CN105112817A - Abrasion-resistant and corrosion-resistant amorphous alloy and preparation method thereof - Google Patents
Abrasion-resistant and corrosion-resistant amorphous alloy and preparation method thereof Download PDFInfo
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- 238000005260 corrosion Methods 0.000 title claims abstract description 47
- 230000007797 corrosion Effects 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title abstract description 14
- 238000005299 abrasion Methods 0.000 title abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 229910052737 gold Inorganic materials 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 239000005300 metallic glass Substances 0.000 claims description 56
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 4
- 238000004512 die casting Methods 0.000 claims description 2
- 239000000956 alloy Substances 0.000 abstract description 32
- 230000003628 erosive effect Effects 0.000 abstract description 13
- 239000012530 fluid Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 30
- 229910045601 alloy Inorganic materials 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007769 metal material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000005275 alloying Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910018507 Al—Ni Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910000714 At alloy Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910007729 Zr W Inorganic materials 0.000 description 1
- 125000000218 acetic acid group Chemical class C(C)(=O)* 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 229910000601 superalloy Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Powder Metallurgy (AREA)
- Prevention Of Electric Corrosion (AREA)
Abstract
The invention discloses abrasion-resistant and corrosion-resistant amorphous alloy and a preparation method thereof. The composition of the amorphous alloy is ZraHfbAlcNidM1eM2f, and a, b, c, d, e and f represent for the molar percentage content of the corresponding atom in the amorphous alloy; the M1 is a mixture of one or more of Si, Cr, Pt, Pd, Au and Ag, and the M2 is a mixture of one or more of Cu, Zn, Mn and Fe. By means of the amorphous alloy material, special corrosion such as corrosion abrasion and erosive abrasion caused by contact between equipment and moving fluid can be improved remarkably; meanwhile, the amorphous alloy material is good in forming property, simple in preparation process and suitable for industrial production.
Description
Technical field
The present invention relates to a kind of wear-resistant corrosion resistant non-crystaline amorphous metal and preparation method thereof, relate in particular to a kind of wear-resistant corrosion resistant Zr base noncrystal alloy and preparation method thereof.
Background technology
Metallic material product in use will be subject to multi-form direct or indirect damage, and wherein modal damage type is abrasion and corrosion.Wearing and tearing refer to that hardware and miscellaneous part interact, the damage gradually caused due to mechanical friction, as the wearing and tearing between the wheel of locomotive and rail.Corrosion refers to that metallic substance is under the effect of surrounding medium, and damage gradually or go bad, the corrosion of metallic substance is one of modal corrosion phenomenon.Metallic substance spreads all over the every field of national economy, and from daily life to national defense industry, as long as use metallic substance part, all inevitably there is the problem of galling and corrosion, not only cause financial loss, some even causes catastrophic accident.In modern industry, the problem for galling and corrosion expands large quantifier elimination, and the metallic substance how obtaining wear-and corrosion-resistant becomes one of emphasis direction of current investigation of materials.
In industrial application, many mechanical means, electronics often work under the envrionment conditions of very severe, as high temperature, damp and hot, salt fog, with contact with sea water, contact soda acid etc., these equipment not only require the good corrosive power of resistance to surrounding medium, also requirement can corrosive wear, erosive wear etc. in tolerance work because of the fluid contact of equipment and motion and the Special Corrosion caused.Current domestic widely used alloy material mostly is iron system, anti-corrosion performance is reached by the Cr content in adjustment alloy, as stainless steel, expansion alloy, superalloy etc., due to the not environmentally property of Fe sill easy-to-rust characteristic and conventional Addition ofelements Cr, Ni, the use of these conventional non-corrosive metals does not often reach requirement in special machine, and expensive.
Non-crystaline amorphous metal developed a kind of novel material rapidly in the last few years, because its inherent high rigidity, high strength, good wear and corrosion behavior make it in field widespread uses such as military project, aerospace and petrochemical industry, as at military industry field, the armor-piercing head that Zr-W non-crystaline amorphous metal is made can reach very high density and intensity, and have from sharp effect, have high Adiabatic Shearing Sensitivity, Environmental compatibility is good simultaneously.
