irradiate electric current: 100nA
Sampling time: 50ms
The content (quality %) of the Al in above-mentioned elementary analysis is by making following standard curve and using this standard curve that the X-ray intensity of EPMA is scaled the content of Al (quality %) and obtain.
[making of standard curve]
The different commercially available AZ31 alloy material of the content of Al, AZ61 alloy material, AZ91 alloy phase are implemented solution treatment (400 DEG C �� 120 hours) when material, using the material after homogenizing as sample. AZ91 alloy phase utilizes after being cut by the solid solution coiled material of sample No.2 when material. Then, the surface of each sample is carried out ICP ICP Atomic Emission Spectrophotometer, measure the content of Al, and, in FE-EPMA, carry out elementary analysis according to said determination condition, measure the X-ray intensity (cps/ �� A) of Al.
Then, as shown in Figure 4, the X-ray intensity that will obtain: y is expressed as the content of Al: the linear function of x, uses the approximate expression of linear function: y=11977x+1542.5 is as standard curve. It addition, the coefficient R of this approximate expression2It is 0.9998, is the approximate expression that reliability is high.
The surface of each sample is analyzed by FE-EPMA and obtains the mapping graph picture (field of view: 24 �� m 18 ��m) relevant to the content of Al by Fig. 1. Fig. 1 (A) represents the coiled material of sample No.1, Fig. 1 (B) represents the solid solution coiled material of sample No.2, Fig. 1 (C) represents the sheet material (rapid heating and cooling material) of sample No.3, and Fig. 1 (D) represents the die-casting material of sample No.100. In FIG, it is indicated with Lycoperdon polymorphum Vitt scale, but indeed according to Al concentration, apply black (Al concentration: in this case 0 mass %)��purplish blue color��sky blue��light blue��green��yellow��orange��red��pink��white (Al concentration: in this case more than 8.75 �� 1.4=12.25 mass %) by the poor order of Al. Fig. 1 (A), Fig. 1 (B), the white particulate body of Fig. 1 (C), Fig. 1 (D) white special-shaped object be rich Al intermetallic compound.
It can be seen that in the die-casting material of sample No.100, the region that Al concentration is very high is many as Suo Shi Fig. 1 (D). In addition we know, there is the low-down region of Al concentration. On the other hand, as shown in Fig. 1 (A)��Fig. 1 (C) known, the coiled material of sample No.1, the solid solution coiled material of sample No.2, sample No.3 sheet material (rapid heating and cooling material) in, the very high region of Al concentration is not locally not in a large number. Particularly it can be seen that in the solid solution coiled material of sample No.2, the region that Al concentration is very high is little and considerably less. In addition we know, in coiled material, solid solution coiled material, sheet material (rapid heating and cooling material), the low-down region of Al concentration substantially all it is absent from. Confirm: die-casting material or extruded material being implemented final solid solution and the sample No.4,5 same with sample No.2 that obtains, the region that Al concentration is very high is little and considerably less, and is created substantially absent the low-down region of Al concentration.
Use this mapping graph picture, obtain Al concentration in the field of view of each sample to be the area occupation ratio of the low concentration region of below 4.2 mass %, Al concentration be 0.8x (=8.75 �� 0.8=7) more than quality % and the area occupation ratio of center compositing area of 1.2x (=8.75 �� 1.2=10.5) below quality %, Al concentration is 0.9x (=8.75 �� 0.9=7.875) more than quality % and the area occupation ratio of 1.2x mass % area below, Al concentration are the area occupation ratio in ultrahigh concentration region of 1.4x (=8.75 �� 1.4=12.25) more than quality %, the maximum of Al concentration and minima. The results are shown in table 1. It addition, Al CONCENTRATION DISTRIBUTION is shown in the figure of Fig. 2.
