CN103380223B - Magnesium alloy materials and manufacture method thereof - Google Patents

Magnesium alloy materials and manufacture method thereof Download PDF

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Publication number
CN103380223B
CN103380223B CN201280009023.8A CN201280009023A CN103380223B CN 103380223 B CN103380223 B CN 103380223B CN 201280009023 A CN201280009023 A CN 201280009023A CN 103380223 B CN103380223 B CN 103380223B
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Prior art keywords
magnesium alloy
face
zone
plate
alloy materials
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CN103380223A (en
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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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    • 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

The invention provides a kind of method that there is the thick magnesium alloy materials of highly corrosion resistant and resistance to rough surface and manufacture described magnesium alloy materials. For example, having in the magnesium that thickness is plate-like portion more than 1.5mm (Mg) alloy material (magnesium alloy plate), in the time by 1/4 the zone definitions that there is described plate-like portion thickness at thickness direction from the surface of described plate-like portion being surf zone and remaining area be defined as to interior zone, the basal plane peak ratio O in described surf zoneFTo the basal plane peak ratio O in described interior zoneCThe ratio O of (degree of orientation of (002) face)F/OCMeet 1.05<OF/OC. Described Mg alloy material is by wherein compared with the inside of described plate-like portion, in the surface of described plate-like portion, as (002) face of the basal plane of Mg alloy crystal take by force to texture form. Because the crystallite dimension in described surf zone is less than the crystallite dimension in described interior zone, so realized highly corrosion resistant. In addition, realized high resistance to rough surface and obtained having the formed body of excellent surface texture by implementing press process thus. By with every time, the reduction ratio below 25%, to twin-roll continuous casting material enforcement multi-pass rolling, obtains tabular Mg alloy material.

Description

Magnesium alloy materials and manufacture method thereof
Technical field
The present invention relates to a kind of method of magnesium alloy materials and the described magnesium alloy materials of manufacture, described inMagnesium alloy materials is applicable to various members if conveying machinery is as the portion of automobile, rolling stock and aircraftPart, the parts of bicycle, the housing of Electrical and Electronic device and other structural elements, andAlso be applicable to the constituent material of described member. Especially, the present invention relates to there is highly corrosion resistantThick magnesium alloy materials with resistance to rough surface.
Background technology
As various members such as mobile electrical and electronic installation as mobile phone and notebook computerHousing, automobile component as the portion of wheel cap and gearshift plectrum, rolling stock parts and bicyclePart, as the constituent material of vehicle frame, enters the lightweight magnesium alloy with high specific strength and specific rigidityGo research. The member being made up of magnesium alloy is mainly by passing through die casting method or the thixotroping method of formingThe founding materials (the AZ91 alloy of American Society for Testing and Materials (ASTM) standard) of manufacturing forms.In recent years, used by by wrought magnesium alloy as the AZ31 alloy structure of ASTM standardThe plate becoming carries out press process and the press process material that obtains. Patent documentation 1 discloses, logicalCross the manufacture of twin roller casting method by the continuous cast materials forming such as the magnesium alloy of AZ91 alloy, andTo carrying out press process by continuous cast materials being rolled to the milled sheet obtaining.
Prior art document
Patent documentation
Patent documentation 1: No. 2006/003899th, International Publication
Summary of the invention
Technical problem
Be conceived to the lightweight of magnesium alloy, as for plastic working material as press process materialRaw material, the plate that has been the relative thin below 1mm to thickness is studied. But, withThe expansion of magnesium alloy purposes scope, required not only to develop above-mentioned thin plate, and developedEye, in the slab of specific strength and specific rigidity, particularly, has the slab of the above thickness of 1.5mm.This thick magnesium alloy plate, manufacture the method for described thick magnesium alloy plate and use described thick magnesium alloyThe plastic working material of plate manufacture is not yet well studied as press process material.
By using die casting method or the thixotroping method of forming to obtain thick magnesium alloy plate. But,Founding materials, as in die casting material, is easy to form internal flaw as hole, and forms in additionBe easy to become inhomogeneous with structure. For example, add the concentrated and crystal grain of elemental composition local height withMachine orientation. Therefore, as compared with rolling stock, founding materials is cast as pressing mold with plastic working materialThe corrosion resistance of producing material material is low. In addition, founding materials is if die casting material is because it is inner scarceFall into and plastic working is poor and be not suitable as thus plastic working raw material.
Therefore, the object of the present invention is to provide one to there is highly corrosion resistant and resistance to rough surfaceThe thick magnesium alloy materials of property and the thick magnesium alloy materials that has carried out plastic working. Of the present invention anotherAn object is that the thick magnesium that provides a kind of manufacture to have highly corrosion resistant and resistance to rough surface closesThe method of gold copper-base alloy.
