CN105112817B - A kind of non-crystaline amorphous metal of wear-and corrosion-resistant and preparation method thereof - Google Patents
A kind of non-crystaline amorphous metal of wear-and corrosion-resistant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of non-crystaline amorphous metal of wear-and corrosion-resistant, consisting of ZraHfbAlcNidM1eM2f, wherein a, b, c, d, e, f is corresponding atomic molar percentage composition in the non-crystaline amorphous metal, and M1 is one or more mixture in Si, Cr, Pt, Pd, Au, Ag element, and M2 is one or more mixture in Cu, Zn, Mn, Fe element.To corrosive wear, erosive wear etc., because equipment is contacted with the fluid of motion, caused Special Corrosion is significantly improved the amorphous alloy material, while the amorphous alloy material forming property is good, preparation process is simple is adapted to industrialized production.
Description
Technical field
The present invention relates to a kind of wear-resistant corrosion resistant non-crystaline amorphous metal and preparation method thereof, relates in particular to a kind of wear-resisting
Damage corrosion resistant Zr base noncrystal alloys and preparation method thereof.
Background technology
Metallic material product will be damaged by the direct or indirect of multi-form in use, most common of which
Damage type is for abrasion and corrodes.Abrasion refers to that hardware and miscellaneous part interact, and is caused due to mechanical friction
Gradually damage, such as the abrasion between the wheel and rail of locomotive.Corrosion refers to that metal material, in the presence of surrounding medium, is gradually damaged
Bad or rotten, the corrosion of metal material is one of modal corrosion phenomenon.Metal material spreads all over the every field of national economy,
From daily life to national defense industry, as long as in place of using metal material, all inevitably there is galling with asking for corroding
Topic, not only causes economic loss, and some even cause catastrophic accident.In modern industry, for galling and corrosion
Problem expand substantial amounts of research, how to obtain wear-and corrosion-resistant metal material become current investigation of materials emphasis direction it
One.
In commercial Application, many plant equipment, electronic equipment often work under the environmental condition of very severe, such as high
Warm, damp and hot, salt fog and contact with sea water, soda acid etc. is contacted, these equipment do not require nothing more than good resistance to surrounding medium corrosion energy
Power, the corrosive wear being also required in tolerance work, erosive wear etc. are contacted and caused spy with the fluid of motion because of equipment
It is different to corrode.Domestic widely used alloy material mostly is ferrum system at present, reaches anti-corrosion property by adjusting the Cr contents in alloy
Can, such as rustless steel, expansion alloy, high temperature alloy etc., due to Fe sill easy-to-rust characteristics and conventional addition element Cr, Ni
Not environmentally property, the use of these conventional corrosion resistant alloys often do not reach requirement in special machine, and expensive.
Non-crystaline amorphous metal is a kind of new material for quickly growing in the last few years, because of its inherent high rigidity, high intensity, good
Good wear and corrosion behavior makes which extensively apply in fields such as military project, Aero-Space and petrochemical industry, such as in military industry field, Zr-W amorphous
Armor-piercing head made by alloy can reach very high density and intensity, and have from sharp effect, while having high Adiabatic Shear quick
Perception, Environmental compatibility are good.
Application No. 201310082019.0 it is entitled《A kind of Fe-based amorphous surfacing welding of wear-and corrosion-resistant and its preparation side
Method》Chinese patent, there is provided a kind of formula be Fe41Co7Cr15Mo14C15B6Y2（Atomic percentage）Fe-based amorphous welding rod, can be by
This obtains the amorphous/nanocrystalline composite overlaying layer with good wear corrosion resisting property.
Application No. 201210426268.2 it is entitled《A kind of high corrosion-resistant iron-based soft magnetic non-crystaline amorphous metal and its preparation side
Method》Chinese patent, molecular formula is FeaCrbNicModPeCfBgSih, a-h represent correspondence atom molar content.With it is existing
Iron-based soft magnetic non-crystaline amorphous metal compare, the non-crystaline amorphous metal simultaneously has high corrosion-resistant, high amorphous formation ability and excellent magnetic
Can, can be as electromagnetic device material in rugged environment, such as damp and hot salt fog, ammonia or various acid, sea water, sewage etc. corrode
Used in medium.
Although Fe base non-crystalline material excellent performances, there is soft magnet performance, and for corrosive wear, erosive wear etc.
Because equipment is contacted with the fluid of motion, caused Special Corrosion is without significantly improving.
