CN102950834A - Insert used in amorphous alloy product, amorphous alloy product, and manufacturing method thereof - Google Patents
Insert used in amorphous alloy product, amorphous alloy product, and manufacturing method thereof Download PDFInfo
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- CN102950834A CN102950834A CN 201110237851 CN201110237851A CN102950834A CN 102950834 A CN102950834 A CN 102950834A CN 201110237851 CN201110237851 CN 201110237851 CN 201110237851 A CN201110237851 A CN 201110237851A CN 102950834 A CN102950834 A CN 102950834A
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Abstract
The invention discloses an insert (1) used in an amorphous alloy product. The insert (1) comprises a first main body and a first engagement part integrally formed with the first main body. The first engagement part comprises a first engagement surface. The first engagement surface comprises a permeable layer comprising a plurality of cavities (11). Three dimensions of the cavities (11) in a three-dimensional space are 10-800mum. The invention also discloses an amorphous alloy product comprising the insert (1) and a manufacturing method of the amorphous alloy product. According to the invention, the first engagement surface of the amorphous alloy product is retreated, such that the permeable layer composed of the cavities with the preset dimensions is formed on the first engagement layer. Therefore, the engagement strength of the molding section and the insert in the amorphous alloy product can be improved.
Description
Technical field
The present invention relates to the forming materials field, particularly, relate to a kind of inserts and comprise the amorphous alloy product of this inserts, and the manufacture method of making this amorphous alloy product.
Background technology
Amorphous alloy material also is known as glassy metal, is the new material that 20 th century later develop rapidly.The main characteristics of amorphous alloy material are the arrangements that the atom of formation alloy is the topological disorder shape, do not have the defectives such as crystal boundary and stacking fault on the structure.Therefore, amorphous alloy material has physics, chemistry and the mechanical property that is different from common crystalline state metal material, such as high-yield strength, high rigidity, super-elasticity (high elastic limit), high abrasion resistance, highly corrosion resistant etc.In addition amorphous alloy material also have low melting point, good casting characteristics, low thermal coefficient of expansion, to the shape of casting mold and the characteristics such as manifolding on surface, can when as cast condition, obtain superior mechanical performance.Above-mentioned advantage so that non-crystaline amorphous metal having great application prospect aspect the consumable electronic product shell.For example, the phone housing that adopts amorphous alloy material to make can solve the problem of the defectives such as cut that easily occur on the shell of common metal material making.
But, because non-crystaline amorphous metal self makes the application of non-crystaline amorphous metal be subject to larger restriction.For example, because non-crystaline amorphous metal hardness is higher, when needs can increase technology difficulty when amorphous alloy product carries out machining or punching; For another example, how amorphous alloy product obtains by the method for casting, if want that obtaining thickness by casting is that 0.1 to 0.3mm goods then can increase the complexity of mould and the difficulty of moulding process greatly.In order to address this problem, the method that usually adopts now is to use the method (insert molding) of mold insert moulding to make amorphous alloy product, making with the crystalline material that is easy to process needs to carry out machining or punching or thickness less than the part of 0.3mm in the amorphous alloy product, then the part of crystalline material manufacturing is put into casting mould, then the non-crystaline amorphous metal liquation of casting is with final acquisition amorphous alloy product.
When the method for using produced by insert molding is made amorphous alloy product, can use the crystalline alloy material that the part that has labyrinth in the goods is carried out prefabricated, and then carry out the combination of amorphous alloy material and crystalline alloy material.But in the amorphous alloy product that this method makes, the bond strength between amorphous alloy material and the crystalline alloy material is lower, can't satisfy instructions for use.For example, in use, the problem that amorphous alloy material and crystalline alloy material often can occur getting loose.
Therefore, when using produced by insert molding to make amorphous alloy product, the bond strength that how to improve between amorphous alloy material and the crystalline alloy material becomes the technical problem that this area needs to be resolved hurrily.
Summary of the invention
The purpose of this invention is to provide a kind of inserts for amorphous alloy product, the amorphous alloy product that comprises this inserts and manufacture method, between amorphous alloy material and crystalline alloy material, to obtain higher bond strength.
According to an aspect of the present invention, a kind of inserts for amorphous alloy product is provided, this inserts comprises the first main part and first junction surface integrally formed with this first main part, this first junction surface has the first composition surface, it is characterized in that, but have the penetrating layer that comprises a plurality of holes on this first composition surface, three sizes of described hole in three dimensions are 10 to 800 μ m.
Preferably, but the hole rate of described penetrating layer is 70% to 95%.
Preferably, but a plurality of holes of described penetrating layer form spongelike structures.
Preferably, described hole is: micropore, the aperture of this micropore and the degree of depth are 10 to 800 μ m; Microflute, the width of this microflute and the degree of depth are 10 to 800 μ m; And/or little hole, the degree of depth in this little hole is 10 to 800 μ m.
Preferably, make the ceramic material of material for being formed by the powder particle sintering of described inserts.
Preferably, the material of described inserts is the crystalline alloy material, and the wall thickness of at least a portion of described first main part of described inserts is 0.1 to 3mm.
Preferably, the wall thickness of at least a portion of described the first main part is 0.1 to 0.3mm.
Preferably, be formed with screw thread and/or hole on the first main part of described inserts.
Preferably, the material of making described inserts is amorphous alloy material.
Preferably, the first junction surface of described inserts forms cylindrical or plate shaped.
As another aspect of the present invention, a kind of amorphous alloy product is provided, this amorphous alloy product comprises inserts and forming part, this forming part comprises the second main part and second junction surface integrally formed with this second main part, this second junction surface has the second composition surface, wherein, described inserts is above-mentioned inserts provided by the present invention, described inserts or described forming part are made by amorphous alloy material, described inserts embeds in the described forming part with engaging of described the first composition surface by described the second composition surface, but in the described hole in the described penetrating layer of at least a portion material of described forming part infiltration.
Preferably, described forming part is made by amorphous alloy material, and the fusing point of the material of described inserts is higher than the fusing point of the amorphous alloy material of described forming part.
Preferably, described inserts is made by amorphous alloy material, and described forming part is made by plastic material.
Preferably, described plastic material comprises: polyethylene, polyvinyl chloride, polystyrene, polyvinyl alcohol, polypropylene, polybutene, polyisobutene, polyformaldehyde, polyamide, Merlon, polytetrafluoroethylene (PTFE), PET, epoxy resin, phenolic resins, polyurethane, butadiene rubber, butadiene-styrene rubber, acrylonitrile-butadiene rubber and/or neoprene.