Application number is the Chinese patent of " Fe-based amorphous surfacing welding electrode of a kind of wear-and corrosion-resistant and preparation method thereof " by name of 201310082019.0, provides a kind of formula to be Fe
41co
7cr
15mo
14c
15b
6y
2the Fe-based amorphous welding rod of (atomic percent), can obtain the amorphous/nanocrystalline composite overlaying layer with good wear corrosion resisting property thus.
Application number is the Chinese patent of " a kind of high anti-corrosion iron-based soft magnetic non-crystaline amorphous metal and preparation method thereof " by name of 201210426268.2, and molecular formula is Fe
acr
bni
cmo
dp
ec
fb
gsi
h, a-h represents the molar content of corresponding atom.Compared with existing iron-based soft magnetic non-crystaline amorphous metal, this non-crystaline amorphous metal has high anti-corrosion, high amorphous formation ability and excellent magnetic energy simultaneously, can as electromagnetic device material in rugged environment, as used in the corrosive mediums such as damp and hot salt fog, ammonia or various acid, seawater, sewage.
Although Fe base non-crystalline material excellent performance, has soft magnetic performance, and for corrosive wear, erosive wear etc. because of the fluid contact of equipment and motion and the Special Corrosion caused without remarkable improvement.
Summary of the invention
The invention provides the not only wear-resistant but also corrosion resistant amorphous alloy material of one, and this amorphous alloy material to corrosive wear, erosive wear etc. because of the fluid contact of equipment and motion and the Special Corrosion caused be significantly improved, this amorphous alloy material forming property is good simultaneously, preparation technology is simple, is applicable to suitability for industrialized production.
Technical problem to be solved by this invention is achieved by the following technical programs:
1, composition of raw materials
Described non-crystaline amorphous metal consist of Zr
ahf
bal
cni
dm1
em2
f, wherein a, b, c, d, e, f are atomic molar percentage composition corresponding in described non-crystaline amorphous metal, are respectively 30≤a≤55,5≤b≤15,5≤c≤15,8≤d≤20,5≤e≤10,5≤f≤15; M1 is one or more mixtures in Si, Cr, Pt, Pd, Au, Ag element, and M2 is one or more mixtures in Cu, Zn, Mn, Fe element.
Further, above-mentioned non-crystaline amorphous metal atomic molar percentage composition can be preferably 40≤a≤55,5≤b≤10,10≤c≤15,10≤d≤20,5≤e≤8,8≤f≤15.
Again further preferably, atomic molar percentage composition is respectively 45≤a≤55,8≤b≤10,10≤c≤15,12≤d≤20,5≤e≤8,8≤f≤12.
Zr base block amorphous alloy has higher glass forming ability, solidity to corrosion and forming ability, add Hf atom of the same clan and have certain metalepsy to Zr atom in the alloy, reactive force in alloy between different metal atom is strengthened, and macro manifestations is comparatively compact formed functional for cooling rear alloy structure.The interpolation of Al, Ni strengthens the Forming ability of this non-crystaline amorphous metal on the one hand, and the corrosion of Al and Ni element to surrounding medium simultaneously has resists effect preferably, is added with the lifting benefiting corrosion resisting property in right amount.So add Hf, Al, Ni can obtain the good and good non-crystaline amorphous metal of corrosion resisting property of forming property in Zr base material.
Adding the higher alloying element of equilibrium potential in the alloy can make the equilibrium potential of alloy raise, add the thermodynamic stability of alloy monolithic, namely the solid solution structure that intermetallic is formed makes atomic shell structure change, and the energy of alloy changes, and free energy reduces.In addible element, contriver is found by great many of experiments, the stability of alloy can be increased substantially according to above-mentioned principle one or more mixtures added in Si, Cr, Pt, Pd, Au, Ag element, and strengthen hardness and the corrosion resistance nature of alloy.Simultaneously, because the solid solubility of alloying element in sosoloid is limited often, so the ratio of adding such alloying element is unsuitable high, finds that the 5-10% that alloy atom molar content is accounting for total alloy that such adds can reach good effect through experiment, can 5-8% be preferably further.