The content of the invention
The invention provides a kind of not only wear-resistant but also corrosion resistant amorphous alloy material, and the amorphous alloy material is to corruption
Caused Special Corrosion is significantly improved because equipment is contacted with the fluid of motion for erosion abrasion, erosive wear etc., while the amorphous
Alloy material forming property is good, preparation process is simple, is adapted to industrialized production.
The technical problem to be solved is achieved by the following technical programs：
1st, composition of raw materials
The non-crystaline amorphous metal consists of ZraHfbAlcNidM1eM2f, during wherein a, b, c, d, e, f are the non-crystaline amorphous metal
Corresponding atomic molar percentage composition, respectively 30≤a≤55,5≤b≤15,5≤c≤15,8≤d≤20,5≤e≤10,5
≤f≤15；M1 is one or more mixture in Si, Cr, Pt, Pd, Au, Ag element, during M2 is Cu, Zn, Mn, Fe element
One or more mixture.
Further, above-mentioned non-crystaline amorphous metal atomic molar percentage composition is preferably 40≤a≤55,5≤b≤10,10≤c
≤ 15,10≤d≤20,5≤e≤8,8≤f≤15.
Still 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 alloys have higher glass forming ability, corrosion resistance and forming ability, add Hf of the same clan
Atom has certain metalepsis to Zr atoms in the alloy so that the active force in alloy between different metal atom strengthens,
Macro manifestations are good for the comparatively dense processability of alloy structure after cooling.On the one hand the addition of Al, Ni strengthens the non-crystaline amorphous metal
Forming ability, while has in corrosion of the Al and Ni elements to surrounding medium preferably resist effect, appropriate addition is beneficial to anti-corrosion
The lifting of performance.So adding Hf, Al, Ni in Zr base materials can obtain that forming property is good and the preferable amorphous conjunction of corrosion resisting property
Gold.
The alloying element for adding equilibrium potential higher in the alloy raises can the equilibrium potential of alloy, increased alloy whole
The thermodynamic stability of body, i.e., the solid solution structure for being formed between metal make atomic electron shell structure change, alloy
Energy changes, and free energy is reduced.In addible element, inventor is had found by many experiments, according to above-mentioned principle
One or more mixture in addition Si, Cr, Pt, Pd, Au, Ag element can increase substantially the stability of alloy, and
Strengthen the hardness and decay resistance of alloy.Simultaneously as solid solubility of the alloying element in solid solution is often limited, institute
Unsuitable high with the ratio for adding such alloying element, Jing experiments find that the alloy atom molar content of such addition is accounting for total
The 5-10% of alloy can reach good effect, preferably be further 5-8%.
Simultaneously can add in the alloy increases the alloying element of corrosion system resistance to lift corrosion resistant performance, inventor
Found by many experiments, adding one or more mixture in Cu, Zn, Mn, Fe element according to above-mentioned principle can promote
Alloy surface generates the corrosion product with protective effect so as to reduce corrosion current, and these micro corrosion products are insoluble in corruption
What erosion medium, resistance were high, fine and close is attached to alloy surface by alloy and corrosive medium isolation, extremely effective prevention corrosion process
Carrying out.And Cu, Zn, Mn, Fe element can form solid solution with parent metal and meet alloy to processability and mechanics
The requirement of performance, lifts the overall hardness of non-crystaline amorphous metal.To non-crystaline amorphous metal by adding the ratio of such alloying element at 5%
Overall performance tells on, and the atomic molar percentage composition of addition reaches as high as 15%, and preferred addition scope is 8-15%, further
Preferably 8-12%.
Further improve, the P element that atomic molar percentage composition is 0.1-2% in above-mentioned non-crystaline amorphous metal, can also be added.
Add Ni, Cr, Si, Cu, Zn, Pd, Mn, Fe element in non-crystaline amorphous metal, can be non-in one layer of alloy substrate Surface Realize after melting
The oxide of crystalline state, plays a good protection to alloy, and the addition of P element can promote the shape of this amorphous state oxide layer
Into.The addition content of P element is unsuitable too high, and atomic molar percentage composition is the effect that 0.1-2% can reach.
2nd, preparation method
Raw material of the purity more than 99.9% is carried out proportioning according to above-mentioned non-crystaline amorphous metal composition by step one, and material purity is determined
The quantity of impurity in raw material.Impurity excessively can not only absorb more oxygen element, be unfavorable for the shaping of non-crystaline amorphous metal and follow-up
Processing, and impurity can also form the generation of nuclei of crystallization impact non crystalline structure in molten metal.