The means of dealing with problems
Compare with thixotroping moulding material with die casting material, even if its composition is identical, carried outPlastic working (time processing) as the magnesium alloy materials of rolling in mechanical performance as intensity, hardness and toughProperty, corrosion resistance and plastic working aspect are still more excellent. This be because, at this magnesium alloyIn material, during casting, the formation of defect reduces and makes crystal finer. By to carry outThe magnesium alloy materials of time processing is implemented plastic working (secondary operations) and is obtained as press processMagnesium alloy materials is also excellent aspect mechanical performance and corrosion resistance. Especially, when will by connectThe continuous cast materials that continuous casting is manufactured as twin roller casting method is used as the former material of time processing materialWhen material, continuous cast materials is excellence aspect plastic working because with die casting material phaseRatio, the generation of segregation or thick crystallization precipitate reduces. Therefore, the present inventorThrough by under various conditions to continuous cast materials be rolled manufactured have 1.5mm withThe thick magnesium alloy plate of upper thickness. As a result, the inventor finds the following fact. Under given conditionsThe magnesium alloy thickness of slab of manufacturing also has highly corrosion resistant. In addition, when implementing plastic working as compactingProcessing or when bending, gained plastic working material has a small amount of little concavo-convex in its surface,There is smooth surface (the glossiness beautiful surface of for example tool), this means this plastic working materialThere is high resistance to rough surface. The present invention is with the above-mentioned basis that is found to be.
Magnesium alloy materials of the present invention is made up of magnesium alloy and has a plate-like portion, described plate-like portion toolThere is thickness more than 1.5mm. Described plate-like portion meets following orientation,
[orientation]
When thering is described plate-like portion thickness at thickness direction from the surface of described plate-like portion1/4 zone definitions is surf zone and remaining area is defined as to interior zone,
By (002) face, (100) face, (101) face, (102) face, (110) face in described surf zone(103) intensity at the X-ray diffraction peak of face is defined as respectively IF(002)、IF(100)、IF(101)、IF(102)、IFAnd I (110)F(103),
By (002) face, (100) face, (101) face, (102) face, (110) face in described interior zone(103) intensity at the X-ray diffraction peak of face is defined as respectively IC(002)、IC(100)、IC(101)、IC(102)、ICAnd I (110)C(103),
Degree of orientation by (002) described in described surf zone face: IF(002)/{IF(100)+IF(002)+IF(101)+IF(102)+IF(110)+IF(103) } be defined as basal plane peak ratio OF, and
Degree of orientation by (002) described in described interior zone face: IC(002)/{IC(100)+IC(002)+IC(101)+IC(102)+IC(110)+IC(103) } be defined as basal plane peak ratio OCTime,
Basal plane peak ratio O in described surf zoneFTo the basal plane peak ratio in described interior zoneExample OCRatio OF/OCMeet 1.05 < OF/OC
Magnesium alloy materials of the present invention for example can be by following manufacture method manufacture of the present invention.Be by the raw material that formed by magnesium alloy according to the method for manufacture magnesium alloy materials of the present inventionBe rolled and manufacture the method for magnesium alloy materials, described method comprises following preparation process and rollsStep processed.
Preparation process: prepare by twin roller casting method, the magnesium alloy of melting is cast continuously andThe step of the sheet stock material obtaining;
Rolling step: described raw material are carried out to multi-pass rolling and more than manufacturing and having 1.5mmThe step of the tabular magnesium alloy materials of thickness.
In described rolling step, the reduction ratio of described each passage is below 25%.
Reduction ratio (%) is defined as to { (raw-material thickness t before rolling hereinbAfter-rollingRaw-material thickness taRaw-material thickness t before)/rollingb}×100。
Manufacturing method according to the invention, can as raw material by use continuous cast materialsAdvantageously implement the rolling of multi-pass, in described continuous cast materials, can become rising of crackle etc.The defect of point or crystallization precipitate, segregation exist on a small quantity or substantially do not exist. In addition, byWhen the relative reduction ratio that reduces each passage, implement multi-pass rolling, in rolling stockPortion compares, and is enough to the surface part of rolling stock to give the plastic working realizing by rolling.In other words, can make the table of rolling stock by repeating to implement rolling with relatively low reduction ratioFace structure and internal structure are mutually different. Therefore, manufacture method of the present invention provides a kind of by phaseMagnesium alloy materials (the allusion quotation that structure in different surf zones and the structure in interior zone form mutuallyType ground is milled sheet (a kind of form of magnesium alloy materials of the present invention)). More specifically, surface regionStructure in territory is that the basal plane of wherein magnesium alloy crystal is mainly fully to provide plasticity to add by rollingWork and texture that the mode parallel with rolling direction (direction that the raw material that are rolled move) is orientated(texture that the c-axis of magnesium alloy crystal is orientated in the mode vertical with rolling direction). In interior zoneStructure be more random structure in the orientation ratio surf zone of basal plane of wherein magnesium alloy crystal.
