CN103380223A - Magnesium alloy and manufacturing method for same - Google Patents

Magnesium alloy and manufacturing method for same Download PDF

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Publication number
CN103380223A
CN103380223A CN2012800090238A CN201280009023A CN103380223A CN 103380223 A CN103380223 A CN 103380223A CN 2012800090238 A CN2012800090238 A CN 2012800090238A CN 201280009023 A CN201280009023 A CN 201280009023A CN 103380223 A CN103380223 A CN 103380223A
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CN
China
Prior art keywords
magnesium alloy
plate
interior region
thickness
surf zone
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CN2012800090238A
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CN103380223B (en
Inventor
大石幸广
森信之
井上龙一
河部望
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Sumitomo Electric Industries Ltd
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Sumitomo Electric Industries Ltd
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Priority to JP2011-038889 priority Critical
Priority to JP2011038889A priority patent/JP5757105B2/en
Application filed by Sumitomo Electric Industries Ltd filed Critical Sumitomo Electric Industries Ltd
Priority to PCT/JP2012/054419 priority patent/WO2012115191A1/en
Publication of CN103380223A publication Critical patent/CN103380223A/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • C22C23/02Alloys based on magnesium with aluminium as the next major constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21BROLLING OF METAL
    • B21B3/00Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences Rolling of aluminium, copper, zinc or other non-ferrous metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0622Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by two casting wheels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/02Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
    • B22D21/04Casting aluminium or magnesium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/06Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon

Abstract

Provided is a magnesium alloy which is thick and exhibits excellent corrosion resistance and excellent surface-deterioration resistance, and a production method for the same. A magnesium (Mg) alloy (typically a magnesium alloy plate) having a plate-shaped section having a thickness of at least 1.5mm, wherein, if the region as far as 1/4 of the thickness, in the thickness direction, from the surface of the plate-shaped section is the surface region, and the remaining section is the inner-section region, the ratio (OF/Oc) of the base surface peak ratio (OF) of the surface region to the base surface peak ratio (Oc) (orientation joint of the (002) surface) of the inner-section region satisfies 1.5F/Oc.; In this magnesium alloy, the surface of the plate-shaped section is formed by means of an aggregate structure in which the (002) surface, which is the base surface of the Mg alloy crystals, is strongly oriented in comparison with the inner-section, and the alloy exhibits excellent corrosion resistance because the grain size in the surface region is typically smaller than that in the inner-section region, and due to the excellent surface deterioration resistance a molded product having excellent surface quality can be obtained by carrying out press working. A plate-shaped Mg alloy can be obtained by rolling, for a plurality of passes, a twin-roll continuous cast material, with the rolling reduction for all the passes being 25% or less.

Description

Magnesium alloy materials and manufacture method thereof
Technical field
The present invention relates to the method for a kind of magnesium alloy materials and the described magnesium alloy materials of manufacturing, described magnesium alloy materials is applicable to the parts of various members such as conveying machinery such as automobile, rail vehicle and aircraft, the parts of bike, the housing of Electrical and Electronic device and other structural member, and be applicable to the constituent material of described member.Especially, the present invention relates to have the thick magnesium alloy materials of high corrosion resistance and anti-surface irregularity.
Background technology
, the lightweight magnesium alloy with high specific strength and specific rigidity is studied such as housing, trolley part such as the wheel cap of mobile electrical and electronic installation such as mobile telephone and notebook computer and the parts of gearshift plectrum, rail vehicle parts and bike such as the constituent material of vehicle frame as various members.The member that is made of magnesium alloy is mainly formed by the cast material (the AZ91 alloy of American Society for Testing and Materials (ASTM) standard) of making by die casting method or the thixotroping method of forming.In recent years, used by the plate that the AZ31 alloy by wrought magnesium alloy such as ASTM standard is consisted of and carried out the press process material that press process obtains.Patent documentation 1 discloses, the continuous cast materials that is consisted of by the magnesium alloy such as the AZ91 alloy by the manufacturing of twin roller casting method, and to carrying out press process by continuous cast materials being rolled the milled sheet that obtains.
The prior art document
Patent documentation
Patent documentation 1: international disclosing No. 2006/003899
Summary of the invention
Technical problem
Being conceived to the lightweight of magnesium alloy, as the starting material that are used for plastic working material such as press process material, has been that the plate of the relative thin below the 1mm is studied to thickness.Yet, along with the expansion of magnesium alloy purposes scope, require not only to develop above-mentioned thin plate, and developed the slab that is conceived to specific tenacity and specific rigidity, particularly, have the slab of the above thickness of 1.5mm.This thick magnesium alloy plate, make the method for described thick magnesium alloy plate and use the plastic working material of described thick magnesium alloy plate manufacturing such as press process material not yet to be well studied.