Preferably, the amorphous alloy material of described forming part is: rare-earth-base amorphous alloy, Fe-based amorphous alloy, zirconium-base amorphous alloy, copper-zirconium-base amorphous alloy and/or titanium-based amorphous alloy.
Preferably, the second junction surface of described forming part forms the shape that the first junction surface with described inserts is complementary.
Preferably, described amorphous alloy product is at least a portion of the housing of consumer electronics product.
As another aspect of the present invention, a kind of manufacture method of amorphous alloy product is provided, this amorphous alloy product comprises inserts and forming part, and inserts or forming part made by amorphous alloy material, described manufacture method comprises:
A) prefabricated inserts, this inserts comprise the first main part and the first junction surface integrally formed with this first main part, and this first junction surface has the first composition surface, and described inserts is put into mould;
B) material that will make forming part is heated to predetermined temperature, and insert described mould, thereby formation forming part, this forming part comprises the second main part and second junction surface integrally formed with this second main part, this second junction surface has the second composition surface, described inserts embeds in the described forming part by described the second composition surface and engaging of described the first composition surface, to obtain amorphous alloy product
Wherein, but the described inserts that described step obtains in a) is put into first composition surface at the first junction surface of mould and is had the penetrating layer that comprises a plurality of holes, three sizes of described hole in three dimensions are 10 to 800 μ m, at described step b) but in make the material of described forming part at least a portion infiltrate in the described hole of described penetrating layer.
Preferably, but the hole rate of the described penetrating layer of first composition surface at the first junction surface of the described inserts that described step obtains in a) is 70% to 95%.
Preferably, the first composition surface of described inserts carried out preliminary treatment after, but a plurality of holes of described penetrating layer form spongelike structures.
Preferably, but the described hole of described penetrating layer is: micropore, the aperture of this micropore and the degree of depth are 10 to 800 μ m; Microflute, the width of this microflute and the degree of depth are 10 to 800 μ m; And/or little hole, the degree of depth in this little hole is 10 to 800 μ m.
Preferably, at described step b) in, described predetermined temperature is higher than the fusing point of described non-crystaline amorphous metal.
Preferably, described inserts is made by the crystalline alloy material.
Preferably, described step a) also comprises, first composition surface at the first junction surface of described inserts is carried out sandblast, shot-peening, Laser Processing and/or chemical attack.
Preferably, described step a) also comprises: before described inserts is put into mould, carry out machining at the first main part of described inserts, so that the wall thickness of at least a portion of the first main part of described inserts is 0.1 to 3mm.
Preferably, the wall thickness of at least a portion of the first main part of described inserts is 0.1 to 0.3mm.
Preferably, described step a) also comprises: before described inserts is put into mould, carry out machining at the first main part of described inserts, to form screw thread or hole at described the first main part.
Preferably, described inserts is made by ceramic material, and described step a) also comprises: use the powder particle sintering to form the described inserts of being made by described ceramic material.
Preferably, described step a) also is included in described inserts put into and this inserts is carried out preheating before the mould, so that insert the temperature of the described inserts of described mould is: 200 to 300 degree.
Preferably, described inserts (1) is made by non-crystaline amorphous metal, and described forming part (2) is made by plastic material, and described predetermined temperature is not less than the melting temperature of described plastic material.
Preferably, described step a) also is included in described inserts put into and this inserts is carried out preheating before the mould, so that insert the temperature of the described inserts of described mould is: 50 to 100 degree.
In the manufacturing of traditional amorphous alloy product, when prefabricated inserts, in order to satisfy the needs of producing in enormous quantities, usually first composition surface at the first junction surface of inserts has relatively simple shape (as cylindrical or plate shaped), and first composition surface at the first junction surface of this inserts has relatively high machining accuracy, engages with forming part being convenient in the produced by insert molding process.
Yet the present inventor is through long-term research discovery, and the surface accuracy of the first composition surface of the inserts of raising amorphous alloy product is higher, can not correspondingly improve the bond strength of forming part and inserts.
Therefore, just be based on the above-mentioned cognition to amorphous alloy product, the present inventor has proposed technique scheme.Specifically, carry out preliminary treatment by the first composition surface to the inserts that is used for amorphous alloy product, but make this first composition surface have the penetrating layer that comprises a plurality of holes, thereby can improve forming part in the amorphous alloy product and the bond strength between the inserts.
Other features and advantages of the present invention will partly be described in detail in the specific embodiment subsequently.
Description of drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and consists of the part of specification, is used from explanation the present invention with the following specific embodiment one, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is in the amorphous alloy product according to one embodiment of the present invention, the cutaway view enlarged diagram at the joint interface place of forming part and inserts;
Fig. 2 is the enlarged diagram at the first junction surface of the inserts of the amorphous alloy product among Fig. 1;
Fig. 3 is the stereogram according to the amorphous alloy product of one embodiment of the present invention;
Fig. 4 is the stereogram of the inserts of the amorphous alloy product among Fig. 3;
Fig. 5 is the stereogram according to the amorphous alloy product of another embodiment of the invention;
Fig. 6 is the stereogram of the inserts of the amorphous alloy product among Fig. 5;
Fig. 7 is the flow chart according to the manufacture method of amorphous alloy product of the present invention; With
Fig. 8 be the test amorphous alloy product of the present invention bond strength the time used stretching style.
Description of reference numerals
1 inserts, 2 forming parts
11 holes, 3 holes
The specific embodiment
Below in conjunction with accompanying drawing the specific embodiment of the present invention is elaborated.Should be understood that, the specific embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
As depicted in figs. 1 and 2, the invention provides a kind of inserts 1, this inserts 1 is mainly used in the produced by insert molding of amorphous alloy product, amorphous alloy product among Fig. 1 obtains by the method for produced by insert molding, comprise inserts 1 and forming part 2, any one in inserts 1 and the forming part 2 is made by amorphous alloy material.
As shown in Figure 2, inserts 1 comprises the first main part and first junction surface integrally formed with this first main part, this first junction surface has the first composition surface, wherein, but have the penetrating layer that comprises a plurality of holes 11 on this first composition surface, three sizes of described hole 11 in three dimensions are 10 to 800 μ m.In the present invention, inserts 1 can be made by crystalline material, also can be made by non-crystalline material.