In the time that magnesium alloy materials of the present invention is above-mentioned specific milled sheet (, when magnesium of the present invention closesWhen gold copper-base alloy is all made up of plate-like portion), the structure in surf zone is to have knitting of specific orientationStructure, more specifically, as (002) face of the basal plane of magnesium alloy crystal take by force to texture, and inStructure in portion region is the structure that wherein (002) face is orientated more weakly compared with surf zone.(002) face take by force to texture refer to that being shown in plastic working fully applies by plasticity and add during as rollingA kind of index of the distortion that work causes. Owing to fully having implemented plastic working as rolling, so magnesiumThe crystallite dimension of alloy is oriented in decline, and this has improved the gross area of grain boundary. As a result, depositImpurity element the ratio of grain boundary is relatively declined and there is thus the basis of above-mentioned ad hoc structureThe magnesium alloy materials of invention has highly corrosion resistant. Especially, when being exposed under outside atmosphereWhen surf zone has than the finer structure of interior zone, obtain higher corrosion resistance. CauseThis, magnesium alloy materials of the present invention is thick and have a highly corrosion resistant. In addition, by as aboveDifferent structure between surf zone and interior zone forms magnesium alloy materials, thus, and magnesium alloyMaterial has different performances between surf zone and interior zone, and (for example mechanical performance is as firmlyDegree, intensity, resistance to impact and toughness, corrosion resistance and freedom from vibration). This by utilizingPoor performance, can expect magnesium alloy materials of the present invention for various members and as various structuresThe raw material of part. In addition, magnesium alloy materials of the present invention has good plastic working as pressedProcessability processed or bendability, because the little (texture of degree of orientation of basal plane ((002) face) in interior zoneMiddle orientation density degree is little). Thus, magnesium alloy materials can suitably carry out plastic working as compactingProcessing or bending raw material. Surf zone is made up of micro crystal structure. Therefore, even realExecute the plastic working such as press process, be still difficult for forming on raw-material surface large also concavo-convexThe plastic working material (a kind of form of magnesium alloy materials of the present invention) with smooth surface is provided. CauseThis, magnesium alloy materials of the present invention has high resistance to rough surface. Gained plastic working material alsoThere is good Surface Texture.
According to the embodiment of magnesium alloy materials of the present invention, flat when by described surf zoneAll crystallite dimension is defined as DFAnd the average grain size in described interior zone is defined as to DCTime, the average grain size D in described interior zoneCTo the average crystal grain in described surf zoneDimension DFRatio DC/DFMeet 1.5 < DC/DF
According to above-mentioned embodiment, the crystallite dimension in interior zone is greater than the crystalline substance in surf zoneParticle size. In other words, the crystallite dimension in surf zone is fully less than the crystal grain in interior zoneSize, this has improved the length of grain boundary as above and has realized thus highly corrosion resistant.According to above-mentioned embodiment, because surf zone is made up of micro crystal structure, so obtain goodGood plastic working and Gao Nai rough surface. In addition, due to the crystal grain chi in interior zoneThe very little crystallite dimension being greater than in surf zone, realizes high-fire resistance thus.
According to the embodiment of magnesium alloy materials of the present invention, when by the dimension in described surf zoneFamily name (Vickers) hardness (Hv) is defined as HFAnd the Vickers hardness in described interior zone is defined as HCTime, the Vickers hardness H in described interior zoneCTo the Vickers hardness in described surf zoneHFRatio HC/HFMeet HC/HF<0.85。
According to above-mentioned embodiment, the Vickers hardness in interior zone is lower than the dimension in surf zoneFamily name's hardness. In other words, the Vickers hardness in surf zone is fully higher than the Vickers in interior zoneHardness, realizes high abrasion resistance thus.
Magnesium alloy materials of the present invention can be by containing various interpolation elements (residue: Mg and assortedMatter) magnesium alloy form. Especially, contain the alloy that adds element with high concentration, particularly,Contain with total contents more than 5.0 quality % the magnesium alloy that adds element and there is good mechanical performanceAs intensity and hardness, highly corrosion resistant, anti-flammability, heat resistance etc., but depend on interpolation elementType.
The instantiation that adds element comprises at least one element being selected from as lower: Al, Zn,Mn, Si, Be, Ca, Sr, Y, Cu, Ag, Sn, Li, Zr, Ce, Ni, Au and rareEarth elements (except Y and Ce). The example of impurity is Fe.
The Mg-Al series alloy that contains Al has highly corrosion resistant and also has good mechanicalnessCan be as intensity and hardness. Therefore,, according to the embodiment of magnesium alloy materials of the present invention, magnesium closesGold content above using 5.0 quality % and below 12 quality % contains Al as adding element. WithAl content and increase, above-mentioned effect is tended to strengthen. Al content be preferably 7 quality % above andMore preferably more than 7.3 quality %. On Al content, be limited to 12 quality % and preferred 11 quality %,Because in the time that Al content exceedes 12 quality %, plastic working declines. Especially, contain 8.3The magnesium alloy of the Al of quality %~9.5 quality % provides high intensity and corrosion resistance. Except AlOutside the total content of element be that 0.01 quality % is above and 10 quality % are following and preferred 0.1 matterMore than amount % and below 5 quality %.
The instantiation of Mg-Al series alloy comprises the AZ series alloy in ASTM standard(Mg-Al-Zn series alloy, Zn:0.2 quality %~1.5 quality % is as AZ31 alloy, AZ61Alloy and AZ91 alloy), AM series alloy (Mg-Al-Mn series alloy, Mn:0.15 matterAmount %~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-CaSeries alloy, Ca:0.2 quality %~6.0 quality %) and AJ series alloy (Mg-Al-Sr systemRow alloy, Sr:0.2 quality %~7.0 quality %). Contain 8.3 quality %~9.5 quality %'sThe example of the alloy of Al comprises the Mg-Al-Zn of the Zn that also contains 0.5 quality %~1.5 quality %Series alloy is as AZ91 alloy.