By using die casting method or the thixotroping method of forming to obtain thick magnesium alloy plate.Yet, in cast material such as die casting material, be easy to form subsurface defect such as hole, and the Nomenclature Composition and Structure of Complexes is easy to become inhomogeneous in addition.For example, add the concentrated and crystal grain random orientation of elemental composition local height.Therefore, compare with plastic working material such as rolling stock, the erosion resistance of cast material such as die casting material is low.In addition, cast material such as die casting material are because internal defects and plastic working is poor and be not suitable as thus the plastic working starting material.
Therefore, the object of the present invention is to provide a kind of thick magnesium alloy materials that has the thick magnesium alloy materials of high corrosion resistance and anti-surface irregularity and carried out plastic working.Another object of the present invention is to provide a kind of manufacturing to have the method for the thick magnesium alloy materials of high corrosion resistance and anti-surface irregularity.
The means of dealing with problems
Compare with the thixotroping formed material with the die casting material, even its composition is identical, carried out plastic working (time processing) such as rolling magnesium alloy materials in mechanical property such as intensity, hardness and toughness, erosion resistance and plastic working aspect are still more excellent.This is because in this magnesium alloy materials, the formation of defective reduces and so that crystal is finer during the casting.By the magnesium alloy materials that has carried out time processing being implemented magnesium alloy materials that plastic working (secondary processing) obtains such as press process also excellent aspect mechanical property and the erosion resistance.Especially, in the time will being used as the starting material of time processing material by the continuous cast materials that Continuous casting process such as twin roller casting method are made, continuous cast materials is excellent aspect plastic working, because compare with the die casting material, the generation of segregation or thick crystallization precipitate reduces.Therefore, the present inventor has made the thick magnesium alloy plate with the above thickness of 1.5mm by under various conditions continuous cast materials being rolled.As a result, the inventor finds the following fact.The magnesium alloy thickness of slab of making under given conditions also has high corrosion resistance.In addition, when implementing plastic working such as press process or bending, gained plastic working material has a small amount of little concavo-convex in its surface, namely has smooth-flat-surface (for example glossiness beautiful surface of tool), this means that this plastic working material has high anti-surface irregularity.The present invention is with the above-mentioned basis that is found to be.
Magnesium alloy materials of the present invention is made of magnesium alloy and has plate-like portion, and described plate-like portion has the above thickness of 1.5mm.Described plate-like portion satisfies following orientation,
[orientation]
When 1/4 the zone definitions that will be from the surface of described plate-like portion has described plate-like portion thickness at thickness direction is surf zone and remaining area is defined as interior region,
The intensity at the X-ray diffraction peak of (002) face, (100) face, (101) face, (102) face, (110) face and (103) face in the described surf zone is defined as respectively I F(002), I F(100), I F(101), I F(102), I F(110) and I F(103),
The intensity at the X-ray diffraction peak of (002) face, (100) face, (101) face, (102) face, (110) face and (103) face in the described interior region is defined as respectively I C(002), I C(100), I C(101), I C(102), I C(110) and I C(103),
Degree of orientation with (002) described in described surf zone face: I F(002)/{ I F(100)+I F(002)+I F(101)+I F(102)+I F(110)+I F(103) } be defined as basal plane peak ratio O F, and
Degree of orientation with (002) described in described interior region face: I C(002)/{ I C(100)+I C(002)+I C(101)+I C(102)+I C(110)+I C(103) } be defined as basal plane peak ratio O CThe time,
Basal plane peak ratio O in the described surf zone FTo the basal plane peak ratio O in the described interior region CRatio O F/ O CSatisfy 1.05<O F/ O C
Magnesium alloy materials of the present invention for example can be by following manufacture method manufacturing of the present invention.For by the starting material that are made of magnesium alloy are rolled the method for making magnesium alloy materials, described method comprises following preparation step and rolling step according to the method for manufacturing magnesium alloy materials of the present invention.
Preparation step: the step of preparing by the twin roller casting method magnesium alloy of melting to be cast continuously the sheet stock material that obtains;
Rolling step: described starting material are carried out multi-pass rolling and make the step of the tabular magnesium alloy materials with the above thickness of 1.5mm.
In described rolling step, the draft of described each passage is below 25%.
Draft (%) is defined as { (raw-material thickness t before rolling herein b-rolling afterwards raw-material thickness t aRaw-material thickness t before)/rolling b} * 100.
Manufacturing method according to the invention, by using continuous cast materials can advantageously implement the rolling of multi-pass as starting material, in described continuous cast materials, can become the starting point of crackle etc. defective or crystallization precipitate, segregation exists on a small quantity or substantially do not exist.In addition, by in the draft of each passage of relative reduce, implementing multi-pass rolling, compare with the inside of rolling stock, be enough to give plastic working by rolling realization to the surface portion of rolling stock.In other words, by repeat to implement with relatively low draft rolling can be so that the surface tissue of rolling stock be mutually different with internal structure.Therefore, manufacture method of the present invention provides a kind of magnesium alloy materials (typically being milled sheet (a kind of form of magnesium alloy materials of the present invention)) that is made of the structure in the mutually different surf zones and the structure in the interior region.More specifically, the structure in the surf zone is that the basal plane of wherein magnesium alloy crystal is mainly fully to provide plastic working and texture (texture that the c-axis of magnesium alloy crystal is orientated in the mode vertical with rolling direction) that the mode parallel with rolling direction (direction that the starting material that are rolled move) is orientated by rolling.Structure in the interior region is more at random structure in the orientation ratio surf zone of basal plane of wherein magnesium alloy crystal.
