CN106676352B - The low cost and high performance high Ca/Al ratio Mg-XAl-YCa-ZZn alloy of one kind and preparation method - Google Patents
The low cost and high performance high Ca/Al ratio Mg-XAl-YCa-ZZn alloy of one kind and preparation method Download PDFInfo
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- CN106676352B CN106676352B CN201611109220.3A CN201611109220A CN106676352B CN 106676352 B CN106676352 B CN 106676352B CN 201611109220 A CN201611109220 A CN 201611109220A CN 106676352 B CN106676352 B CN 106676352B
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 77
- 239000000956 alloy Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- 239000006104 solid solution Substances 0.000 claims abstract description 16
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 238000009749 continuous casting Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001125 extrusion Methods 0.000 claims description 17
- 238000005266 casting Methods 0.000 claims description 10
- 229910018137 Al-Zn Inorganic materials 0.000 claims description 8
- 229910018573 Al—Zn Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 238000000265 homogenisation Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000011282 treatment Methods 0.000 claims description 4
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 238000005728 strengthening Methods 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 238000005204 segregation Methods 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims 2
- 230000000171 quenching effect Effects 0.000 claims 1
- 239000011575 calcium Substances 0.000 abstract description 65
- 239000011777 magnesium Substances 0.000 abstract description 42
- 229910000861 Mg alloy Inorganic materials 0.000 abstract description 30
- 230000007797 corrosion Effects 0.000 abstract description 20
- 238000005260 corrosion Methods 0.000 abstract description 20
- 239000013078 crystal Substances 0.000 abstract description 8
- 239000003063 flame retardant Substances 0.000 abstract description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000010304 firing Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 229910017706 MgZn Inorganic materials 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000007670 refining Methods 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000010287 polarization Effects 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910021323 Mg17Al12 Inorganic materials 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001192 hot extrusion Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- -1 magnesium-calcium-aluminium Chemical compound 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Extrusion Of Metal (AREA)
Abstract
The invention discloses a kind of Mg-XAl-YCa-ZZn alloy and preparation methods.The alloy includes following components, and Ca=2-4wt%, Al=2-4wt%, Zn=2.9-6wt%, surplus is the solid solution of Mg or Mg, and Ca/Al mass ratio is 0.8-1.2 in alloy.The alloy by direct water-cooling semi-continuous casting, obtain surround Mg matrix containing netted Al2The microscopic structure of Ca and the solid solution structure of granular MgZn phase, using squeezing into step refining crystal grain, while by Al2Ca and Ca2Mg6Zn3Reticular structure be sufficiently broken into the particle of micron and sub-micron, it is tiny to obtain even tissue, crystal grain, the apparent composite material of invigoration effect.The present invention is low in cost, and resulting materials are light and mechanical property, flame retardant property, corrosion resistance and processing performance are very excellent, overcome perishable existing magnesium alloy, easy firing and are difficult to the defects of processing.There is high industrial application value in every field.
Description
Technical field
The invention discloses a kind of Mg-XAl-YCa-ZZn alloy and preparation methods, it is a kind of low cost and high performance
The Mg-Ca-Al-Zn alloy and preparation method of high Ca/Al ratio；Belong to magnesium alloy or magnesium-based composite material preparation technical field.
Background technique
Magnesium alloy has the characteristics that high specific strength, dimensional stability are high, machining property is good and is easily recycled.?
The industries such as automobile, aerospace, electronics have broad application prospects.However magnesium alloy is perishable, easy firing, is difficult to be thermally processed into
Type so that the large-scale industrialization application of magnesium alloy is restricted, therefore improve magnesium alloy processing performance, improve it is anticorrosive
Performance and ignition temperature are always an important topic of magnesium alloy research.The ignition temperature of most of existing magnesium alloys is not
Height usually adds rare earth element in alloy substrate, is such as added into AZ91 alloy for the ignition temperature for improving magnesium alloy
Burning point reaches 750 DEG C after 0.3wt%Be, and burning point reaches 724 DEG C after 1wt%Ce is added；1wt%La is added into ZM5 magnesium alloy
The burning point of alloy reaches 711 DEG C, and 0.12wt% mischmetal burning point is added and reaches 820 DEG C.This undoubtedly increases magnesium alloy cost
And quality.