Above and preferred 0.1 quality % above and always containing below 5 quality % with 0.001 quality %Amount contains and is selected from least one in Y, Ce, Ca, Si, Sn and rare earth element (except Y and Ce)Planting element and residue is the magnesium alloy of Mg and impurity, and high-fire resistance and anti-flammability are provided. WhenWhile containing rare earth element, more than its total content is preferably 0.1 quality %. Especially, when containing YTime, more than its content is preferably 0.5 quality %.
Invention advantageous effects
Be there is highly corrosion resistant and resistance to rough surface thick according to magnesium alloy materials of the present inventionMagnesium alloy materials. In the method for manufacture magnesium alloy materials according to the present invention, can manufacture toolThere is the thick magnesium alloy materials of highly corrosion resistant and resistance to rough surface.
Detailed description of the invention
Now the present invention is further elaborated.
[magnesium alloy materials]
(composition)
Magnesium alloy materials of the present invention is by the Mg and typical above-mentioned the adding that contain more than 50 quality %The magnesium alloy of added elements forms.
(form)
Plate-like portion in magnesium alloy materials of the present invention refer to have a pair of be parallel to each other surface andThe basic part uniformly in interval (distance) between 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. In the time meeting this condition,Magnesium alloy materials can have by make a part of thickness and other such as the processing of cutting processingThe local different form of thickness of part, for example, comprises the shape that for example joins the projection on it toState, the reeded form of tool and there is the form of the through hole that connects top and bottom.
The representative configuration with the magnesium alloy materials of the present invention of described plate-like portion is that magnesium alloy materials is wholeBody has the form (magnesium alloy plate) of plate-like shape. The shape (flat shape) of magnesium alloy plate can beRectangle, circle etc. Magnesium alloy plate can be for by the volume obtaining that continuous long slab is reeledMaterial form or there is predetermined length and the form of the short slab of shape. Magnesium alloy plate can be according to manufactureMethod and there are various forms. The example of form comprises milled sheet, under milled sheet is implementedHeat treatment plate and the rectification plate of stating heat treatment and rectification and obtain respectively, and by milled sheet,Heat treatment plate or rectification plate are implemented the abrasive sheet and the coated panel that grind and be coated with and obtain respectively.
Magnesium alloy materials of the present invention can also be implemented plastic working (two to magnesium alloy plate for passing throughInferior processing) as press process, for example bending and stretch and the formed body that obtains, or have and pass throughPart rapidoprint (this of the plastic working portion that the enforcement plastic working of magnesium alloy plate part is obtainedWen Zhong, at least a portion in formed body or part rapidoprint is described plate-like portion). Described one-tenthBody can be for to have casing or the framework of U-shaped cross-section or to comprise discoideus top and circleCylindrical sidewall portion cover cylindrical body, described casing or framework comprise top (bottom) and from topThe vertically extending side wall portion of periphery of (bottom). At least described top is corresponding with plate-like portion. Magnesium closesThe form of gold copper-base alloy can be according to the selection that should be used for of expecting.
(thickness)
In magnesium alloy materials of the present invention, described plate-like portion has thickness more than 1.5mm.Can the thickness of application more than 1.5mm, select any thickness according to expecting. Herein, forImprove the thickness of described plate-like portion, also need to improve the thickness that serves as raw-material founding materials.If improve the thickness of founding materials, rolling is because above-mentioned defect etc. declines. Therefore,In order to manufacture thick milled sheet (a kind of form of magnesium alloy materials of the present invention), described plate with high production rateThe thickness of shape portion is preferably below 10mm and especially preferably below 5mm.
In the time that magnesium alloy materials of the present invention is described formed body or described part rapidoprint,During plastic working, experience for example,, compared with in the part of small deformation (plate-like portion), has kept serving as moulding substantiallyStructure and the mechanical performance of the raw-material described magnesium alloy plate of property processing.