When magnesium alloy materials of the present invention is above-mentioned specific milled sheet (, when magnesium alloy materials of the present invention all is made of plate-like portion), structure in the surf zone is the texture with specific orientation, more specifically, as (002) face of the basal plane of magnesium alloy crystal take by force to texture, and the structure in the interior region be wherein with the structure of comparing (002) face in the surf zone and being orientated more weakly.(002) face take by force to texture refer to be shown in plastic working such as rolling during fully apply a kind of index of the distortion that is caused by plastic working.Owing to fully implemented plastic working such as rolling, so the grain-size of magnesium alloy is oriented in decline, this has improved the total area of grain boundary.As a result, the impurity element of existence has high corrosion resistance to the relative magnesium alloy materials of the present invention that also has thus above-mentioned ad hoc structure that descends of ratio of grain boundary.Especially, when the surf zone under being exposed to outside atmosphere has than the finer structure of interior region, obtain higher erosion resistance.Therefore, magnesium alloy materials of the present invention is thick and have a high corrosion resistance.In addition, consist of magnesium alloy materials by the different structure between aforesaid surf zone and the interior region, thus, magnesium alloy materials has different performance (for example mechanical property such as hardness, intensity, shock-resistance and toughness, erosion resistance and freedom from vibration) between surf zone and interior region.By utilizing this poor performance, can expect magnesium alloy materials of the present invention is used for the starting material that various members also are used as various members.In addition, magnesium alloy materials of the present invention has good plastic working such as press processability or bendability, because the degree of orientation of basal plane ((002) face) is little in the interior region (orientation density degree is little in the texture).Thus, magnesium alloy materials can suitably carry out plastic working such as press process or crooked starting material.Surf zone is made of the micro crystal structure.Therefore, even the plastic working of enforcement such as press process still is difficult for forming concavo-convex greatly on raw-material surface and the plastic working material with smooth-flat-surface (a kind of form of magnesium alloy materials of the present invention) being provided.Therefore, magnesium alloy materials of the present invention has high anti-surface irregularity.Gained plastic working material also has good Surface Texture.
According to the embodiment of magnesium alloy materials of the present invention, when the average grain size in the described surf zone is defined as D FAnd the average grain size in the described interior region is defined as D CThe time, the average grain size D in the described interior region CTo the average grain size D in the described surf zone FRatio D C/ D FSatisfy 1.5<D C/ D F
According to above-mentioned embodiment, the grain-size in the interior region is greater than the grain-size in the surf zone.In other words, the grain-size in the surf zone is fully less than the grain-size in the interior region, and this has improved the length of aforesaid grain boundary and has realized thus high corrosion resistance.According to above-mentioned embodiment, owing to surf zone is made of the micro crystal structure, so obtain good plastic working and Gao Nai surface irregularity.In addition, because the grain-size in the interior region realizes high heat resistance thus greater than the grain-size in the surf zone.
According to the embodiment of magnesium alloy materials of the present invention, when the Vickers in the described surf zone (Vickers) hardness (Hv) is defined as H FAnd the Vickers' hardness in the described interior region is defined as H CThe time, the Vickers' hardness H in the described interior region CTo the Vickers' hardness H in the described surf zone FRatio H C/ H FSatisfy H C/ H F<0.85.
According to above-mentioned embodiment, the Vickers' hardness in the interior region is lower than the Vickers' hardness in the surf zone.In other words, the Vickers' hardness in the surf zone fully is higher than the Vickers' hardness in the interior region, realizes thus high abrasion resistance.
Magnesium alloy materials of the present invention can be made of the magnesium alloy that contains various interpolation elements (residuum: Mg and impurity).Especially, contain the alloy that adds element with high density, particularly, contain the magnesium alloy that adds element with the total content more than the 5.0 quality % and have good mechanical property such as intensity and hardness, high corrosion resistance, flame retardant resistance, thermotolerance etc., but depend on the type of adding element.
The specific examples that adds element comprises at least a element that is selected from as lower: Al, Zn, Mn, Si, Be, Ca, Sr, Y, Cu, Ag, Sn, Li, Zr, Ce, Ni, Au and rare earth element (except Y and the Ce).The example of impurity is Fe.
The Mg-Al series alloy that contains Al has high corrosion resistance and also has good mechanical property such as intensity and hardness.Therefore, according to the embodiment of magnesium alloy materials of the present invention, magnesium alloy with more than the 5.0 quality % and the content below the 12 quality % contain Al as adding element.Along with Al content increases, above-mentioned effect is tended to strengthen.Al content is preferably more than the 7 quality % and more preferably more than the 7.3 quality %.Be limited to 12 quality % and preferred 11 quality % on the Al content, because when Al content surpasses 12 quality %, plastic working decline.Especially, the magnesium alloy that contains the Al of 8.3 quality %~9.5 quality % provides high intensity and erosion resistance.The total content of the element except Al is more than the 0.01 quality % and below the 10 quality % and more than the preferred 0.1 quality % and below the 5 quality %.