The alloying element of increase corrosion system resistance can be added in the alloy to promote corrosion resistant performance simultaneously; contriver is found by great many of experiments; can impel according to above-mentioned principle one or more mixtures added in Cu, Zn, Mn, Fe element and generate the corrosion product thus reduction corrosion current with provide protection at alloy surface; alloy and corrosive medium completely cut off by the alloy surface that is attached to that the corrosion product of these trace is insoluble to corrosive medium, resistance high, fine and close, very effectively stop the carrying out of corrosion process.And Cu, Zn, Mn, Fe element can both form sosoloid with matrix metal and meets the requirement of alloy to processability and mechanical property, promote the hardness of non-crystaline amorphous metal entirety.The ratio of adding such alloying element can tell on to non-crystaline amorphous metal overall performance 5% time, and the atomic molar percentage composition of interpolation reaches as high as 15%, and preferred interpolation scope is 8-15%, more preferably 8-12%.
Improve further again, the P element that atomic molar percentage composition is 0.1-2% in above-mentioned non-crystaline amorphous metal, can also be added.Ni, Cr, Si, Cu, Zn, Pd, Mn, Fe element is added in non-crystaline amorphous metal; can at the amorphous oxide compound of alloy substrate Surface Realize one deck after melting; alloy plays a good protection, and the interpolation of P element can promote the formation of this non-crystalline state zone of oxidation.The interpolation content of P element is unsuitable too high, and atomic molar percentage composition is the effect that 0.1-2% can reach.
2, preparation method
Step one, raw material purity being greater than 99.9% carries out proportioning according to above-mentioned non-crystaline amorphous metal composition, and material purity determines the quantity of impurity in raw material.Impurity too much not only can absorb more oxygen element, is unfavorable for shaping and the following process of non-crystaline amorphous metal, and impurity also can form the generation that the nuclei of crystallization affect non-crystal structure in molten metal.
Step 2, by the raw material that mixes in vacuum condition or argon gas atmosphere by arc melting or other conventional melting modes by raw material melting, can melt back 2-3 time, wherein vacuum tightness is 10
-1-10
-3pa, argon atmospheric pressure is 0.01-0.05MPa, obtains non-crystaline amorphous metal ingot casting after cooling.Repeatedly the object of melting be to promote further non-crystaline amorphous metal purity, reduce grain boundary impurities segregation, crystal boundary is attenuated, macro-effect not only can increase the hardness of amorphous product, and the ability of the anticorrosive of non-crystaline amorphous metal product and wearing and tearing can be promoted.Vacuum tightness in technique and the pressure condition of argon gas atmosphere all very low, very easily reach in actual production.
Further, after melting, speed of cooling is 10
2-10
3k/s is advisable.
Step 3, obtains above-mentioned non-crystaline amorphous metal product by inhaling the conventional non-crystaline amorphous metal preparation methods such as casting, die casting.The amorphous alloy material prepared by above-mentioned technique can use any ordinary method machine-shaping, without the restriction on processing conditions, is suitable for industrial applications and produces.
Non-crystaline amorphous metal in the present invention can be applicable to, in consumer electronics product, medical device product, aerospace industry, machine instrumentation industry and automotive industry, especially can be used as wear-resistant, corrosion-resistant material and apply.
The present invention has following beneficial effect:
1, the amorphous alloy material in the present invention is wear-resistant, hardness is high.
2, the amorphous alloy material corrosion resistance and good in the present invention, especially to corrosive wear, erosive wear etc. because of the fluid contact of equipment and motion and the Special Corrosion caused be significantly improved.
3, the amorphous alloy material in the present invention forms size can reach 30mm, and preparation technology is simple, is applicable to suitability for industrialized production.
Embodiment
1, embodiment 1
Purity is greater than the raw material of 99.9% according to the non-crystaline amorphous metal composition Zr in following table
ahf
bal
cni
dm1
em2
fcarry out proportioning, wherein a, b, c, d, e, f are atomic molar percentage composition corresponding in non-crystaline amorphous metal.M1 is one or more mixtures in Si, Cr, Pt, Pd, Au, Ag element, and M2 is one or more mixtures in Cu, Zn, Mn, Fe element.