(structure)
<orientation>
In magnesium alloy materials of the present invention, the surf zone at least above-mentioned plate-like portion is by havingThe structure of basal plane texture forms and interior zone is made up of the structure with little basal plane degree of orientation.When be exposed to surf zone under outside atmosphere by (002) face wherein take by force to structure while forming,Realize as mentioned above higher corrosion resistance. Along with getting between surf zone and interior zoneTo the poor increase of degree, expection can improve corrosion resistance, case hardness and resistance to rough surface. SoAnd, if the poor excessive increase of degree of orientation becomes and is difficult to evenly implement plastic working as compactingProcessing. Therefore, the ratio O at above-mentioned basal plane peakF/OCPreferably meet OF/OC≤1.2。
<average grain size>
In the representative configuration of magnesium alloy materials of the present invention, the crystallite dimension in interior zone is largeCrystallite dimension in surf zone. In this form, as mentioned above, interior zone hasHigh-fire resistance and the surf zone with relatively little crystallite dimension have highly corrosion resistant and hardness.Especially, in the time that surf zone is made up of relatively fine structure, realize high rigidity real thusExisting high abrasion resistance. This makes to be difficult to form scratch and good Surface Texture is provided. Therefore,Expect that magnesium alloy materials of the present invention can be suitably for requiring structural material of durability etc. Along withThe poor increase of average grain size between surf zone and interior zone, expection can improve corrosion-resistantProperty, resistance to rough surface and case hardness. But, if the poor excessive increase of average grain size,Become and be difficult to evenly implement plastic working as press process. Therefore, above-mentioned average grain sizeRatio DC/DFPreferably meet DC/DF≤2.0。
Close at the thick plate-like magnesium by implementing rolling manufacture as mentioned above with the above thickness of 1.5mmIn the situation of gold copper-base alloy, the whole region on thickness direction is realized even and fine particle diameter and is subject toTo restriction. In magnesium alloy materials of the present invention, the average crystalline substance in surf zone and interior zoneParticle size is more than 3.5 μ m. But, because plastic working sexual orientation is under with crystallite dimensionFall and improve, so the average crystal grain chi of the surf zone of described plate-like portion and interior zoneThe very little 20 μ m that are preferably are below also especially preferably below 10 μ m. Average grain size walks with rollingReduction ratio in rapid and raw-material heating-up temperature and change, and tend to increase with reduction ratio andHeating-up temperature declines and declines.
(mechanical performance)
Magnesium alloy materials of the present invention has better compared with die casting material with founding materialsMechanical performance is as intensity, hardness and toughness, because magnesium alloy materials has been carried out to rolling. For example,As mentioned above, the Vickers hardness in surf zone is higher than the Vickers hardness in interior zone. Along withThe poor increase of Vickers hardness between surf zone and interior zone, case hardness increases relatively. SoAnd if the poor excessive increase of Vickers hardness (case hardness excessively increases), press processability declines.Therefore, the ratio H of Vickers hardness (Hv)C/HFPreferably meet 0.7≤HC/HF. Vickers hardness definitelyValue is tended to increase with the increase of adding constituent content, but depends on raw-material rolling conditionAs reduction ratio and raw-material heating-up temperature. When magnesium alloy materials of the present invention is plastic working materialWhen material (formed body) or part rapidoprint, hardness is tended to further improve because of work hardening.
(other structures)
By surperficial at least a portion of magnesium alloy materials of the present invention is carried out anti-corrosion treatment asChemical conversion processing or anodized, to form corrosion-resistant coating, have realized higher corrosion-resistantProperty. In addition, by surperficial at least a portion of magnesium alloy materials of the present invention is coated withForm coating, improved design and commercial value.
[manufacture method]
Now each step of the above-mentioned manufacture method of the present invention is further elaborated.
(preparation process)
<casting>
In manufacture method of the present invention, continuous cast materials is used as to parent material. ContinuouslyIn casting, can implement rapid solidification. Therefore, even when adding when element to comprise in a large number,Still can reduce the formation of segregation and oxide, this can inhibition meeting having as crackle starting pointBe greater than the generation of the thick crystallization precipitate of 10 μ m sizes. Thus, can manufacture and have wellPlastic working is as the founding materials of rolling. In continuous casting process, can also be with continuous sideThe long founding materials of formula manufacture. The long material of manufacturing by continuous casting process can be used as rollingRaw material. In the time using long raw material, can manufacture long rolling stock. Continuous casting processExample comprises double roller therapy, two-tape method and belt wheel method. Double roller therapy or two-tape method are applicable to manufacture tabularFounding materials, and double roller therapy is particularly suitable. Preferably use by describing in patent documentation 1Casting method manufacture continuous cast materials. Can be with the rolling stock (milled sheet) that obtains expectingMode suitably select thickness, width and the length of founding materials. The thickness of founding materials is preferredFor 10mm is below also especially preferably below 5mm, because be easy to make in blocked up founding materialsBecome segregation. When by the continuous cast materials obtaining when the long material, with drum to thisContinuous cast materials is reeled, because be easy to, continuous cast materials is transferred to next step.When the coiling beginning of founding materials is heated to approximately 100 DEG C~approximately 200 DEG C to castingWhen producing material material is reeled, though contain a large amount of interpolation elements and the alloy that is easy to crack asAZ91 alloy is still easy to bending. Even in the little situation of winding diameter, still can not produceIn the situation of crackle, founding materials is reeled. Can be by the continuous cast materials cutting obtainingThe sheet material that becomes to have desired length is to obtain rolling raw material. In this case, hadThe rolling stock (milled sheet) of desired length.
<solution processing>
By implemented solution processing before founding materials is rolled, can make to cast materialThe composition homogenize of material also can improve toughness by abundant the element such as Al solid solution. At 350 DEG CAbove and especially under the heating-up temperature more than 380 DEG C and below 420 DEG C, solutionization is processed and implemented1 hour above and 40 hours following retention time. In the situation of Mg-Al series alloy,Retention time preferably extends with the increase of Al content. After the described retention time, add from describedIn the cooling step that hot temperature degree rises, accelerate cooling as water cooling or the cooling raising of air blast by useCooldown rate (preferably more than 50 DEG C/min), can suppress separating out of thick precipitate.