The specific examples of Mg-Al series alloy comprises AZ series alloy (the Mg-Al-Zn series alloy in the ASTM standard, Zn:0.2 quality %~1.5 quality % such as AZ31 alloy, AZ61 alloy and AZ91 alloy), AM series alloy (Mg-Al-Mn series alloy, Mn:0.15 quality %~0.5 quality %), AS series alloy (Mg-Al-Si series alloy, Si:0.01 quality %~20 quality %), Mg-Al-RE (rare earth element) series alloy, AX series alloy (Mg-Al-Ca series alloy, Ca:0.2 quality %~6.0 quality %) and AJ series alloy (Mg-Al-Sr series alloy, Sr:0.2 quality %~7.0 quality %).The example of alloy that contains the Al of 8.3 quality %~9.5 quality % comprises Mg-Al-Zn series alloy such as the AZ91 alloy of the Zn that also contains 0.5 quality %~1.5 quality %.
Take more than the 0.001 quality % and more than the preferred 0.1 quality % and the total content below the 5 quality % contain at least a element that is selected from Y, Ce, Ca, Si, Sn and the rare earth element (except Y and the Ce) and residuum as the magnesium alloy of Mg and impurity, high heat resistance and flame retardant resistance are provided.When containing rare earth element, its total content is preferably more than the 0.1 quality %.Especially, when containing Y, its content is preferably more than the 0.5 quality %.
The invention advantageous effects
Be the thick magnesium alloy materials with high corrosion resistance and anti-surface irregularity according to magnesium alloy materials of the present invention.In the method for manufacturing magnesium alloy materials according to the present invention, can make the thick magnesium alloy materials with high corrosion resistance and anti-surface irregularity.
Embodiment
Now the present invention is further elaborated.
[magnesium alloy materials]
(composition)
Magnesium alloy materials of the present invention consists of by containing Mg more than the 50 quality % and the magnesium alloy of typical above-mentioned interpolation element.
(form)
Plate-like portion in the magnesium alloy materials of the present invention refers to have the basic uniform part in interval (distance) between a pair of surface that is parallel to each other and two surfaces,, has the part of uniform thickness that is.Magnesium alloy materials of the present invention has plate-like portion in its at least a portion.When satisfying this condition, magnesium alloy materials can have by such as the processing of cutting processing so that the thickness of the part form different with the thickness part of other parts, for example, the form that comprises the reeded form of form, tool that for example joins the projection on it to and have the through hole that connects top and bottom.
Representative configuration with magnesium alloy materials of the present invention of described plate-like portion is the form (magnesium alloy plate) that magnesium alloy materials integral body has plate-like shape.The shape of magnesium alloy plate (planeform) can be rectangle, circle etc.Magnesium alloy plate can or have predetermined length and the form of the short slab of shape for the coiled material form that obtains by continuous long slab is reeled.Magnesium alloy plate can have various forms according to manufacture method.The example of form comprises milled sheet, the thermal treatment plate and the rectification plate that obtain respectively by following thermal treatment and rectification are implemented in milled sheet, and abrasive sheet and coated panel by milled sheet, thermal treatment plate or rectification plate being implemented grind and be coated with and obtain respectively.
Magnesium alloy materials of the present invention can also be implemented plastic working (secondary processing) such as press process to magnesium alloy plate for passing through, for example crooked and stretch and the molding that obtains, perhaps have by magnesium alloy plate partly being implemented the part work material (at least a portion in molding or the part work material is described plate-like portion) of the plastic working section that plastic working obtains herein.Described molding can for casing or framework with U-shaped cross-section or comprise discoideus top and cylindrical lateral wall section cover cylindrical body, described casing or framework comprise top (bottom) and the peripheral vertically extending side wall portion of (bottom) from the top.At least described top is corresponding with plate-like portion.The form of magnesium alloy materials can be according to the selection that should be used for of expectation.
(thickness)
In magnesium alloy materials of the present invention, described plate-like portion has the above thickness of 1.5mm.Can be according to selecting any thickness the thickness of expectation application more than 1.5mm.In order to improve the thickness of described plate-like portion, also need to improve the thickness that serves as raw-material cast material herein.If improve the thickness of cast material, then rolling property descends owing to defects etc.Therefore, in order to make thick milled sheet (a kind of form of magnesium alloy materials of the present invention) with high productivity, the thickness of described plate-like portion is preferably below the following and especially preferred 5mm of 10mm.
When magnesium alloy materials of the present invention is described molding or described part work material, during plastic working in the part (for example plate-like portion) of experience than small deformation, substantially kept serving as structure and the mechanical property of the raw-material described magnesium alloy plate of plastic working.