Fig. 3 be each sample No.1��3,100 scanning electron microscope: the microphotograph (5000 times) of SEM. Fig. 3 (the A)��grayish coccoid of Fig. 3 (C), Fig. 3 (D) grayish special-shaped object represent precipitate. As Suo Shi Fig. 3 (D) it can be seen that in the die-casting material of sample No.100, precipitate greatly and is abnormity. Big and for abnormity the situation in this ultrahigh concentration region very high with obtaining Al concentration in mapping graph picture is consistent. On the other hand, known, in the sheet material (rapid heating and cooling material) of the sample No.3 shown in the solid solution coiled material of sample No.2 shown in the coiled material of sample No.1 shown in Fig. 3 (A), Fig. 3 (B), Fig. 3 (C), precipitate is all less, and the coccoid of circle all exists equably. Particularly it can be seen that in the coiled material of sample No.1, round coccoid of uniform size exists on the whole dispersedly, the precipitate of the solid solution coiled material of sample No.2 is very little and considerably less. The situation that this ultrahigh concentration Regional Dispersion less with mapping graph picture exists is consistent. Sample No.4,5 solid solution material the same with the solid solution coiled material of sample No.2, precipitate is very little and considerably less. Utilizing EDS (X-ray energy spectrometer: EnergyDispersiveX-raySpectrometer) that the composition of above-mentioned grayish coccoid and special-shaped object has been investigated, result is Mg17Al12, the intermetallic compound containing Al, Mg such as Al (MnFe). The existence of this intermetallic compound can also by utilizing its Nomenclature Composition and Structure of Complexes of investigation such as X-ray diffraction to distinguish.
Each sample No.1��5, the mean diameter (��m) of the intermetallic compound of 100 and the ratio (area %) of total area have been measured. Its result is also depicted in table 1. Mean diameter or area ratio easily can calculate by utilizing commercially available image processing apparatus that above-mentioned microphotograph is carried out image procossing.
The mean diameter of intermetallic compound is carried out as follows mensuration. Each sample is taken respectively on thickness of slab direction to 5 cross sections, take respectively from the observation image in each cross section arbitrary three visuals field (this, 1 visual field: the region of 22.7 �� m 17 ��m). At this, the above-mentioned visual field is selected from face side region to 100 ��m, the through-thickness surface from each sample. Each field of view is obtained respectively the equivalent diameter (the equivalent area diameter of a circle of the area of each intermetallic compound) of each intermetallic compound existed in a field of view, by the summation of above-mentioned equivalent diameter divided by the quantity of intermetallic compound existed in a field of view, the value using obtained: (total of equivalent diameter)/(total number) is as the mean diameter of this field of view. And, for each sample, the meansigma methods of the mean diameter of 15 field of view is shown in Table 1.
The ratio adding up to area of intermetallic compound is carried out as follows mensuration. Field of view is taken as mentioned above from face side region, each field of view is investigated respectively the area of all intermetallic compounds existed in a field of view and calculates total area, with this total area area (in this case 385.9 ��m divided by a field of view2), the value using obtained: (total area)/(area of field of view) is as the area ratio of this field of view. And, for each sample, the meansigma methods of the area ratio of 15 field of view is shown in Table 1.
To each sample No.1��5,100 carry out brine corrosion test, measure corrosion weight loss (�� g/cm2), Mg stripping quantity (�� g/cm2). The results are shown in table 1.
Test as brine corrosion, carry out salt spraytest based on JISH8502 (1999), and measure corrosion weight loss in the following manner. By sample No.1��5,100 making corrosion test films, after measuring the quality (initial value) of this corrosion test film, implement to shelter to the unwanted position of corrosion test film in the way of making corrosion test film expose the test face of size set in advance. The corrosion test film sheltered is loaded in corrosion testing apparatus, be erected in the way of relative to this device inclined bottom surface predetermined angular configuration (this, the angle that device bottom surface is formed with test film: 70 �㡫80 ��). When experimental liquid (the NaCl aqueous solution of 5 mass %, temperature: 35 �� 2 DEG C) is formed vaporific after be sprayed onto on corrosion test film keep the scheduled time (in this case 96 hours). After the scheduled time, corrosion test film is taken out from corrosion testing apparatus, remove after sheltering, based on the method that JISZ2371 (2000) reference table 1 is recorded, dissolved by chromic acid and remove the corrosion product generated on corrosion test film. Measure the quality removing the corrosion test film after corrosion product, with the difference of this quality and the above-mentioned initial value area testing face divided by corrosion test film, using the value of gained as corrosion weight loss (�� g/cm2)��
Test as brine corrosion, carry out salt water immersion test under the following conditions, following mensuration Mg stripping quantity. By sample No.1��5,100 making corrosion test films, implement to shelter to the unwanted position of corrosion test film in the way of making corrosion test film expose the test face of size set in advance. The corrosion sheltered test film is being completely infused in experimental liquid (the NaCl aqueous solution of 5 mass %, liquid measure: the area (exposing area) in the test face of test film is set to (A) cm2Time be (A) �� 20ml) in state under keep the scheduled time (in this case 96 hours, be maintained at the room temperature (25 �� 2 DEG C) under air-conditioning). After the scheduled time, recovery test liquid, via ICP-AES, the Mg ionic weight in experimental liquid is carried out quantitatively, with the Mg ionic weight area divided by the test face of corrosion test film, using the value of gained as Mg stripping quantity (�� g/cm2)��
As shown in Table 1, sample No.1��5 are at least in face side region, Al concentration is that 0.8x mass %��1.2x mass % is (at this, x=8.75) center compositing area accounts for 50 more than area %, and, being absent from the low concentration region that Al concentration is below 4.2 mass %, the ultrahigh concentration region that Al concentration is more than 1.4x mass % is 17.5 below area %. Particularly, it is known that, in sample No.1��5, ultrahigh concentration region is 15 below area %, Al concentration be the region of 0.9x mass %��1.2x mass % is 30 more than area %. I.e., it is possible to say that the deviation of the Al concentration of sample No.1��5 is little. This situation from the figure of Fig. 2 it can also be seen that. As shown in Figure 2 it can be seen that the distribution of the Al concentration of sample No.1��3 all becomes the Al ensemble average amount at each sample: 8.75 mass % and near there is the distribution at peak. In addition we know, sample No.1��3 are absent from the position that Al concentration is extremely low. Sample No.4,5 also show that the Al CONCENTRATION DISTRIBUTION same with sample No.2. And, as shown in Table 1, corrosion weight loss and the Mg stripping quantity of sample No.1��5 that the deviation of this Al concentration is little are few, excellent corrosion resistance.
Particularly known, the solid solution coiled material of sample No.2, the sheet material of sample No.3, sample No.4,5 solid solution material in, not only Al concentration is that the center compositing area of 0.8x mass %��1.2x mass % is very big, it is 70 more than area %, and ultrahigh concentration region that Al concentration is more than 1.4x mass % is very little, to be 5 below area %, Ye You center compositing area the be sample of 90 more than area %, ultrahigh concentration region are the sample of 3 below area %. Namely, it is known that, in sample No.2��5, Al more uniformly exists. It can be seen that wherein, in sample No.2, not only ultrahigh concentration region is considerably less, and the difference of the maxima and minima of Al concentration is less, and Al more uniformly exists. And it can be seen that the corrosion resistance with sample No.2��5 of this uniform composition is more excellent.
In addition we know, implement the solid solution coiled material of the sample No.2 of final solution treatment and sample No.4,5 solid solution material in, intermetallic compound is few to 3 below area %, and the maximum of Al concentration is relatively low. Result, it is believed that the excellent corrosion resistance of sample No.2,4,5. Especially since sample No.2 is long material, therefore, it is possible to contribute to the batch production of the plastic working material of excellent corrosion resistance, higher industrial meaning can be expected.
On the other hand, in the die-casting material of sample No.100, the center compositing area that Al concentration is 0.8x mass %��1.2x mass % is few, and there is the low concentration region that Al concentration is below 4.2 mass %. Particularly, the minima of Al is the value worked as with AZ31 alloy phase. It addition, the area occupation ratio of the intermetallic compound of sample No.100 is big. Result, it is believed that there is the position that corrosion resistance is relatively poor in sample No.100, thus obtaining the result of corrosion-resistant.
[test example 2]
After the sheet material enforcement punch process of sample No.1��5 made in test example 1, similarly measure Al concentration. The coiled material of sample No.1, sample No.2 solid solution coiled material be all by uncoiling and cut into predetermined length and make rectangular slab. Ready each sheet material is preheated at 250 DEG C, with this heated condition for punch process. Total ascent time when above-mentioned pre-warmed retention time and punch process is 2 minutes (less than 0.1 hour).