<rolling>
Described founding materials or the material that carried out solution processing are carried out to multi-pass rolling. ExcellentGating is crossed raw material (founding materials, is being carried out to the material of solution processing or rollingThe rapidoprint of system) be heated to 150 DEG C of above and 400 DEG C of warm-rolling systems of implementing following time orBy hot rolling, implement at least one passage. By raw material are heated to said temperature,Every time reduction ratio is improved, during rolling, be still difficult for cracking etc. Along with described temperatureDegree raises, and the formation of crackle reduces. By being below 400 DEG C by described Temperature Setting, can press downThe heat of the deteriorated and reduction roll that system is caused by the seizure (baked is paid I) on raw material surface is deteriorated. Therefore,Described heating-up temperature is preferably below 350 DEG C, more preferably below 300 DEG C, and especially preferably 150 DEG CAbove and below 280 DEG C. Except raw material, also can heat reduction roll. Reduction rollHeating-up temperature be for example 100 DEG C~250 DEG C.
In manufacture method of the present invention, the reduction ratio of each passage is set as below 25%.Implement multi-pass rolling by the reduction ratio with relatively low, can be raw-material in a concentrated mannerPlastic working is given on surface especially. The reduction ratio of each passage can the scope below 25% inSuitably select. But, if reduction ratio is too low, expect for realizing that the road number of times of thickness increasesAdd, this reduces productivity ratio. Thus, the reduction ratio of each passage is preferably more than 10%.
Such as the temperature of raw-material heating-up temperature, reduction roll and the condition of reduction ratio for respectivelyIndividual passage can change. Therefore, the reduction ratio of each passage can be identical or different. CanTo implement intermediate heat-treatment between passage. By implementing intermediate heat-treatment, can be by centreIntroducing strain in raw material and residual stress before heat treatment removes or reduces and make in centreAfter heat treatment, be easy to be rolled. Can be at 150 DEG C~350 DEG C (preferably below 300 DEG C, morePreferably 250 DEG C~280 DEG C) heating-up temperature under intermediate heat-treatment is implemented to the guarantor of 0.5~3 hourHold the time. After rolling, can implement under these conditions final heat treatment. In addition pass through,Suitably making with lubricator can rolling easy to implement, because can reduce the friction opposing during rollingAnd can prevent raw-material seizure.
In addition, can prune to prevent in the rolling phase to the edge of the founding materials before rollingBetween the Crack Extension that may exist in edge. Can during rolling or after rolling, implement thisPlant and prune with suitable adjustment width.
<other processing>
<<grind>>
After rolling, can implement to grind. In order to remove or reduce the profit using during rollingLubrication prescription and be present in the lip-deep scratch of rolling stock and oxidation film and implement grind. PreferablyUtilization is ground and is cut band enforcement grinding, even because long material, also can be easily right in a continuous mannerIt grinds. Preferably implement to grind to prevent dispersing of powder by wet process.
<<correct>>
After rolling or after grinding, can implement to correct. In order to improve flatness accurateImplementing plastic working implements as press process to correct. In the time correcting, can suitably use and compriseThe gaugger of multiple rollers of arranging with interlace mode. Raw material for example can be heated toWhen 100 DEG C~300 DEG C and especially 150 DEG C~280 DEG C, implement to correct (temperature correction just).
<<plastic working>>
When magnesium alloy materials of the present invention being processed as to formed body or thering is the part of plastic working portionWhen rapidoprint, the method that can be manufactured by the following is manufactured this formed body or part rapidoprint,Described manufacture method comprises that raw material to having carried out the rolling step (the rolling material, grindMill material or correct material) at least a portion implement plastic working as the plastic working of press processStep. Preferably in the temperature range of 200 DEG C~300 DEG C, implement plastic working to improve raw materialPlastic working. Can after plastic working, implement heat treatment to remove during plastic workingStrain and the residual stress of introducing also improves mechanical performance. The heating-up temperature of 100 DEG C~300 DEG CThe lower heat time of heat treatment being implemented to approximately 5~approximately 60 minutes.
<<surface treatment>>
In the time that magnesium alloy materials of the present invention comprises above-mentioned corrosion-resistant coating or coating, can by asLower manufacture method is implemented to manufacture, and described manufacture method comprises the raw material to having carried out rolling stepAt least a portion or the raw-material at least a portion of having carried out plastic working step implement anticorrosionThe surface treatment step that erosion is processed or is coated with. In addition can implement raw-material at least a portion,Be selected from least one in hair polishing, diamond cut, blasting treatment, corrosion and circumgyration incisionKind. Implement this surface treatment with improve corrosion resistance and mechanical protection function and improve design,Metal-like and commercial value.
Based on test example, the specific embodiment of the present invention is further described now.
[test example]
Under various conditions to being rolled by thering are the raw material that the following magnesium alloy forming formsTo manufacture the magnesium alloy plate with the above thickness of 1.5mm. Orientation to magnesium alloy plate, crystal grain chiVery little and Vickers hardness is measured.