When inserts 1 is made by crystalline material, can obtain amorphous alloy product by the method for casting.The non-crystaline amorphous metal of molten condition has excellent copy function, can fill well the hole 11 on first composition surface at the first junction surface of inserts 1,, but infiltrates penetrating layer on first composition surface at the first junction surface of inserts 1 that is.
When the method by casting when carrying out the produced by insert molding of amorphous alloy product, inserts 1 is placed in the casting mould, then the non-crystaline amorphous metal liquation of molten condition is cast.
Preferably, be lower than the fusing point of the material of making inserts 1 when the temperature of the non-crystaline amorphous metal liquation that is used for the moulding amorphous alloy product, but the non-crystaline amorphous metal liquation can flow into the hole 11 of the penetrating layer on first composition surface at the first junction surface of inserts 1 to be solidified, thereby when the non-crystaline amorphous metal liquation solidifies fully, can form forming part 2, the second composition surface of this forming part 2 engages with first composition surface at the first junction surface of inserts 1, and form the structure of similar concavo-convex engagement at the joint interface of forming part 2 and inserts 1, as shown in Figure 3.Clearly, the connected structure of concavo-convex engagement has increased the interface contact area of forming part 2 and inserts 1 greatly, thereby strengthens the bond strength of forming part 2 and inserts 1.In this situation, inserts 1 can be made by the crystalline alloy material (for example stainless steel) that fusing point is higher than amorphous alloy product.
When inserts 1 was made by non-crystaline amorphous metal, forming part 2 can be made by plastic material, and can obtain by the mode of injection moulding described amorphous alloy product this moment.But the plastic material of molten condition can penetrate in the hole of penetrating layer of the first composition surface of inserts 1, thereby has increased the bonding area of inserts 1 with forming part 2, has improved bond strength.
Permeable formation is distributed at least a portion of the first composition surface of inserts 1, has higher bond strength in order to make between forming part 2 in the amorphous alloy product and the inserts 1, hole 11 on first composition surface at the first junction surface of inserts 1 can have higher density, preferably, but the hole rate of described penetrating layer is 70% to 95%.But hole 11 can be evenly distributed in the penetrating layer of the first composition surface of inserts 1, but (for example also can anisotropically be distributed in the penetrating layer of the first composition surface of inserts 1, the hole rate is 70% on the part of the first composition surface, and the hole rate of another part is 95%).But, preferably, but hole 11 be evenly distributed in the penetrating layer of the first composition surface of inserts 1, thereby can in amorphous alloy product, obtain uniform bond strength.And further preferably, permeable formation is distributed on whole first composition surface of inserts 1.
Hole of the present invention rate refers to the gross area in all holes 11 on the first composition surface and the ratio of the gross area of the first composition surface.When being formed with abundant hole 11 on first composition surface at the first junction surface of inserts 1, the material of more making forming part 2 is infiltrated in the described hole 11, increase bonding area, thereby improve bond strength.
Especially when forming part 2 was made for amorphous alloy material, the hole rate was larger, and then the portion size between the adjacent hole 11 is less.Portion size between adjacent hole 11 more hour, the surface energy of this part surface is higher, and surface atom is more active, more easily spreads when contacting with the non-crystaline amorphous metal of melting, even the generation melting phenomenon, form the metallurgical binding between inserts 1 and the forming part 2.As everyone knows, the bond strength of metallurgical binding will be higher than the bond strength of mechanical engagement, therefore obtains higher bond strength between inserts 1 and forming part 2.
As mentioned above, in order to dwindle the size of the part between the adjacent hole 11, but to be preferably be compact arranged in a plurality of holes 11 of described penetrating layer, and further preferably, but a plurality of holes 11 of described penetrating layer form spongelike structures.Thereby so that can be mutually to connect between each hole 11, when but the non-crystaline amorphous metal liquation infiltrates the penetrating layer of the first composition surface at the first junction surface of inserts 1, but can in penetrating layer, form the structure of interlaced connection, help to improve the inserts 1 of amorphous alloy product and the bond strength between the forming part 2.
Described hole 11 can for: micropore, the aperture of this micropore and the degree of depth are 10 to 800 μ m; Microflute, the width of this microflute and the degree of depth are 10 to 800 μ m; And/or little hole, the degree of depth in this little hole is 10 to 800 μ m.But when solidifying, the first composition surface of inserts 1 can infiltrate penetrating layer at the non-crystaline amorphous metal liquation of melting as long as can realize.Wherein, described micropore might not be circular hole, and square hole, polygonal hole etc. can realize being as the criterion with those skilled in the art when all right.
Thereby form closely pore structure, so that be penetrated in the first composition surface of inserts with the amorphous alloy material of melting.Specifically, the inserts 1 that the first composition surface is had pore structure 11 is put into mould, the casting melting non-crystaline amorphous metal the time, the non-crystaline amorphous metal liquation infiltrates in the inserts 1 along the pore structure 11 on the first composition surface, during cooling, can form at the joint circle place of forming part 2 and inserts 1 structure of similar concavo-convex engagement.
But can obtain by several different methods the hole 11 of penetrating layer of the first composition surface of inserts 1.For example, can carry out shot-peening, sandblast, Laser Processing and/or chemical attack by the first composition surface to inserts 1 obtains.
Preferably, can form pore structure 11 at the first composition surface by the method such as chemical attack.Chemical attack claims again metal etch, refers to that metal and the material that touches redox reaction directly occur and the process of oxidized loss.
In the present invention, described chemical attack may further comprise the steps: (1) is carried out etched inserts 1 with needs and is carried out oil removing, makes cleaning surfaces; (2) inserts 1 after using anti-corrosion glue to oil removing is coated with, and protection does not need etched part, then carries out drying 5～10 minutes in 90～110 ℃ of temperature ranges, increases the adhesion between anti-corrosion glue and the inserts 1, the raising corrosion resistance; (3) inserts of coating being finished carries out etching, can adopt chemical etching that workpiece is put into strong acid or highly basic hollow heart eating away is not protected the position, perhaps adopt electrochemical etching with workpiece as anode, in electrolyte, switch on, not protected position is because making anodic solution on the inserts 1; (4) but will be as required the anti-corrosion glue of inserts 1 lip-deep protection finished of etching namely obtain to have on the first composition surface the inserts 1 of penetrating layer after removing.