In the sixties in last century, researcher finds that the creep properties that Ca element is added in Mg-Al alloy and is conducive to improve alloy
Energy and flame retardant property.Solid solubility of the calcium in magnesium is small, maximum value 0.82at.%, is added in Mg- (3~5%) Al magnesium alloy
Ca starts Al occur2Ca phase, when Ca/Al ratio is more than 0.8, β-Mg17Al12It disappears, raw webbed Al2Ca phase.But due to
Al2Ca is hard crisp phase, and the additive amount of Ca can excessively cause the degradation of mechanical property of cast magnesium alloys, all such as intensity and plasticity
It is lower, its use is seriously affected, if Mg-5Ca-5Al alloy casting state yield strength is 105MPa, tensile strength 110MPa prolongs
Rate is stretched less than or equal to 1.5%；Therefore when keeping high Ca/Al, it should control the additional amount of Ca as far as possible.
Summary of the invention
Inventor has done further research on the basis of original patent (application No. is 201510577402.2), meaning
Have found that the room temperature extension property of material is obviously improved after suitable Zn is added outside.The material is also equipped with simultaneously
The characteristics such as intensity is high, specific gravity is small, corrosion resistance is good, ignition temperature is high.
A kind of Mg-XAl-YCa-ZZn alloy of the present invention, including following components, form by mass percentage:
Ca=2-4%, Al=2-4%, Zn=2.9-6%, surplus are the solid solution of Mg or Mg, and in alloy
Ca/Al mass ratio is 0.8-1.2.
As preferred；A kind of Mg-XAl-YCa-ZZn alloy of the present invention, including following components, form by mass percentage:
Ca=2.2-2.6%, Al=2.45-2.88%, Zn=2.9-5%, surplus are the solid solution of Mg or Mg, and Ca/Al in alloy
Mass ratio is 0.8-1.2.
As a further preference；A kind of Mg-XAl-YCa-ZZn alloy of the present invention, including following components, by quality percentage
Than composition: Ca=2.3%, Al=2.47%, Zn=2.9-3.0%, surplus are the solid solution of Mg or Mg.
As a further preference；Another kind Mg-XAl-YCa-ZZn alloy of the invention, including following components, by quality hundred
Divide than composition: forming by mass percentage: Ca=2.55%, Al=2.65%, Zn=4.8-5%, surplus are consolidating for Mg or Mg
Solution
A kind of Mg-XAl-YCa-ZZn alloy of the present invention, the solid solution element in the solid solution of the Mg is Li, Mn, RE, Zr
At least one of.Those skilled in the art should be understood that the additional amount of solid solution element, it should be ensured that the solid solution element of addition is in the base
Without precipitate.As a further preference, the Mn that the Mg-XAl-YCa-ZZn alloy is also 0.57% containing quality percentage.
A kind of Mg-Ca-Al-Zn alloy of the present invention is evenly distributed in the matrix and crystal boundary of the Mg-Al-Ca-Zn alloy
Al2Ca particle and Ca2Mg6Zn3Particle.The Al2Ca particle and Ca2Mg6Zn3Particle is high temperature disperse phase Al2Ca particle and
Ca2Mg6Zn3Particle.
A kind of preparation method of Mg-XAl-YCa-ZZn alloy of the present invention, includes the following steps:
Step 1: by the alloy compositions proportion of design, with the intermediate alloy for taking Al, Ca and Mg or Mg and solid solution element；It is logical
Direct water-cooling semi-continuous casting or chilling casting are crossed, alloy cast ingot is made；
Step 2: being heated to 345-395 DEG C of heat preservation 8- after Mg-Ca-Al-Zn alloy cast ingot vehicle is removed appearance surface oxidized skin
24 hours, carry out Homogenization Treatments, removal segregation；
Step 3: the ingot casting after Homogenization Treatments is squeezed in the extrusion cylinder for being preheated to 350-380 DEG C, squeezing temperature is
400-420 DEG C, obtain bar.
It is cold when a kind of preparation method of Mg-XAl-YCa-ZZn alloy of the present invention, water cooling semi-continuous casting or chilling are cast
But speed is 50-120 DEG C/s.