In this test, manufacture magnesium alloy (the Mg-9.0 matter of working as with AZ91 alloy phase by formingAmount %A1-0.6 quality %Zn) magnesium alloy plate that forms and composition and the AZ31 alloy phase magnesium alloy of working asThe magnesium alloy plate that (Mg-3.1 quality %Al-0.7 quality %Zn) forms.
Manufacture long casting by twin-roll continuous casting method by thering is the above-mentioned above-mentioned magnesium alloy formingPlate (thickness 4.5mm (4.50mm~4.51mm) × width 320mm). Long cast sheet is facedTime reel to manufacture casting coiled material. At 400 DEG C, each casting coiled material solutionization is processed 24 hours.Under the rolling condition shown in Table I to by the solid solution coiled material that has carried out solution processing is enteredRow uncoiling and the raw material that obtain carry out multi-pass rolling, there is 2.0mm to manufacture (2.00mm~2.01mm) or the rolling stock of 1.5mm thickness (magnesium alloy plate). Implement each road by warm-rolling systemInferior (raw-material heating-up temperature: 250 DEG C~280 DEG C, the temperature of reduction roll: 100 DEG C~250 DEG C).The thickness of the rapidoprint by the thickness of founding materials, being rolled and the magnesium obtaining closeThe thickness of gold plate is defined as central portion on the width of tested template and on widthApart 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, the each magnesium alloy plate analysis obtaining is determined in surf zoneBasal plane peak ratio OFTo the basal plane peak ratio O in interior zoneCRatio OF/OC. Table II is aobviousShow result. Implement X-ray diffraction by the surface to magnesium alloy plate, in effects on surface regionBasal plane peak ratio OFMeasure. By thering is 1/4 of magnesium alloy plate thickness on thickness directionRegion (surf zone) chemistry from the surface of magnesium alloy plate remove to expose inner and then rightExposing surface is implemented X-ray diffraction, to the basal plane peak ratio O in interior zoneCMeasure.To (002) face, (100) face, (101) face, (102) face, (110) face and (103) face in each regionPeak intensity measures to determine ratio OF/OC
Basal plane peak ratio OF:IF(002)/{IF(100)+IF(002)+IF(101)+IF(102)+IF(110)+IF(103)}
Basal plane peak ratio OC:IC(002)/{IC(100)+IC(002)+IC(101)+IC(102)+IC(110)+IC(103)}
[average grain size]
According to " (Steels-micrographic is measured in the microphotograph of steel-apparent grain sizeDeterminationoftheapparentgrainsize) JISG0551 (2005) " each to what obtain(μ m) measures average grain size in interior zone and the surf zone of magnesium alloy plate. CutGet the cross section (cross section and longitudinal section) of each magnesium alloy plate on thickness direction and utilize optical microphotographMirror (400 times) observes to determine that to each cross section surf zone is (on thickness direction from surfaceThere is the region of 1/4 thickness) and interior zone (remaining area obtaining by removing surf zone)Cross section in three visuals field (sum in the visual field in each region: 6) average grain size separately.Table II has shown in surf zone the mean value (D of the average grain size in six visuals field altogetherF)With the mean value (D of the average grain size in six visuals field altogether in interior zoneC). Also determineAverage grain size D in interior zoneCAverage grain size D in effects on surface regionFRatioDC/DF. Table II has shown result.
[Vickers hardness]
Interior zone to the each magnesium alloy plate obtaining and the Vickers hardness of surf zone (Hv) are carried outMeasure. In situation as the measurement of average grain size, intercept each magnesium alloy plate in thickness sideCross section (cross section and longitudinal section) upwards. By pressure head being pressed against on each cross section of surf zoneVickers hardness H in effects on surface regionFMeasure. By pressure head being pressed against to interior zoneOn each cross section to the Vickers hardness H in interior zoneCMeasure. Table II has shown surf zoneCross section in the mean value (H of Vickers hardnessF) and the cross section of interior zone in Vickers hardness averageValue (HC). Also determine the Vickers hardness H in interior zoneCVickers hardness in effects on surface regionHFRatio HC/HF. Table II has shown result.
[corrosion test]
Corrosion resistance to the each magnesium alloy plate obtaining is measured. According to JISZ2371 (2000)Prepare test film (thickness is identical with the thickness of the magnesium alloy plate obtaining). Implement salt spray test and holdContinuous 96 hours to measure the test corrosion loss in weight (mg/cm afterwards2). Table II has shown result.
Can be clear according to Table I and II, by with every time reduction ratio below 25% to continuous castingProducing material material carries out multi-pass rolling, and a kind of thick magnesium alloy plate (magnesium alloy materials) is provided, and it hasThickness more than 1.5mm and the wherein structure in interior zone (basal plane peak ratio) on thickness directionMutually different from the structure (basal plane peak ratio) in surf zone. In this magnesium alloy plate, insideMechanical performance in region is different from the mechanical performance in surf zone.