(structure)
<orientation 〉
In magnesium alloy materials of the present invention, the surf zone in the above-mentioned at least plate-like portion is made of the structure with basal plane texture and interior region is made of the structure with little basal plane degree of orientation.Surf zone under being exposed to outside atmosphere by (002) face wherein take by force to structure when consisting of, realized as mentioned above higher erosion resistance.Along with the poor increase of the degree of orientation between surf zone and the interior region, expection can improve erosion resistance, surface hardness and anti-surface irregularity.Yet if the poor excessive increase of degree of orientation, becoming is difficult to evenly implement plastic working such as press process.Therefore, the ratio O at above-mentioned basal plane peak F/ O CPreferably satisfy O F/ O C≤ 1.2.
<average grain size 〉
In the representative configuration of magnesium alloy materials of the present invention, the grain-size in the interior region is greater than the grain-size in the surf zone.In this form, as mentioned above, the surf zone that interior region has high heat resistance and has a relatively little grain-size has high corrosion resistance and hardness.Especially, when surf zone is made of relatively fine structure, realizes high rigidity and realize thus high abrasion resistance.This is so that be difficult to form scratch and good Surface Texture is provided.Therefore, expect that magnesium alloy materials of the present invention can be suitably be used for requiring the structured material of weather resistance etc.Along with the poor increase of the average grain size between surf zone and the interior region, expection can improve erosion resistance, anti-surface irregularity and surface hardness.Yet if the poor excessive increase of average grain size, becoming is difficult to evenly implement plastic working such as press process.Therefore, the ratio D of above-mentioned average grain size C/ D FPreferably satisfy D C/ D F≤ 2.0.
Have by implementing rolling manufacturing as mentioned above in the situation of thick plate-like magnesium alloy materials of the above thickness of 1.5mm, the whole zone on thickness direction realizes that even and fine particle diameter is restricted.In magnesium alloy materials of the present invention, the average grain size in surf zone and the interior region is more than the 3.5 μ m.Yet, owing to the plastic working sexual orientation improves in the decline with grain-size, so the average grain size of the surf zone of described plate-like portion and interior region all is preferably below the 20 μ m and below the especially preferred 10 μ m.Average grain size changes with the draft in the rolling step and raw-material Heating temperature, and tends to descend with draft increase and Heating temperature.
(mechanical property)
Magnesium alloy materials of the present invention is compared with cast material such as die casting material has better mechanical property such as intensity, hardness and toughness, because carried out rolling to magnesium alloy materials.For example, as mentioned above, the Vickers' hardness in the surf zone is higher than the Vickers' hardness in the interior region.Along with the poor increase of the Vickers' hardness between surf zone and the interior region, surface hardness increases relatively.Yet if the poor excessive increase of Vickers' hardness (surface hardness excessively increases), press processability descends.Therefore, the ratio H of Vickers' hardness (Hv) C/ H FPreferred satisfied 0.7≤H C/ H FThe absolute value of Vickers' hardness tends to increase with the increase of adding constituent content, but depends on raw-material rolling condition such as draft and raw-material Heating temperature.When magnesium alloy materials of the present invention was plastic working material (molding) or part work material, hardness was tended to further improve because of work hardening.
(other structures)
By at least a portion on the surface of magnesium alloy materials of the present invention is carried out anti-corrosive treatment such as chemical conversion processing or anodic oxidation treatment to form corrosion-resistant coating, realized higher erosion resistance.In addition, be coated with to form coating by at least a portion to the surface of magnesium alloy materials of the present invention, improved design and commercial value.
[manufacture method]
Now each step of the above-mentioned manufacture method of the present invention is further elaborated.
(preparation step)
<casting 〉
In manufacture method of the present invention, continuous cast materials is used as parent material.In Continuous casting process, can implement rapid solidification.Therefore, even when to comprise in a large number when adding element, still can reduce the formation of segregation and oxide compound, this can the inhibition meeting as the generation greater than the thick crystallization precipitate of 10 μ m sizes of having of crackle starting point.Thus, can make the cast material with good plastic working such as rolling property.In Continuous casting process, can also make in a continuous manner long cast material.Long material by the Continuous casting process manufacturing can be used as the rolling starting material of using.When using long starting material, can make long rolling stock.The example of Continuous casting process comprises double roller therapy, two-tape method and belt wheel method.Double roller therapy or two-tape method are applicable to make tabular cast material, and double roller therapy is particularly suitable.The preferred continuous cast materials of making by the castmethod of describing in the patent documentation 1 that uses.Can suitably select in the mode of the rolling stock (milled sheet) that obtains expecting thickness, width and the length of cast material.The thickness of cast material is preferably below the following and especially preferred 5mm of 10mm, because be easy to cause segregation in blocked up cast material.When the continuous cast materials that will obtain is used as long material, with drum this continuous cast materials is reeled, because be easy to continuous cast materials is transferred to next step.When being heated to about 100 ℃~about 200 ℃ in the coiling beginning with cast material, cast material being reeled, still be easy to bending even contain a large amount of interpolation elements and the alloy that is easy to crack such as AZ91 alloy.Even in the little situation of winding diameter, still can in situation about not cracking, reel to cast material.The continuous cast materials that obtains can be cut into have desired length sheet material to obtain the rolling starting material of using.In this case, obtain having the rolling stock (milled sheet) of desired length.