M1, M2 select proportioning following (numerical value after the symbol of element is Elements Atom molar content):
By the raw material that mixes in argon gas atmosphere by arc melting or other conventional melting modes by raw material melting, melt back 3 times, argon atmospheric pressure is 0.05MPa, obtains non-crystaline amorphous metal ingot casting after cooling.The change of argon atmospheric pressure in allowed band does not affect fusion process.After melting, speed of cooling is 10
2-10
3k/s, in scope, depending on concrete alloying constituent, changes non-crystaline amorphous metal product without impact in allowed band.Obtain above-mentioned non-crystaline amorphous metal product finally by pressure casting method, product is tested.
Vickers' hardness test, environmental corrosion test, erosive wear test are carried out to non-crystaline amorphous metal product, wherein Vickers' hardness test is carried out according to " GB/T7997-2014 Wimet Vickers' hardness testing method ", unification selects HV5 to test, and the acetic acid salt spray test in " GB/T10125-2012 artificial atmosphere corrosion test salt-fog test " is chosen in environmental corrosion test.Erosive wear test is nonstandard test, test condition is: select 20-80 object quartz sand as erosion particle, spray to test surfaces with erosion speed 10m/s under normal temperature and pressure conditions, erosion particle in the slurry concentration is 8%, impact angle is 45 degree, final test erosive wear unit weight loss.
Test result is as follows:
From embodiment 1 test result, the non-crystaline amorphous metal hardness in the present invention is high, and in salt spray corrosion test, performance is excellent, has the ability of extremely strong environment resistant corrosion; Can find out according to erosive wear unit weight loss result, the non-crystaline amorphous metal On Erosion in the present invention has extraordinary improvement result.Meanwhile, it is large that the non-crystaline amorphous metal in the present invention forms size, practical, and preparation technology is simple, is applicable to suitability for industrialized production.
Comparative example 1
Zr-Hf-Al-Ni quad alloy contrast properties test, non-crystaline amorphous metal preparation method and testing method identical with embodiment 1.Experimental raw proportioning is as follows, and numerical value is Elements Atom molar content.
Test result is as follows:
From comparative example 1 test result, less than Zr-Hf-Al-Ni quad alloy has compared with the non-crystaline amorphous metal in the present invention in hardness, environmental corrosion resisting ability, erosion-wear-resisting ability and formation size.
Comparative example 2
The performance test of common metal material contrast, test result is as follows:
From comparative example 2 test result, the non-crystaline amorphous metal in the present invention has very large lifting compared with corrosion-resistant, the abrasion resistance properties of common metal material.
Comparative example 3
Only add M1 part contrast properties test, non-crystaline amorphous metal preparation method and testing method identical with embodiment 1.Experimental raw proportioning is as follows, and numerical value is Elements Atom molar content.
M1 selects proportioning following (numerical value after the symbol of element is Elements Atom molar content):
Test result is as follows:
From comparative example 3 test result, although only the composition added in M1 has extraordinary improvement to hardness, environment resistant corrosive power and Anti-erosion wear resistance, effect is still not as good as the non-crystaline amorphous metal in embodiment 1.
Comparative example 4
Only add M2 part contrast properties test, non-crystaline amorphous metal preparation method and testing method identical with embodiment 1.Experimental raw proportioning is as follows, and numerical value is Elements Atom molar content.
M1 selects proportioning following (numerical value after the symbol of element is Elements Atom molar content):
Test result is as follows:
From comparative example 4 test result, although only the composition added in M2 has extraordinary improvement to hardness, environment resistant corrosive power and Anti-erosion wear resistance, effect is still not as good as the non-crystaline amorphous metal in embodiment 1.
Finally it should be noted that, above embodiment is only in order to illustrate the technical scheme of the embodiment of the present invention but not to be limited, although be described in detail the embodiment of the present invention with reference to preferred embodiment, those of ordinary skill in the art is to be understood that and still can modifies to the technical scheme of the embodiment of the present invention or equivalent replacement, and these are revised or be equal to the scope that replacement also can not make amended technical scheme disengaging embodiment of the present invention technical scheme.