After the first composition surface of inserts 1 carried out chemical attack, but that the hole 11 of the penetrating layer that forms at the first composition surface is arranged as is spongy, that is, described a plurality of holes 11 mutual commissures, similar with arranging of hole in the sponge.Thereby when casting non-crystaline amorphous metal liquation, but in the hole 11 in the non-crystaline amorphous metal liquation infiltration penetrating layer, form the structure of interlaced connection, help to improve the inserts 1 of amorphous alloy product and the bond strength between the forming part 2.
Preferably, inserts 1 is made by the crystalline alloy material that is easy to process.Described crystalline alloy material can be aluminium alloy, magnesium alloy, steel, nickel alloy, copper alloy and/or titanium alloy.But the material of making inserts 1 is not limited to above-mentioned material.
Preferably, inserts 1 can be made by following material:
Aluminium alloy: 1000 series alloys are the most frequently used in a present conventional industry series such as 1050,1060,1100 etc.; 3000 series alloys such as 3003,3A21 etc., take manganese element as Main Ingredients and Appearance, have preferably antirust function; 5000 series alloys, such as 5052,5005,5083,5A05 etc., essential element is magnesium, claims again almag, has density low, and tensile strength is high, and the percentage elongation advantages of higher is widely used in conventional industry; 6000 series alloys such as 6061, mainly contain two kinds of elements of magnesium and silicon, have the advantages such as workability is good, good processability, easy coating, are applicable to make electronic product casing and are easy to and decorate.
Magnesium alloy: wrought magnesium alloy, Mg-Mn are such as MB1, MB2 etc., Mg-Al-Zn series MB5, MB6, MB7 etc., Mg-Zn-Zr series MB7, MB15 etc.; Cast magnesium alloy, Mg-Zn-Zr series ZM1, ZM2, ZM4, ZM8 etc., Mg-RE-Zr series ZM3 etc., Mg-Al-Zn series ZM5, ZM10 etc.
Steel: various stainless steels, ferritic stainless steel such as Cr17, Cr17Mo2Ti, Cr25, Cr25Mo3Ti, Cr28 etc., austenitic stainless steel such as 1Cr18Ni9,0Cr19Ni9 etc., martensitic stain less steel such as 1Cr13,3Cr13 etc.
Nickel alloy: pure nickel such as N2, N4 etc.; Monel such as NCu40-2-1, NCu28-2.5-1.5 etc.
Copper alloy: fine copper; The brass class, basis brass such as H96, H90, H80, H68 etc., ledrite such as HPb63-3, HPb60-2, HPb59-1 etc., one-ton brass HSn62-1 etc., aldubra HAl60-1-1 etc., iron brass HFe59-1-1, HFe58-1-1 etc., manganese brass HMn58-2 etc. and other brass; The bronze class, tin bronze QSn4-3, QSn4-4-2.5, QSn6.5-0.1 etc., aluminium bronze QA15, QA17, QA19-2, QA110-3-1.5 etc., manganese bronze QMn1.5, QMn5 etc., beryllium-bronze QBe2 and other bell metals.
Titanium alloy: such as Ti-6Al-4V, Ti-5Al-2.5Sn, Ti-2Al-2.5Zr, Ti-32Mo, Ti-Mo-Ni, Ti-Pd, SP-700, Ti-6242, Ti-10-5-3, Ti-1023, BT9, BT20 etc.
Usually, the method that amorphous alloy product passes through casting obtains, yet when the method acquisition thickness that uses casting is 0.1 to 3mm goods, can greatly increase the complexity of casting mould and casting technique.Therefore, advantage of the present invention is, when amorphous alloy product comprised that thickness is 0.1 to 3mm part, this thickness was that the thickness of the main part that 0.1 to 3mm part can be by making inserts 1 reaches 0.1 to 3mm and realizes.For example, can the thickness of crystalline alloy material be machined to 0.1 to 3mm by the method such as rolling and obtain inserts 1.When the material of making inserts 1 had good ductility, the wall thickness of at least a portion of the first main part of inserts 1 of the present invention can also be for 0.1 to 0.3mm, can be as having the shell structure of thin-walled.
If require inserts 1 to be the Shell-Class structure, can also draw to being rolling to certain thickness sheet material the corresponding shell structure of acquisition.
In order to satisfy the instructions for use of amorphous alloy product, usually can have some on the amorphous alloy product and need to pass through the functional structure that machining (such as punching, boring, tapping) forms.Because non-crystaline amorphous metal has higher hardness, is not easy to carry out machining, therefore, need to carry out machining at inserts 1.
Amorphous alloy product as shown in Figure 3, this amorphous alloy product are phone housing, have the hole 3 of inlaying the first-class device of shooting on this phone housing.The part that has hole 3 on this phone housing is inserts 1 (as shown in Figure 4), and the frame part of phone housing is made by amorphous alloy material.Thereby can obtain the functional hole on the phone housing, can make again this phone housing have higher intensity.
As shown in Figure 5 amorphous alloy product again, this amorphous alloy product also can be a kind of shell structure, the part that has screwed hole on this housing is inserts 1 (as shown in Figure 6).
Described ceramic particle can be alumina particle, silicon nitride particle, boron nitride particle, boron carbide particles, silicon-carbide particle etc.
In order to satisfy some specific demand, must comprise the part that plastic material is made in the amorphous alloy product.For example, in phone housing, in order to receive signal, the part of cell phone rear cover can be made by plastic material.Therefore, the material of making this inserts 1 can also be the non-crystaline amorphous metal material.When inserts 1 was amorphous alloy material, the material of making forming part 2 was generally plastic material.Ready-made inserts 1 is inserted in the mould, and then the plastic material with melting injects mould, and cooling can obtain inserts 1 and be the amorphous alloy product of plastic material for amorphous alloy material, forming part 2.Certainly, the amorphous alloy product that this plastic material engages with amorphous alloy material not merely is applicable to phone housing, can also be applicable to other various communication apparatus.
The first junction surface of inserts 1 can form cylindrical (such as double-screw bolt) or plate shaped.When the first junction surface of inserts 1 when being cylindrical, then the first composition surface is this columniform circumferential surface, preferably, this columniform whole circumferential surface is carried out preliminary treatment, but so that its surface has penetrating layer.When the first junction surface of inserts 1 when being plate shaped, then this plate shaped side is the first composition surface of this inserts 1, preferably, preliminary treatment is carried out in these all plate shaped sides, but so that its surface has penetrating layer.