<solution processing 〉
By before cast material is rolled, implementing the solution processing, can make the composition homogenize of cast material and can will improve toughness such as the abundant solid solution of the element of Al.Implementing more than 1 hour the solution processing and the hold-time below 40 hours more than 380 ℃ and under the Heating temperature below 420 ℃ more than 350 ℃ and especially.In the situation of Mg-Al series alloy, the hold-time preferably prolongs with the increase of Al content.The cooling step from described Heating temperature after the described hold-time, accelerate cooling such as water cooling or air blast cooling raising rate of cooling (preferred more than 50 ℃/minute) by using, can suppress separating out of thick precipitate.
<rolling
Described cast material or the material that carried out the solution processing are carried out multi-pass rolling.Preferably by in the warm-rolling system that is heated to starting material (cast material, the material that has carried out the solution processing or the work material that is being rolled) more than 150 ℃ and implements in below 400 ℃ or by hot rolling, implement at least one passage.By starting material are heated to said temperature, even every time draft improves, still be difficult for cracking during rolling etc.Along with described temperature raises, the formation of crackle reduces.By being below 400 ℃ with described Temperature Setting, can suppress the thermal degradation when of the deteriorated and reduction roll that the seizure (baked is paid I) by the starting material surface causes.Therefore, described Heating temperature is preferably below 350 ℃, and is more preferably below 300 ℃, especially preferred more than 150 ℃ and below 280 ℃.Except starting material, also can heat reduction roll.The Heating temperature of reduction roll is for example 100 ℃~250 ℃.
In manufacture method of the present invention, the draft of each passage is set as below 25%.By implementing multi-pass rolling with relatively low draft, plastic working is given on raw-material surface especially in a concentrated manner.The draft of each passage can suitably be selected in the scope below 25%.Yet, if draft is excessively low, being used for realizing that the road number of times of expectation thickness increases, this reduces productivity.Thus, the draft of each passage is preferably more than 10%.
Can change for each passage such as the temperature of raw-material Heating temperature, reduction roll and the condition of draft.Therefore, the draft of each passage can be identical or different.Can between passage, implement intermediate heat treatment.By implementing intermediate heat treatment, can remove or reduce so that after intermediate heat treatment, be easy to and be rolled before intermediate heat treatment, introducing strain in the starting material and unrelieved stress.Can be with 0.5~3 hour hold-time of intermediate heat treatment enforcement under the Heating temperature of 150 ℃~350 ℃ (preferred below 300 ℃, more preferably 250 ℃~280 ℃).After rolling, can implement under these conditions final thermal treatment.In addition, with lubricator can be easy to implement rolling by suitably making, because can reduce the friction opposing during rolling and can prevent raw-material seizure.
In addition, can prune to prevent the crack propagation that may exist in edge during rolling to the edge of the cast material before rolling.Can during rolling or after rolling, implement this pruning with suitable Adjustment width.
<other processing 〉
<<grind〉〉
After rolling, can implement to grind.In order to remove or to reduce the lubricant that uses during rolling and be present in the lip-deep scratch of rolling stock and oxide film and implement to grind.Preferred utilization is ground and is cut band enforcement grinding, even because long material also can easily grind it in a continuous manner.Preferably implement to grind to prevent dispersing of powder by wet process.
<<correct〉〉
After rolling or after grinding, can implement to correct.Implement to correct in order to improve Flatness and accurate enforcement plastic working such as press process.When correcting, can suitably use the gaugger that comprises a plurality of rollers of arranging with interlace mode.Can when starting material being heated to for example 100 ℃~300 ℃ and especially 150 ℃~280 ℃, implement to correct (temperature correction just).
<<plastic working〉〉
When magnesium alloy materials of the present invention being processed as molding or having the part work material of plastic working section, the method that can be manufactured by the following is made this molding or part work material, and described manufacture method comprises the plastic working step of at least a portion of the starting material that carried out the rolling step (the rolling material, abrasive substance or rectification material) being implemented plastic working such as press process.Preferably in 200 ℃~300 ℃ temperature range, implement plastic working to improve raw-material plastic working.Can after plastic working, implement thermal treatment to remove strain and the unrelieved stress of during plastic working, introducing and to improve mechanical property.Under 100 ℃~300 ℃ Heating temperature, thermal treatment is implemented about 5~about 60 minutes heat-up time.
<<surface treatment〉〉
When magnesium alloy materials of the present invention comprises above-mentioned corrosion-resistant coating or coating, the method that can be manufactured by the following is implemented to make, and described manufacture method comprises the raw-material at least a portion of having carried out rolling step or carried out raw-material at least a portion enforcement anti-corrosive treatment of plastic working step or the surface treatment step of coating.In addition, can implement to be selected from least a in hair polishing, diamond cutting, sandblasting, corrosion and the circumgyration incision to raw-material at least a portion.Implement this surface treatment to improve erosion resistance and mechanical protection function and to improve design, metal-like and commercial value.