The punch process material (plastic working material) obtained all has the Al CONCENTRATION DISTRIBUTION same with sample No.1��5. Therefore, can expect that the corrosion resistance of these punch process materials is also excellent.
It addition, the invention is not restricted to above-mentioned embodiment, can suitably be modified when without departing from present subject matter. For example, it is possible to suitably change the composition (particularly the content of Al) of magnesium alloy, the shape of magnesium alloy materials, specification (thickness, width, length), manufacturing condition etc.
Industrial applicability
The magnesium alloy materials of the present invention can be suitable as the member of formation of various electric/electronic device class, particularly can be suitable as the housing, the expectation component in each field of high intensity, the such as member of formation of the transporting equipment such as automobile component and aircraft, frame member, the bag etc. that carry use or small-sized electric/electronic device class. Or, the magnesium alloy materials of the present invention can be suitable as the raw material of above-mentioned component.
Claims (11)
1. a magnesium alloy materials, by the Al containing more than 7.3 mass % and below 16 mass % and have the magnesium alloy on a surface and constitute, it is characterised in that
When the content of the Al that described magnesium alloy materials is overall is set to x mass %,
In described surface, the content of Al is 50 more than area % for (x �� 0.8) more than quality % and (x �� 1.2) quality % area below,
In described surface, the content of Al is the region of (x �� 1.4) more than quality % is 17.5 below area %,
The content being created substantially absent Al is 4.2 mass % area below,
In described surface, the mean diameter containing at least one intermetallic compound in Al and Mg is less than 3.0 ��m.
2. magnesium alloy materials as claimed in claim 1, it is characterised in that
In described surface, the content of Al is 70 more than area % for (x �� 0.8) more than quality % and (x �� 1.2) quality % area below,
In described surface, the content of Al is the region of (x �� 1.4) more than quality % is 5 below area %.
3. magnesium alloy materials as claimed in claim 1 or 2, it is characterised in that in described surface, the content of Al is 50 more than area % for (x �� 0.9) more than quality % and (x �� 1.2) quality % area below.
4. magnesium alloy materials as claimed in claim 1 or 2, it is characterised in that in the cross section in the face side region of described magnesium alloy materials, the total area containing at least one intermetallic compound in Al and Mg is 3 below area %.
5. magnesium alloy materials as claimed in claim 1 or 2, it is characterised in that described magnesium alloy materials is sheet material.
6. magnesium alloy materials as claimed in claim 1 or 2, it is characterised in that described magnesium alloy materials is that the sheet material of long size is wound the coiled material obtained.
7. magnesium alloy materials as claimed in claim 1 or 2, it is characterised in that described magnesium alloy materials is that sheet material is implemented the plastic working material that plastic working obtains.
8. a magnesium alloy component, the magnesium alloy materials according to any one of claim 1��7 is constituted.
9. magnesium alloy component as claimed in claim 8, it is the component of electrical equipment, electronic equipment or transporting equipment.
10. magnesium alloy component as claimed in claim 8, it is the component of automobile or aircraft.
11. magnesium alloy component as claimed in claim 8, it is the housing of electrical equipment, the housing of electronic equipment, frame member or bag.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010292517A JP2012140655A (en) | 2010-12-28 | 2010-12-28 | Magnesium alloy sheet material |
| JP2010-292519 | 2010-12-28 | ||
| JP2010292519A JP2012140657A (en) | 2010-12-28 | 2010-12-28 | Magnesium alloy material |
| JP2010292518A JP2012140656A (en) | 2010-12-28 | 2010-12-28 | Magnesium alloy material |
| JP2010-292518 | 2010-12-28 | ||
| JP2010-292517 | 2010-12-28 | ||