As shown in Figure 1, as another aspect of the present invention, the invention provides a kind of amorphous alloy product, this amorphous alloy product comprises inserts 1 and forming part 2, this forming part 2 comprises the second main part and second junction surface integrally formed with this second main part, this second junction surface has the second composition surface, wherein, one in inserts 1 or the forming part 2 is made by amorphous alloy material, inserts 1 is above-mentioned inserts 1 provided by the invention, inserts 1 by the second composition surface with the first engaging of composition surface in the insert molding section 2, but in the hole 11 in the described penetrating layer of at least a portion material of forming part 2 infiltration.
In the amorphous alloy product that forming part 2 is made by amorphous alloy material, during the contacting of the non-crystaline amorphous metal of melting and inserts 1, but can infiltrate in the hole 11 in the penetrating layer, thereby have certain thickness non-crystaline amorphous metal permeable formation in the joint formation of forming part 2 and inserts 1.After the joint formation of forming part 2 and inserts 1 has certain thickness non-crystaline amorphous metal permeable formation, can make forming part 2 complementary with the material advantage of inserts 1.For example, when inserts 1 is made by stainless steel material, because the joint at forming part 2 and inserts 1 has formed the non-crystaline amorphous metal permeable formation, at this joint, stainless steel can remedy the deficiency of amorphous alloy material toughness, and the non-crystaline amorphous metal material then can remedy the deficiency of stainless steel intensity and hardness aspect.
As described in the text, when forming part 2 is made by amorphous alloy material, can adopt the method for casting to obtain described amorphous alloy product.
When using the method moulding amorphous alloy product of the present invention of casting, preferably, the fusing point of the material of inserts 1 is higher than the fusing point of the amorphous alloy material of forming part 2.
And also have this different system in the non-crystaline amorphous metal, because of the difference of main body composition exists must performance difference.Iron-based intensity hardness is higher; Rare earth based is with low cost; Copper base, titanium base, zirconium base Performance Ratio are more comprehensive.When therefore being that conventional material is combined with, should be taken into account that the demand of applied environment and product is selected different non-crystalline materials, thereby reach better technique effect.
The forming part 2 of amorphous alloy product of the present invention can use the non-crystaline amorphous metal of any composition to make, and for example, can be: Fe-based amorphous alloy, zirconium-base amorphous alloy, copper-zirconium-base amorphous alloy and/or titanium-based amorphous alloy.
Can select the amorphous alloy material of forming part 2 according to the material of inserts 1.For example, being the aluminium alloy of 200-300MPa when being connected with intensity, can preferentially select intensity at the rare-earth-base amorphous alloy material of 800-1000MPa; And when being connected with the material such as stainless steel, if there is not special requirement, then mainly connect with zirconium base, amorphous alloy material that titanium base equal strength hardness is higher; The toughness of most non-crystaline amorphous metal all is better than ceramic material, so when more crisp ceramic material is connected, can make a choice in multiple non-crystaline amorphous metal.
Preferably, when making amorphous alloy product of the present invention, select the amorphous alloy material of following composition to make forming part 2:
Zr
aAl
bCu
cNi
dY
e，45≤a≤65，10≤b≤35，5≤c≤12，5≤d≤14，0≤e≤5。Wherein a, b, c, d, e are atomic percentage.
Zr
aAl
bCu
cNi
dM
e，30≤a≤70，9≤b≤35，5≤c≤35，5≤d≤14，0≤e≤5。Wherein M is one or more elements among Nb, Sc, Ta, Ni, Co, Y, Ag, Fe, Sn, Al, Hf, the Be; A, b, c, d, e are atomic percentage.
(Zr，Ti)
a(Cu，Ni)
bBe
cTM
d，40≤a≤60，15≤b≤35，5≤c≤25，5≤d≤30。Wherein M is one or more elements among Nb, Sc, Ta, Y, Ag, Fe, Sn, Al, the Hf; A, b, c, d are atomic percentage.
Ti
aCu
bTL
cTD
dWherein, TL is one or more among Ni, Fe, Co, Mn, Ru, Ag, Pd, Pt, the Sn, and TD is one or more among Al, Be, Y, the Sc, a, b, c, d, e are atomic percentage, 40≤a≤55,25≤b≤45,0≤c≤4,1≤d≤7, and a, b, c, d sum are 100.
Fe
aCr
bMo
cT
dB
eY
f, 40≤a≤70,0＜b≤20,0＜c≤20,0＜d≤10,0＜e≤30,0＜f≤10, wherein a, b, c, d, e, f are atomic percentage, and a+b+c+d+e+f=100.T is one or more elements in Zr, Al, Ti, Mn, the W element in the above-mentioned chemical formula.
In having the amorphous alloy product of specific (special) requirements, some should comprise the part that plastic material is made, such as the housing of communication apparatus.In this case, inserts 1 is made by amorphous alloy material, and forming part 2 can be made by plastic material.
Preferably, described plastic material can comprise: polyethylene, polyvinyl chloride, polystyrene, polyvinyl alcohol, polypropylene, polybutene, polyisobutene, polyformaldehyde, polyamide, Merlon, polytetrafluoroethylene (PTFE), PET, epoxy resin, phenolic resins, polyurethane etc.; Rubber such as butadiene rubber, butadiene-styrene rubber, acrylonitrile-butadiene rubber and/or neoprene.
Above inserts 1 has been done detailed description for the forming process of the amorphous alloy product that amorphous alloy material is made, forming part 2 is made for plastic material and the first composition surface of inserts 1 and the second composition surface of forming part 2, repeated no more here.
In the situation that inserts 1 by non-crystalline material make, forming part 2 made by plastic material, can carry out various required machinings in forming part 2, such as tapping, boring etc.
In amorphous alloy product of the present invention, the second junction surface of forming part 2 forms the shape that the first junction surface with inserts 1 is complementary.For example, when the first junction surface of inserts 1 when being cylindrical, the second junction surface of forming part forms and can hold this columniform hole; For another example, when the first junction surface of inserts 1 when being plate shaped, the second junction surface of forming part 2 forms and can hold this plate shaped cavity.