Based on test example the specific embodiment of the present invention is further specified now.
[test example]
Under various conditions to being rolled to make the magnesium alloy plate with the above thickness of 1.5mm by having the starting material that the following magnesium alloy that forms consists of.Orientation, grain-size and Vickers' hardness to magnesium alloy plate are measured.
In this test, made by forming the magnesium alloy plate that the magnesium alloy (Mg-9.0 quality %A1-0.6 quality %Zn) of working as with the AZ91 alloy phase consists of and forming magnesium alloy plate with magnesium alloy (the Mg-3.1 quality %Al-0.7 quality %Zn) formation that the AZ31 alloy phase is worked as.
Made long cast sheet (thickness 4.5mm (4.50mm~4.51mm) * width 320mm) by the twin-roll continuous casting method by having the above-mentioned above-mentioned magnesium alloy that forms.Long cast sheet is reeled to make the casting coiled material temporarily.Under 400 ℃ with each casting coiled material solution processing 24 hours.Under the rolling condition shown in the Table I, to carrying out multi-pass rolling by the solid solution coiled material that has carried out the solution processing being carried out the starting material that uncoiling obtains, have 2.0mm (2.00mm~2.01mm) or the rolling stock of 1.5mm thickness (magnesium alloy plate) with manufacturing.Implement each passage (raw-material Heating temperature: 250 ℃~280 ℃, the temperature of reduction roll: 100 ℃~250 ℃) by warm-rolling system.The thickness of the thickness of the thickness of cast material, the work material that is being rolled and the magnesium alloy plate that obtains is defined as on the width of tested template central part and on width apart from the mean value of the thickness of 3 of the totals of two points of the position of edge 50mm.
[Table I]
[orientation]
By X-ray diffraction each magnesium alloy plate that obtains is analyzed to determine the basal plane peak ratio O in the surf zone FTo the basal plane peak ratio O in the interior region CRatio O F/ O CTable II has shown the result.Implement X-ray diffraction, the basal plane peak ratio O in the effects on surface zone by the surface to magnesium alloy plate FMeasure.By will be in 1/4 zone (surf zone) that thickness direction has magnesium alloy plate thickness from the surface of magnesium alloy plate chemistry remove to expose inner and then exposing surface implemented X-ray diffraction, to the basal plane peak ratio O in the interior region CMeasure.The peak intensity of (002) face, (100) face, (101) face, (102) face, (110) face and (103) face in each zone is measured to determine ratio O F/ O C
Basal plane peak ratio O F: I F(002)/{ I F(100)+I F(002)+I F(101)+I F(102)+I F(110)+I F(103) }
Basal plane peak ratio O C: I C(002)/{ I C(100)+I C(002)+I C(101)+I C(102)+I C(110)+I C(103) }
[average grain size]
According to the photomicrography of the steel-apparent grain fineness number " measure (Steels-micrographic determination of the apparent grain size) JIS G0551 (2005) " interior region and the average grain size in the surf zone (μ m) of each magnesium alloy plate of obtaining are measured.Intercept each magnesium alloy plate the cross section on the thickness direction (cross section and vertical section) and utilize opticmicroscope (400 times) each cross section is observed with the cross section of determining surf zone (in the zone that from the surface, has 1/4 thickness on the thickness direction) and interior region (remaining area that obtains by removing surf zone) three visuals field (sum in the visual field in each zone: 6) separately average grain size.Table II has shown in the surf zone altogether mean value (the D of the average grain size in six visuals field F) and interior region in the mean value (D of the average grain size in six visuals field altogether C).Also determined the average grain size D in the interior region CAverage grain size D in the effects on surface zone FRatio D C/ D FTable II has shown the result.
[Vickers' hardness]
The interior region of each magnesium alloy plate of obtaining and the Vickers' hardness (Hv) of surf zone are measured.In the situation as the measurement of average grain size, intercept the cross section (cross section and vertical section) of each magnesium alloy plate on thickness direction.By the Vickers' hardness H in the effects on surface zone on each cross section that pressure head is pressed against surf zone FMeasure.By on each cross section that pressure head is pressed against interior region to the Vickers' hardness H in the interior region CMeasure.Table II has shown the mean value (H of Vickers' hardness in the cross section of surf zone F) and the cross section of interior region in the mean value (H of Vickers' hardness C).Also determined the Vickers' hardness H in the interior region CVickers' hardness H in the effects on surface zone FRatio H C/ H FTable II has shown the result.
[corrosion test]
Erosion resistance to each magnesium alloy plate of obtaining is measured.Prepared test film (thickness is identical with the thickness of the magnesium alloy plate that obtains) according to JIS Z2371 (2000).Implement salt-fog test and continue 96 hours with the corrosion weight loss (mg/cm after the experiment with measuring 2).Table II has shown the result.