In the time that the each magnesium alloy plate obtaining is carried out to press process (heating-up temperature of magnesium alloy plate:250 DEG C~270 DEG C), all samples have all successfully carried out press process. At each press process materialIn the measurement of structure of flat in, the magnesium before the structure of flat and press processThe structure of alloy sheets is basic identical, and basal plane peak ratio and average grain size and press process itFront magnesium alloy plate is basic identical. In addition, to the surface in the sweep of press process materialRoughness Ra is measured. Table II has shown result, and it makes can be clear, at surf zoneAnd between interior zone, there is the sample of different structure, particularly, by surf zone whereinSpecimen coding B, C, E, F, H, I, K and L that the structure that particle diameter is little forms have approximately 0.5 μ mFollowing little surface roughness Ra also has smooth surface thus.
Confirmed according to above-mentioned result of the test, there is thickness and be more than 1.5mm thick plate-like portion andWherein the structure of plate-like portion changes and has the magnesium alloy material of specific orientation on thickness directionMaterial has high resistance to rough surface. Also confirm, when magnesium alloy materials has by relatively fineStructure form surf zone time, magnesium alloy materials has highly corrosion resistant.
Above-mentioned embodiment can under the condition that does not deviate from the scope of the invention, suitably change andBe not limited to above-mentioned structure. For example, the thickness of the composition of magnesium alloy, magnesium alloy materials and shape,And in rolling step, reduction ratio and the road number of times of each passage can suitably change.
Industrial applicability
Magnesium alloy materials of the present invention can be suitably for needing the each of corrosion resistance and mar proofMember in kind of field as automobile component, rolling stock parts, aircraft components, bicycle assembly parts,And the parts of Electrical and Electronic device; Described member constituent material; And they bag andRaw material. Can be suitably for the manufacture of this according to the method for manufacture magnesium alloy materials of the present inventionBright above-mentioned magnesium alloy materials.

Claims (4)

1. a magnesium alloy materials, it is made up of magnesium alloy and has a plate-like portion,
Wherein said plate-like portion has thickness more than 1.5mm, and
Described plate-like portion meets following orientation,
[orientation]
When thering is described plate-like portion thickness at thickness direction from the surface of described plate-like portion1/4 zone definitions is surf zone and remaining area is defined as to interior zone,
By (002) face, (100) face, (101) face, (102) face, (110) face in described surf zone(103) intensity at the X-ray diffraction peak of face is defined as respectively IF(002)、IF(100)、IF(101)、IF(102)、IFAnd I (110)F(103),
By (002) face, (100) face, (101) face, (102) face, (110) face in described interior zone(103) intensity at the X-ray diffraction peak of face is defined as respectively IC(002)、IC(100)、IC(101)、IC(102)、ICAnd I (110)C(103),
Degree of orientation by (002) described in described surf zone face: IF(002)/{IF(100)+IF(002)+IF(101)+IF(102)+IF(110)+IF(103) } be defined as basal plane peak ratio OF, and
Degree of orientation by (002) described in described interior zone face: IC(002)/{IC(100)+IC(002)+IC(101)+IC(102)+IC(110)+IC(103) } be defined as basal plane peak ratio OCTime,
Basal plane peak ratio O in described surf zoneFTo the basal plane peak ratio in described interior zoneExample OCRatio OF/OCMeet 1.05 < OF/OC
Wherein, when the average grain size in described surf zone is defined as to DFAnd by describedAverage grain size in portion region is defined as DCTime, the average crystal grain chi in described interior zoneVery little DCTo the average grain size D in described surf zoneFRatio DC/DFMeet 1.5 <DC/DF
2. magnesium alloy materials according to claim 1, wherein, when by described surf zoneIn Vickers hardness (Hv) be defined as HFAnd the Vickers hardness in described interior zone (Hv) is definedFor HCTime, the Vickers hardness H in described interior zoneCHard to the Vickers in described surf zoneDegree HFRatio HC/HFMeet HC/HF<0.85。
3. magnesium alloy materials according to claim 1 and 2, wherein said magnesium alloy is with 5.0Quality % content above and below 12 quality % contains Al as adding element.
4. one kind by being rolled and manufacturing claim the raw material that are made up of magnesium alloyThe method of the magnesium alloy materials in 1~3 described in any one, described method comprises:
Prepare, by twin roller casting method, the magnesium alloy of melting is cast continuously to obtain tabularRaw-material preparation process;
Before founding materials is rolled more than 350 DEG C and below 420 DEG C, add hot temperatureUnder degree, solutionization is processed and implemented more than 1 hour and the solution of 40 hours following retention timesTreatment step; With
Manufacture and have having carried out the material of described solution processing to carry out multi-pass rollingThe rolling step of the tabular magnesium alloy materials of the above thickness of 1.5mm,
The reduction ratio of wherein said each passage is below 25%, but does not comprise 25%,
Wherein in rolling step, by raw material be heated to 150 DEG C above and below 280 DEG C, andAnd reduction roll is heated to 100 DEG C~250 DEG C.
CN201280009023.8A 2011-02-24 2012-02-23 Magnesium alloy materials and manufacture method thereof Expired - Fee Related CN103380223B (en)

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