Step 2, the raw material for mixing is passed through in vacuum condition or argon gas atmosphere electric arc melting or other conventional meltings
Mode by raw material melting, can melt back 2-3 time, wherein vacuum is 10-1-10-3Pa, argon atmospheric pressure are 0.01-
0.05MPa, obtains non-crystaline amorphous metal ingot casting after cooling.Repeatedly the purpose of melting be further lifted non-crystaline amorphous metal degree of purity,
Reduce the segregation of grain boundary impurities, make crystal boundary attenuate, the hardness of amorphous product not only can be increased on macro-effect, and can be carried
Rise the ability of the anticorrosive of non-crystaline amorphous metal product and abrasion.The pressure condition of vacuum and argon gas atmosphere in technique is all very
It is low, easily reach in actual production.
Further, after melting, rate of cooling is 102-103K/s is advisable.
Step 3, obtains above-mentioned non-crystaline amorphous metal product by inhaling the conventional non-crystaline amorphous metal preparation method such as casting, die casting.By upper
State the amorphous alloy material that technique prepares and can use any conventional method machine-shaping, without the restriction on processing conditionss, be adapted to
Produce in industrial applications.
Non-crystaline amorphous metal in the present invention can be applicable to consumer electronics product, medical device product, aerospace industry, machine
In instruments and meters industry and auto industry, especially can be applied as wear-resistant, corrosion-resistant material.
The present invention has the advantages that：
1st, in the present invention amorphous alloy material is wear-resistant, hardness is high.
2nd, the amorphous alloy material corrosion resistance and good in the present invention, especially to corrosive wear, erosive wear etc. because setting
The standby fluid with motion is contacted and caused Special Corrosion is significantly improved.
3rd, the amorphous alloy material in the present invention forms size up to 30mm, preparation process is simple, is adapted to industrialized production.
Specific embodiment
1st, embodiment 1
By raw material of the purity more than 99.9% according to the non-crystaline amorphous metal composition Zr in following tableaHfbAlcNidM1eM2fMatched somebody with somebody
Than wherein a, b, c, d, e, f are corresponding atomic molar percentage composition in non-crystaline amorphous metal.M1 is that Si, Cr, Pt, Pd, Au, Ag are first
One or more mixture in element, M2 are one or more mixture in Cu, Zn, Mn, Fe element.
M1, M2 select proportioning as follows（Numerical value after the symbol of element is Elements Atom molar content）：
By the raw material for mixing in argon gas atmosphere by electric arc melting or other conventional melting modes by raw material melting, instead
Remelt is refined 3 times, and argon atmospheric pressure is 0.05MPa, and non-crystaline amorphous metal ingot casting is obtained after cooling.Argon atmospheric pressure is in allowed band
Interior change does not affect fusion process.After melting, rate of cooling is 102-103In the range of K/s is, depending on concrete alloying component
It is fixed, change in allowed band on non-crystaline amorphous metal product without impact.Above-mentioned non-crystaline amorphous metal product is obtained finally by pressure casting method,
Product is tested.
Vickers hardness test, environmental corrosion test, wherein erosive wear test, Vickers hardness are carried out to non-crystaline amorphous metal product
Test basis《GB/T 7997-2014 hard alloy vickers hardness test methods》Carry out, unification is tested from HV5, ring
Border corrosion test is chosen《GB/T 10125-2012 artificial atmosphere corrosion testing salt spray tests》In acetic acid salt spray test.Punching
Erosion wear testing is nonstandard test, and test condition is：The quartz sand of 20-80 mesh is selected as erosion particle, in normal temperature and pressure bar
Sprayed to test surfaces with erosion speed 10m/s under part, concentration is 8% to erosion particle in the slurry, and impact angle is 45 degree, most
Erosive wear unit weight loss is tested eventually.
Test result is as follows：
From 1 test result of embodiment, the non-crystaline amorphous metal hardness in the present invention is high, shows excellent in salt spray corrosion test
It is different, there is the ability of extremely strong environment resistant corrosion；Can be seen that according to erosive wear unit weight loss result, the amorphous in the present invention is closed
Golden On Erosion has extraordinary improvement result.Meanwhile, the non-crystaline amorphous metal in the present invention forms size greatly, practical, system
Standby process is simple, is adapted to industrialized production.
Comparative example 1
The test of Zr-Hf-Al-Ni quaternary alloys contrast properties, non-crystaline amorphous metal preparation method and method of testing and 1 phase of embodiment
Together.Experimental raw proportioning is as follows, and numerical value is Elements Atom molar content.
Test result is as follows：
From 1 test result of comparative example, Zr-Hf-Al-Ni quaternary alloys are in hardness, environmental corrosion resisting ability, erosion resistance
Less than wear resistance and being formed have compared with the non-crystaline amorphous metal in the present invention in size.