Claims (8)
1. a non-crystaline amorphous metal for wear-and corrosion-resistant, is characterized in that: described non-crystaline amorphous metal consist of Zr
ahf
bal
cni
dm1
em2
f, wherein a, b, c, d, e, f are atomic molar percentage composition corresponding in described non-crystaline amorphous metal, are respectively 30≤a≤55,5≤b≤15,5≤c≤15,8≤d≤20,5≤e≤10,5≤f≤15; M1 is one or more mixtures in Si, Cr, Pt, Pd, Au, Ag element, and M2 is one or more mixtures in Cu, Zn, Mn, Fe element.
2. non-crystaline amorphous metal according to claim 1, is characterized in that: atomic molar percentage composition is respectively 40≤a≤55,5≤b≤10,10≤c≤15,10≤d≤20,5≤e≤8,8≤f≤15.
3. non-crystaline amorphous metal according to claim 1, is characterized in that: atomic molar percentage composition is respectively 45≤a≤55,8≤b≤10,10≤c≤15,12≤d≤20,5≤e≤8,8≤f≤12.
4. non-crystaline amorphous metal according to claim 1-3, is characterized in that: can also add the P element that atomic molar percentage composition is 0.1-2%.
5. prepare a method for non-crystaline amorphous metal as described in claim 1-3, it is characterized in that:
Step one, raw material purity being greater than 99.9% carries out proportioning according to above-mentioned non-crystaline amorphous metal composition;
Step 2, by the raw material that mixes in vacuum condition or argon gas atmosphere by arc melting or other conventional melting modes by raw material melting, can melt back 2-3 time, wherein vacuum tightness is 10
-1-10
-3pa, argon atmospheric pressure is 0.01-0.05MPa, obtains non-crystaline amorphous metal ingot casting after cooling;
Step 3, obtains above-mentioned non-crystaline amorphous metal product by inhaling the conventional non-crystaline amorphous metal preparation methods such as casting, die casting.
6. non-crystaline amorphous metal preparation method according to claim 5, is characterized in that: after melting, speed of cooling is 10
2-10
3k/s.
7. an application for non-crystaline amorphous metal described in claim 1-3, is characterized in that: described non-crystaline amorphous metal can be applicable in consumer electronics product, medical device product, aerospace industry, machine instrumentation industry and automotive industry.
8. an application for non-crystaline amorphous metal described in claim 1-3, is characterized in that: described non-crystaline amorphous metal can be used as wear-resistant, corrosion-resistant material and applies.
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| CN105220083A (en) * | 2015-10-21 | 2016-01-06 | 东莞宜安科技股份有限公司 | Non-crystaline amorphous metal of a kind of wear-and corrosion-resistant and its preparation method and application |
| CN105714216A (en) * | 2016-02-29 | 2016-06-29 | 宋佳 | High-tenacity and high-plasticity amorphous alloy and preparation method and application thereof |
| CN108411225A (en) * | 2018-03-27 | 2018-08-17 | 深圳市锆安材料科技有限公司 | A kind of zirconium-base amorphous alloy and preparation method thereof |
| CN111750014A (en) * | 2019-03-27 | 2020-10-09 | 泰明顿服务责任有限公司 | Friction lining, method for producing a friction lining and use of a friction lining |
| CN112063938A (en) * | 2020-09-27 | 2020-12-11 | 浙江大学台州研究院 | Amorphous alloy sewing machine needle and manufacturing method thereof |
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| CN108411225A (en) * | 2018-03-27 | 2018-08-17 | 深圳市锆安材料科技有限公司 | A kind of zirconium-base amorphous alloy and preparation method thereof |
| CN108411225B (en) * | 2018-03-27 | 2020-07-17 | 深圳市锆安材料科技有限公司 | Zirconium-based amorphous alloy and preparation method thereof |
| CN111750014A (en) * | 2019-03-27 | 2020-10-09 | 泰明顿服务责任有限公司 | Friction lining, method for producing a friction lining and use of a friction lining |
| CN111750014B (en) * | 2019-03-27 | 2023-10-24 | 泰明顿服务责任有限公司 | Friction lining, method for producing a friction lining and use of a friction lining |
| CN112063938A (en) * | 2020-09-27 | 2020-12-11 | 浙江大学台州研究院 | Amorphous alloy sewing machine needle and manufacturing method thereof |
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