| PCT/JP2011/080455 WO2012091112A1 (en) | 2010-12-28 | 2011-12-28 | Magnesium alloy material |
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| CN103282526A CN103282526A (en) | 2013-09-04 |
| CN103282526B true CN103282526B (en) | 2016-06-01 |
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| US (1) | US20140308157A1 (en) |
| EP (1) | EP2660343B1 (en) |
| KR (2) | KR20130089664A (en) |
| CN (1) | CN103282526B (en) |
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| CN103658173B (en) * | 2013-12-13 | 2016-01-06 | 内蒙古科技大学 | A kind of method based on billet production different performance magnesium alloy plate |
| US11198926B2 (en) * | 2013-12-17 | 2021-12-14 | Northwestern University | Alloys and methods of forming same |
| GB2527486A (en) | 2014-03-14 | 2015-12-30 | Imp Innovations Ltd | A method of forming complex parts from sheet metal alloy |
| CN105401031A (en) * | 2015-11-13 | 2016-03-16 | 太仓旺美模具有限公司 | Formula for magnesium alloy metal material |
| CN105779837A (en) * | 2016-05-25 | 2016-07-20 | 河南科技大学 | Gd containing sacrificial anode magnesium alloy |
| CN106868366A (en) * | 2017-02-14 | 2017-06-20 | 山东银光钰源轻金属精密成型有限公司 | A kind of production technology of automotive magnesium alloy gearbox designs support |
| AT521500B1 (en) * | 2018-12-18 | 2020-02-15 | Lkr Leichtmetallkompetenzzentrum Ranshofen Gmbh | Process for increasing corrosion resistance of a component formed with a magnesium-based alloy against galvanic corrosion and also a corrosion-resistant component obtainable with it |
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| CN1443862A (en) * | 2002-03-12 | 2003-09-24 | 高田株式会社 | Method for making magnesium alloy product |
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| JPS63282232A (en) * | 1987-05-15 | 1988-11-18 | Showa Denko Kk | High-strength magnesium alloy for plastic working and its production |
| JPH0578775A (en) * | 1991-09-20 | 1993-03-30 | Toyota Motor Corp | Magnesium alloy excellent in corrosion resistance |
| JPH05171332A (en) * | 1991-12-17 | 1993-07-09 | Toyota Motor Corp | Mg-al alloy die casting member excellent in creep resistance and its manufacture |
| JP4253847B2 (en) * | 2004-11-30 | 2009-04-15 | 住友電気工業株式会社 | Magnesium alloy wire, method for producing the same, and magnesium alloy molded body |
| JP2006348349A (en) * | 2005-06-16 | 2006-12-28 | Katsuyoshi Kondo | Magnesium alloy-powder raw material, high proof-stress magnesium alloy, method for manufacturing magnesium alloy-powder raw material and method for manufacturing high proof-stress magnesium alloy |
| JP5158675B2 (en) * | 2007-06-27 | 2013-03-06 | 三菱アルミニウム株式会社 | Magnesium alloy sheet material excellent in corrosion resistance and surface treatment and method for producing the same |
| BRPI0919653A2 (en) * | 2008-10-22 | 2015-12-08 | Sumitomo Electric Industries | product formed of magnesium alloy and magnesium alloy sheet |
| JP2010242146A (en) * | 2009-04-03 | 2010-10-28 | Toyota Central R&D Labs Inc | Magnesium alloy and magnesium alloy member |
| JP5522400B2 (en) * | 2009-12-11 | 2014-06-18 | 住友電気工業株式会社 | Magnesium alloy material |
| JP5637386B2 (en) * | 2010-02-08 | 2014-12-10 | 住友電気工業株式会社 | Magnesium alloy plate |
| KR101799615B1 (en) * | 2010-11-16 | 2017-11-20 | 스미토모덴키고교가부시키가이샤 | Magnesium alloy sheet and method for producing same |
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- 2011-12-28 KR KR1020137015544A patent/KR20130089664A/en active Application Filing
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| CN1113106C (en) * | 1997-07-17 | 2003-07-02 | 松下电器产业株式会社 | Magnesium alloy molded product and method for producing the same |
| CN1443862A (en) * | 2002-03-12 | 2003-09-24 | 高田株式会社 | Method for making magnesium alloy product |
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| CN103282526A (en) | 2013-09-04 |
| EP2660343A4 (en) | 2015-04-08 |
| TWI515303B (en) | 2016-01-01 |
| CA2823292C (en) | 2016-06-14 |
| TW201241189A (en) | 2012-10-16 |
| KR20130089664A (en) | 2013-08-12 |
| WO2012091112A1 (en) | 2012-07-05 |
| US20140308157A1 (en) | 2014-10-16 |
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| KR20150125729A (en) | 2015-11-09 |
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| EP2660343A1 (en) | 2013-11-06 |
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