Comparative example 2
Common metal material contrast properties are tested, and test result is as follows：
From 2 test result of comparative example, the non-crystaline amorphous metal in the present invention is corrosion-resistant, wear-resisting compared with common metal material
Damaging performance has very big lifting.
Comparative example 3
Only add the contrast properties test of M1 parts, non-crystaline amorphous metal preparation method and method of testing are same as Example 1.It is real
Test proportioning raw materials as follows, numerical value is Elements Atom molar content.
M1 selects proportioning as follows（Numerical value after the symbol of element is Elements Atom molar content）：
Test result is as follows：
From 3 test result of comparative example, although the composition in only addition M1 is to hardness, environment resistant corrosive power and anti-impact
Erosion wear resistance has extraordinary improvement, but effect still not as good as the non-crystaline amorphous metal in embodiment 1.
Comparative example 4
Only add the contrast properties test of M2 parts, non-crystaline amorphous metal preparation method and method of testing are same as Example 1.It is real
Test proportioning raw materials as follows, numerical value is Elements Atom molar content.
M1 selects proportioning as follows（Numerical value after the symbol of element is Elements Atom molar content）：
Test result is as follows：
From 4 test result of comparative example, although the composition in only addition M2 is to hardness, environment resistant corrosive power and anti-impact
Erosion wear resistance has extraordinary improvement, but effect still not as good as the non-crystaline amorphous metal in embodiment 1.
It is last it should be noted that above example is only to illustrate the technical scheme of the embodiment of the present invention rather than which is entered
Row is limited, although being described in detail to the embodiment of the present invention with reference to preferred embodiment, one of ordinary skill in the art
It should be understood that still the technical scheme of the embodiment of the present invention can be modified or equivalent, and these are changed or wait
Amended technical scheme can not be also made to depart from the scope of embodiment of the present invention technical scheme with replacement.
Claims (7)
1. a kind of non-crystaline amorphous metal of wear-and corrosion-resistant, it is characterised in that：The non-crystaline amorphous metal consists of ZraHf
bAlcNidM1eM2f, wherein a, b, c, d, e, f is corresponding atomic molar percentage composition in the non-crystaline amorphous metal, distinguishes 40
≤ a≤55,5≤b≤10,10≤c≤15,10≤d≤20,5≤e≤8,8≤f≤15；M1 is the one kind in Si, Cr element
Or various mixture, M2 is one or more mixture in Zn, Mn element.
2. non-crystaline amorphous metal according to claim 1, it is characterised in that：Atomic molar percentage composition respectively 45≤a≤55,8
≤ b≤10,10≤c≤15,12≤d≤20,5≤e≤8,8≤f≤12.
3. the non-crystaline amorphous metal as described in claim 1-2 is arbitrary, it is characterised in that：It is 0.1-2% also to add atomic molar percentage composition
P elements.
4. a kind of method for preparing the non-crystaline amorphous metal as described in claim 1-3 is arbitrary, it is characterised in that：
Raw material of the purity more than 99.9% is carried out proportioning according to above-mentioned non-crystaline amorphous metal composition by step one；
Step 2, by the raw material for mixing in vacuum condition or argon gas atmosphere by electric arc melting or other conventional melting modes
By raw material melting, melt back 2-3 time, wherein vacuum are 10-1-10-3Pa, argon atmospheric pressure are 0.01-0.05MPa,
Non-crystaline amorphous metal ingot casting is obtained after cooling；
Step 3, obtains above-mentioned non-crystaline amorphous metal product by conventional non-crystaline amorphous metal preparation method.
5. non-crystaline amorphous metal preparation method according to claim 4, it is characterised in that：After melting, rate of cooling is 102-103K/s。
6. a kind of application of the non-crystaline amorphous metal as described in any one of claim 1-3, it is characterised in that：The non-crystaline amorphous metal can be applied
In consumer electronics product, medical device product, aerospace industry, machine instrumentation industry and auto industry.
7. a kind of application of the non-crystaline amorphous metal as described in any one of claim 1-3, it is characterised in that：The non-crystaline amorphous metal can conduct
Wear-resistant, corrosion-resistant material is applied.
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| CN105220083B (en) * | 2015-10-21 | 2017-05-31 | 东莞宜安科技股份有限公司 | A kind of non-crystaline amorphous metal 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 |
| 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 |
| DE102019107915B4 (en) * | 2019-03-27 | 2022-11-03 | Tmd Friction Services Gmbh | Use of aluminum alloys for corrosion protection in friction linings |
| 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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