Preferably, amorphous alloy product of the present invention is at least a portion of the housing of consumer electronics product.Consumer electronics product refers to for individual and family and broadcasting, TV-related Voice ﹠ Video product, for example, television set, video disc player (VCD, SVCD, DVD), video recorder, video camera, radio, radio cassette player, combination audio, phonograph, compact disc player (CD), phone, PC, work-at-home equipment, domestic electronic health care facility, automobile electronics, code camera, mobile phone, PDA etc.Deng.
Amorphous alloy product as shown in Figure 3, this amorphous alloy product are phone housing, have the hole 3 of inlaying the first-class device of shooting on this phone housing.The part that has hole 3 on this phone housing is inserts 1 (as shown in Figure 4), and the frame part of phone housing is made by amorphous alloy material.Thereby can obtain the functional hole on the phone housing, can make again this phone housing have higher intensity.
As shown in Figure 5 amorphous alloy product again, this amorphous alloy product also can be phone housing, the part that this phone housing has screwed hole is inserts 1 (as shown in Figure 6).
Manufacture method flow chart below in conjunction with the amorphous alloy product of the present invention shown in Fig. 7, manufacture method to amorphous alloy product of the present invention is described in detail, described amorphous alloy product comprises inserts 1 and forming part 2, and any one in inserts 1 and the forming part 2 is made by amorphous alloy material.
The manufacture method of amorphous alloy product of the present invention may further comprise the steps:
A) prefabricated inserts 1, this inserts 1 comprise the first main part and the first junction surface integrally formed with this first main part, and this first junction surface has the first composition surface, and this inserts 1 is put into mould;
B) material that will make forming part 2 is heated to predetermined temperature, and insert described mould, thereby form forming part 2, this forming part 2 comprises the second main part and second junction surface integrally formed with this second main part, this second junction surface has the second composition surface, inserts 1 by described the second composition surface with described the first engaging of composition surface in the insert molding section 2, with the acquisition amorphous alloy product
Wherein, but described step a) first composition surface at the first junction surface of the middle inserts 1 that obtains has the penetrating layer that comprises a plurality of holes 11, three sizes of described hole 11 in three dimensions are 10 to 800 μ m, at described step b) but in make the material of forming part 2 at least a portion infiltrate in the described hole 11 of described penetrating layer.
Preferably, but the hole rate of the penetrating layer of first composition surface at the first junction surface of the inserts 1 that step obtains in a) is 70% to 95%.
For inserts 1 and the bond strength between the forming part 2 of the amorphous alloy product that makes acquisition are higher, preferably, the first composition surface of inserts 1 carried out preliminary treatment after, but a plurality of holes 11 of described penetrating layer form spongelike structures.
Preferably, but the described hole 11 of described penetrating layer be: micropore, the aperture of this micropore and the degree of depth are 10 to 800 μ m; Microflute, the width of this microflute and the degree of depth are 10 to 800 μ m; And/or little hole, the degree of depth in this little hole is 10 to 800 μ m.Thereby can be after the non-crystaline amorphous metal liquation solidifies along the first composition surface of inserts 1 obtain to have the non-crystaline amorphous metal permeable formation at the joint of forming part 2 and inserts 1.
When adopting casting, can be at described step b) in, described non-crystaline amorphous metal is heated to the temperature more than the fusing point of this non-crystaline amorphous metal.During casting, as for fixing in the die cavity of casting mould, then the non-crystaline amorphous metal with melting injects casting mould with inserts 1.But when contacting with the first surface of inserts 1, the non-crystaline amorphous metal of melting infiltrates the penetrating layer of the first composition surface of inserts 1.
When forming part 2 was made by amorphous alloy material, inserts 1 can be made by the crystalline alloy material.
When inserts 1 is made by the crystalline alloy material, for but the first composition surface that makes inserts 1 has penetrating layer, usually, the preliminary treatment of first composition surface at the first junction surface of inserts 1 comprised: the first composition surface to inserts 1 carries out sandblast, shot-peening, Laser Processing and/or chemical attack.And, by chemical attack, but can make a plurality of holes 11 of the described penetrating layer on the first composition surface of inserts 1 form spongelike structure.
In order to satisfy the instructions for use of amorphous alloy product, usually can have some on the amorphous alloy product and need to pass through the functional structure that machining (such as punching, boring, tapping) forms.Because non-crystaline amorphous metal has higher hardness, is not easy to carry out machining, need to carry out machining at inserts 1.Therefore, described step a) also comprises: before inserts 1 is put into mould, carry out machining at the main part of inserts 1.Specifically carry out the machining of which kind of form, decide according to the function of inserts 1 in amorphous alloy product.
When amorphous alloy product need to comprise that thickness is 0.1 to 3mm part, this thickness was that the thickness of the main part that 0.1 to 3mm part can be by making inserts 1 reaches 0.1 to 3mm and realizes.For example, can make at least a portion thickness of the main part of inserts 1 by the method such as rolling is 0.1 to 3mm.
When the material of making inserts 1 had good ductility, the wall thickness of at least a portion of the first main part of inserts 1 of the present invention can also be for 0.1 to 0.3mm,, can be as having the shell structure of thin-walled.
Amorphous alloy product as shown in Figure 3, need to be on inserts machining hole 3, amorphous alloy product as shown in Figure 5, then need to be on inserts 1 machining screw.
For fear of the non-crystaline amorphous metal liquation with after the first composition surface of inserts 1 contacts, in the forming core crystallization of the first composition surface place, should improve the temperature of inserts 1, therefore, preferably, described step a) also comprises: described preliminary treatment also comprises carries out preheating to described inserts 1.Preferably, through the temperature of inserting the inserts 1 of described mould after the preheating be: 200 to 300 degrees centigrade.Inserts 1 is heated to prevents between 200 to 300 degrees centigrade that the non-crystaline amorphous metal liquation from the forming core crystallization of place, the first composition surface of inserts 1, can keep again the surface texture of the first composition surface.
When inserts 1 was made by amorphous alloy material, forming part 2 can be made by plastic material, and in this case, described predetermined temperature is more than or equal to the melting temperature of described plastic material.
And when inserts 1 had amorphous alloy material to make, preferably, but the method by chemical attack obtained the penetrating layer on first composition surface at the first junction surface.