Can be clear according to Table I and II, by with every time draft below 25% continuous cast materials being carried out multi-pass rolling, a kind of thick magnesium alloy plate (magnesium alloy materials) is provided, its have the above thickness of 1.5mm and wherein on thickness direction the structure in the interior region (basal plane peak ratio) mutual different with structure (basal plane peak ratio) in the surf zone.In this magnesium alloy plate, the mechanical property in the interior region is different from mechanical property in the surf zone.
When each magnesium alloy plate that obtains is carried out press process (Heating temperature of magnesium alloy plate: 250 ℃~270 ℃), all samples have all successfully carried out press process.In the measurement of the structure of the flat in each press process material, the structure of the magnesium alloy plate before the structure of flat and the press process is basic identical, and the magnesium alloy plate before basal plane peak ratio and average grain size and the press process is basic identical.In addition, the surface roughness Ra in the curved part of press process material is measured.Table II has shown the result, it is so that can be clear, the sample that between surf zone and interior region, has different structure, particularly, specimen coding B, C, E, F, H, I, K and the L that is made of the little structure of particle diameter in the surf zone wherein has the little surface roughness Ra below about 0.5 μ m and has thus smooth-flat-surface.
Confirmed according to above-mentioned test-results, have thickness and be the above thick plate-like section of 1.5mm and wherein the structure of plate-like portion change and magnesium alloy materials with specific orientation has high anti-surface irregularity at thickness direction.Confirmed that also when magnesium alloy materials had the surf zone that is made of relatively fine structure, magnesium alloy materials had high corrosion resistance.
Above-mentioned embodiment can suitably change and be not limited to above-mentioned structure under the condition that does not deviate from the scope of the invention.For example, draft and the road number of times of each passage can suitably change in the thickness of the composition of magnesium alloy, magnesium alloy materials and shape and the rolling step.
Industrial applicability
Magnesium alloy materials of the present invention can be suitably for the member in the various fields that need erosion resistance and wearability such as the parts of trolley part, rail vehicle parts, aircraft components, bicycle assembly parts and Electrical and Electronic device; Described member constituent material; And their bag and starting material.Method according to manufacturing magnesium alloy materials of the present invention can be suitably for the manufacture of above-mentioned magnesium alloy materials of the present invention.

Claims (5)

1. magnesium alloy materials, it is made of magnesium alloy and has a plate-like portion,
Wherein said plate-like portion has the above thickness of 1.5mm, and
Described plate-like portion satisfies following orientation,
[orientation]
When 1/4 the zone definitions that will be from the surface of described plate-like portion has described plate-like portion thickness at thickness direction is surf zone and remaining area is defined as interior region,
The intensity at the X-ray diffraction peak of (002) face, (100) face, (101) face, (102) face, (110) face and (103) face in the described surf zone is defined as respectively I F(002), I F(100), I F(101), I F(102), I F(110) and I F(103),
The intensity at the X-ray diffraction peak of (002) face, (100) face, (101) face, (102) face, (110) face and (103) face in the described interior region is defined as respectively I C(002), I C(100), I C(101), I C(102), I C(110) and I C(103),
Degree of orientation with (002) described in described surf zone face: I F(002)/{ I F(100)+I F(002)+I F(101)+I F(102)+I F(110)+I F(103) } be defined as basal plane peak ratio O F, and
Degree of orientation with (002) described in described interior region face: I C(002)/{ I C(100)+I C(002)+I C(101)+I C(102)+I C(110)+I C(103) } be defined as basal plane peak ratio O CThe time,
Basal plane peak ratio O in the described surf zone FTo the basal plane peak ratio O in the described interior region CRatio O F/ O CSatisfy 1.05<O F/ O C
2. magnesium alloy materials according to claim 1, wherein, when the average grain size in the described surf zone is defined as D FAnd the average grain size in the described interior region is defined as D CThe time, the average grain size D in the described interior region CTo the average grain size D in the described surf zone FRatio D C/ D FSatisfy 1.5<D C/ D F
3. magnesium alloy materials according to claim 1 and 2, wherein, when the Vickers' hardness in the described surf zone (Hv) is defined as H FAnd the Vickers' hardness in the described interior region (Hv) is defined as H CThe time, the Vickers' hardness H in the described interior region CTo the Vickers' hardness H in the described surf zone FRatio H C/ H FSatisfy H C/ H F<0.85.
4. each described magnesium alloy materials according to claim 1~3, wherein said magnesium alloy with more than the 5.0 quality % and the content below the 12 quality % contain Al as adding element.
5. one kind by being rolled the method for making magnesium alloy materials to the starting material that are made of magnesium alloy, and described method comprises:
Preparation casts the preparation step of the sheet stock material that obtains continuously to the magnesium alloy of melting by the twin roller casting method; With
Described starting material carried out multi-pass rolling and make the rolling step of the tabular magnesium alloy materials with the above thickness of 1.5mm,
The draft of wherein said each passage is below 25%.
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