In mould, when the plastic material of molten condition contacts with the first composition surface of inserts 1, but the plastic material of a part of melting can infiltrate the penetrating layer of the first composition surface.Because plastic material has different chemical property with amorphous alloy material, therefore, for prevent plastic material engage with amorphous alloy material, cool off after cracking, the phenomenon such as come off, preferably, can before being inserted mould, inserts 1 carry out preheating to inserts 1, expand to some extent when making inserts 1 than room temperature state, thereby can shrink together with the forming part 2 that plastic material forms in the process of cooling, that avoids that contraction because of plastic material causes comes off from inserts 1.The fusing point of plastic material between 100 to 200 degrees centigrade, therefore, preferably, is preheated to 50 to 100 degrees centigrade with inserts 1 and gets final product greatly.
In the situation that inserts 1 by non-crystalline material make, forming part 2 made by plastic material, can carry out various required machinings in forming part 2, such as tapping, boring etc.
Embodiment
Inserts 1 is made by stainless steel 0Cr18Ni9; to put into iron chloride content 700g/L through the inserts 1 of oil removing and coating conservation treatment; hydrochloric acid 100g/L; phosphoric acid 25g/L; the chemical etching liquor of sulfuric acid 90g/L cleans up the removal coating for surface protection carrying out etching under 30 ℃ the temperature conditions after 15 minutes, but can obtain to have the first composition surface of penetrating layer; but should penetrating layer comprise that average pore size was 100 μ m, mean depth is the micropore of 80 μ m.Put into casting mould after inserts 1 is heated to 250 ℃, then with the non-crystaline amorphous metal Zr of molten condition
45Al
10Cu
32Ni
9Y
4Liquation pours into casting mould, and cooling obtains amorphous alloy product.When testing the bond strength between forming part 2 and the inserts 1, with reference to the method for testing sample preparation (as shown in Figure 8) in the GB/T228-2002 metal material tensile test at room temperature method, and the forming part 2 of utilizing CMT5105 microcomputer controlled electronic omnipotent (pulling force) experimental machine to test the amorphous alloy product that obtains is 185MPa with the bond strength of inserts 1 at the joint interface place, utilize ZBC1251-2 liquid crystal fully-automatic metal balance weight impact testing machine, than pendulum impact test method amorphous alloy product is carried out impact test with reference to the GBT 229-2007 summer, forming part 2 and the impact flexibility of inserts 1 at the joint interface place of the amorphous alloy product of acquisition are 196KJ/m
2
According to the manufacture method of the amorphous alloy product described in the embodiment 1, difference is, inserts 1 is made by aluminium alloy 1050.Forming part 2 and the bond strength of inserts 1 at the joint interface place of the amorphous alloy product that obtains are 94MPa, and impact flexibility is 196KJ/m
2
According to the manufacture method of the amorphous alloy product described in the embodiment 1, difference is, described inserts 1 is made by stainless steel Cr17Mo2Ti, and the material of forming part 2 is: Zr
51.6Al
9.9Cu
30.3Y
0.8But the first composition surface to the first junction surface of inserts 1 carries out the penetrating layer that blasting treatment obtains, but should penetrating layer be that forming part 2 and the bond strength of inserts 1 at the joint interface place that little hole of 10 μ m forms the amorphous alloy product that obtains is 108MPa by mean depth, impact flexibility is 139KJ/m
2
Embodiment 4
Manufacture method according to the amorphous alloy product described in the embodiment 1, difference is, described inserts 1 is made by stainless steel 0Cr17Ni12Mo2, but the first composition surface to the first junction surface of inserts 1 carries out the penetrating layer that Laser Processing obtains, but should penetrating layer comprise that mean breadth was that 800 μ m, mean depth are the microflute of 800 μ m, the material of forming part 2 is: (Zr, Ti)
50(Cu, Ni)
20Be
13TY
7, forming part 2 and the bond strength of inserts 1 at the joint interface place of the amorphous alloy product of acquisition are 132MPa, impact flexibility is 152KJ/m
2
Carry out preliminary treatment by the first composition surface to the inserts that is used for amorphous alloy product, make on this first composition surface to form the penetrating layer that is formed by the hole with preliminary dimension, thereby can improve forming part in the amorphous alloy product and the bond strength between the inserts.
Below describe by reference to the accompanying drawings preferred embodiment of the present invention in detail; but; the present invention is not limited to the detail in the above-mentioned embodiment; in technical conceive scope of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Need to prove in addition, each concrete technical characterictic described in the above-mentioned specific embodiment in reconcilable situation, can make up by any suitable mode, for fear of unnecessary repetition, the present invention is to the no longer separately explanation of various possible combinations.
In addition, also can carry out any combination between the various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (31)
1. the inserts (1) that is used for amorphous alloy product, this inserts (1) comprises the first main part and first junction surface integrally formed with this first main part, this first junction surface has the first composition surface, it is characterized in that, have on this first composition surface comprise a plurality of holes (11) but penetrating layer, described hole (11) three sizes in three dimensions are 10 to 800 μ m.
2. inserts according to claim 1 (1) is characterized in that, but the hole rate of described penetrating layer is 70% to 95%.
3. inserts according to claim 1 (1) is characterized in that, but described a plurality of holes (11) of described penetrating layer form spongelike structure.
4. the described inserts of any one (1) in 3 according to claim 1 is characterized in that, described hole (11) are: micropore, the aperture of this micropore and the degree of depth are 10 to 800 μ m; Microflute, the width of this microflute and the degree of depth are 10 to 800 μ m; And/or little hole, the degree of depth in this little hole is 10 to 800 μ m.
5. inserts according to claim 1 (1) is characterized in that, the material of this inserts (1) is the crystalline alloy material, and the wall thickness of at least a portion of described first main part of this inserts (1) is 0.1 to 3mm.
6. inserts according to claim 5 (1) is characterized in that, the wall thickness of at least a portion of described the first main part is 0.1 to 0.3mm.
7. according to claim 5 or 6 described inserts (1), it is characterized in that, be formed with screw thread and/or hole (3) on first main part of this inserts (1).
8. inserts according to claim 1 (1) is characterized in that, makes the ceramic material of material for being formed by the powder particle sintering of described inserts (1).
9. inserts according to claim 1 (1) is characterized in that, the material of making this inserts (1) is amorphous alloy material.
10. according to claim 1-3, the described inserts of any one (1) among the 5-6,8 and 9, it is characterized in that, first junction surface of this inserts (1) forms cylindrical or plate shaped.
11. amorphous alloy product, this amorphous alloy product comprises inserts (1) and forming part (2), this forming part (2) comprises the second main part and second junction surface integrally formed with this second main part, this second junction surface has the second composition surface, it is characterized in that, described inserts (1) is the described inserts of any one (1) in the claim 1 to 10, described inserts (1) or described forming part (2) are made by amorphous alloy material, described inserts (1) embeds in the described forming part (2) by described the second composition surface and engaging of described the first composition surface, described forming part (2) but at least a portion material infiltrate in the described hole (11) in the described penetrating layer.
12. amorphous alloy product according to claim 11 is characterized in that, described forming part (2) is made by amorphous alloy material, and the fusing point of the material of described inserts (1) is higher than the fusing point of the amorphous alloy material of described forming part (2).
13. amorphous alloy product according to claim 11 is characterized in that, described inserts (1) is made by amorphous alloy material, and described forming part (2) is made by plastic material.
14. amorphous alloy product according to claim 13, it is characterized in that, described plastic material comprises: polyethylene, polyvinyl chloride, polystyrene, polyvinyl alcohol, polypropylene, polybutene, polyisobutene, polyformaldehyde, polyamide, Merlon, polytetrafluoroethylene (PTFE), PET, epoxy resin, phenolic resins, polyurethane, butadiene rubber, butadiene-styrene rubber, acrylonitrile-butadiene rubber and/or neoprene.
15. the described amorphous alloy product of any one in 14 is characterized in that according to claim 11, described amorphous alloy material is: rare-earth-base amorphous alloy, Fe-based amorphous alloy, zirconium-base amorphous alloy, copper-zirconium-base amorphous alloy and/or titanium-based amorphous alloy.
16. the described amorphous alloy product of any one in 14 is characterized in that according to claim 11, the second junction surface of described forming part (2) forms the shape that the first junction surface with described inserts (1) is complementary.
17. the described amorphous alloy product of any one in 14 is characterized in that according to claim 11, this amorphous alloy product is at least a portion of the housing of consumer electronics product.
18. the manufacture method of amorphous alloy product, this amorphous alloy product comprise inserts (1) and forming part (2), and inserts (1) or forming part (2) made by amorphous alloy material, described manufacture method comprises:
A) prefabricated inserts (1), this inserts (1) comprise the first main part and the first junction surface integrally formed with this first main part, and this first junction surface has the first composition surface, and described inserts (1) is put into mould;
B) material that will make forming part (2) is heated to predetermined temperature, and insert described mould, thereby form forming part (2), this forming part (2) comprises the second main part and second junction surface integrally formed with this second main part, this second junction surface has the second composition surface, described inserts (1) embeds in the described forming part (2) by described the second composition surface and engaging of described the first composition surface, to obtain amorphous alloy product
It is characterized in that, first composition surface at the first junction surface of the described inserts (1) that described step obtains in a) have comprise a plurality of holes (11) but penetrating layer, three sizes of described hole (11) in three dimensions are 10 to 800 μ m, at described step b) in make described forming part (2) but at least a portion of material infiltrate in the described hole (11) of described penetrating layer.
19. the manufacture method of amorphous alloy product according to claim 18 is characterized in that, the described inserts (1) that described step obtains in a) but the hole rate of described penetrating layer of the first composition surface at the first junction surface be 70% to 95%.
20. according to the manufacture method that requires 18 or 19 described amorphous alloy products in the right, but a plurality of holes (11) of described penetrating layer form spongelike structure.
21. according to claim 18 or the manufacture method of 19 described amorphous alloy products, it is characterized in that, but the described hole (11) of described penetrating layer is: micropore, the aperture of this micropore and the degree of depth are 10 to 800 μ m; Microflute, the width of this microflute and the degree of depth are 10 to 800 μ m; And/or little hole, the degree of depth in this little hole is 10 to 800 μ m.
22. the manufacture method of amorphous alloy product according to claim 18 is characterized in that, at described step b) in, described predetermined temperature is higher than the fusing point of described non-crystaline amorphous metal.
23. the manufacture method of amorphous alloy product according to claim 22 is characterized in that, described inserts (1) is made by the crystalline alloy material.
24. the manufacture method of amorphous alloy product according to claim 23, it is characterized in that, described step a) also comprises, first composition surface at the first junction surface of described inserts (1) is carried out sandblast, shot-peening, Laser Processing and/or chemical attack.
25. the manufacture method of amorphous alloy product according to claim 23, it is characterized in that, described step a) also comprises: before described inserts (1) is put into mould, the first main part at described inserts (1) carries out machining, so that the wall thickness of at least a portion of the first main part of described inserts (1) is 0.1 to 3mm.
26. the manufacture method of amorphous alloy product according to claim 25 is characterized in that, the wall thickness of at least a portion of the first main part of described inserts (1) is 0.1 to 0.3mm.
27. the manufacture method of amorphous alloy product according to claim 23, it is characterized in that, described step a) also comprises: before described inserts (1) is put into mould, the first main part at described inserts (1) carries out machining, to form screw thread or hole (3) at described the first main part.
28. the manufacture method of amorphous alloy product according to claim 21, it is characterized in that, described inserts (1) is made by ceramic material, and described step a) also comprises: use powder particle to carry out sintering and form the described inserts (1) of being made by described ceramic material.
29. the manufacture method of the described amorphous alloy product of any one in 28 according to claim 21, it is characterized in that, described step a) also is included in described inserts (1) put into and this inserts (1) is carried out preheating before the mould, so that insert the temperature of the described inserts (1) of described mould is: 200 to 300 degrees centigrade.
30. the manufacture method of amorphous alloy product according to claim 18, it is characterized in that, described inserts (1) is made by amorphous alloy material, and described forming part (2) is made by plastic material, and described predetermined temperature is not less than the melting temperature of described plastic material.
31. the manufacture method of amorphous alloy product according to claim 30, it is characterized in that, described step a) also is included in described inserts (1) put into and this inserts (1) is carried out preheating before the mould, so that insert the temperature of the described inserts (1) of described mould is: 50 to 100 degrees centigrade.
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| CN 201110237851 CN102950834A (en) | 2011-08-18 | 2011-08-18 | Insert used in amorphous alloy product, amorphous alloy product, and manufacturing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110237851 CN102950834A (en) | 2011-08-18 | 2011-08-18 | Insert used in amorphous alloy product, amorphous alloy product, and manufacturing method thereof |
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Application publication date: 20130306 |