A kind of preparation method of Mg-XAl-YCa-ZZn alloy of the present invention, it is netted that second step acquisition surrounds containing for Mg matrix
Al2The microscopic structure of Ca and the solid solution structure of granular MgZn phase.
A kind of preparation method of Mg-XAl-YCa-ZZn alloy of the present invention, extrusion speed 0.5-2.5m/min, extrusion ratio
For 15-25.
A kind of preparation method of Mg-XAl-YCa-ZZn alloy of the present invention, in cast alloy matrix, Al2Ca and Ca2Mg6Zn3
The Al that particle is formed along cast alloy matrix2Ca reticular structure is distributed in situ, Al after extruding2Ca and Ca2Mg6Zn3Particle
Granularity is 0.1-2 microns, and alloy substrate grain size is 0.5-5 microns, Al2Ca and Ca2Mg6Zn3It is High-Temperature Strengthening phase.
A kind of preparation method of Mg-XAl-YCa-ZZn alloy of the present invention, when prepared alloy includes by mass percentage
When Ca=2.3%, Al=2.47%, Zn=2.98%, Mn=0.57%, the room temperature tensile intensity of As-extruded alloy is
350MPa, yield strength 300MPa, elongation percentage 10%.When prepared alloy includes Ca=by mass percentage
2.55%, when Al=2.65%, Zn=4.97%, Mn=0.57%, the room temperature tensile intensity of As-extruded alloy is 360MPa, bends
Take intensity be 340MPa, elongation percentage 9.0%.
The present invention uses Ca/Al mass ratio=0.8-1.2 component proportion, is cast, is mentioned using semi-continuous casting or chilling
For the cooling velocity that is exceedingly fast, it is made the alloy cast ingot with fine isometric crystal grains, there are netted Al in alloy substrate tissue2Ca phase
With graininess Ca2Mg6Zn3Then phase utilizes extrusion process means, on the one hand, keep alloy substrate crystal grain more tiny；Another party
Face, sufficiently broken high calcium aluminium are broken for micron and/or submicron particles, close magnesium-calcium-aluminium than the reticular structure of alloy
Gold becomes Mg (α-Mg)-Al2Ca-Ca2Mg6Zn3Generated in-situ composite material, both are mutually high temperature disperse phase, in time very well
Solid solubility temperature will not be dissolved into the matrix of Mg, therefore greatly increase the yield strength of the material, elevated temperature strength, stretch
Long rate, ignition temperature, corrosion resistance and processing performance.
Compared with existing technologies, the invention has the benefit that
Mg-Ca-Al-Zn As-extruded alloy yield strength prepared by the present invention is about 300MPa, elongation 10-15%,
The addition of alloy element Zn considerably increases its plasticity；There is higher-strength in 175-250 DEG C of temperature range；The material has good
Good corrosion resistance, at a temperature of 30 DEG C in the total immersion test of 3.5%NaCl solution, corrosion rate is better than under equal conditions
AZ31.Bar after extruding does not crack yet in rolling reduction 80%, has cashed its good processability.
It can be seen that Mg-Ca-Al-Zn alloy prepared by the present invention has good mechanical property, higher high temperature strong
Degree, very high ignition temperature, very high corrosion resistance and superplasticity, overcome perishable existing magnesium alloy, easy firing, are difficult to
The defects of hot-working.The alloy invention is somewhat solving perishable magnesium alloy, easy firing, is being difficult to hot worked difficulty
Topic, can effectively expand the application value of magnesium alloy industrially.
The alloy invention is than patent (201510018019.3) high alumina high calcium, high Ca/Al ratio of application before applicant
Mg-Ca-Al alloy has higher plasticity, better corrosion resistance, more good processing performance, lighter specific gravity, mechanics
Performance, elevated temperature strength, flame retardant property and superplasticity are suitable therewith, somewhat solve perishable magnesium alloy, easy firing,
It is difficult to hot worked problem, has more industrial application value.
Detailed description of the invention
Attached drawing 1 is microscopic structure of the embodiment of the present invention 1 using the as cast condition Mg-2Ca-2Al-3Zn of continuous casting process preparation
And EDS analysis chart.
Attached drawing 2 is the Mg-2Al-2Ca-3Zn ingot casting of the embodiment of the present invention 1 through microscopic structure after extruding.
Attached drawing 3 is the sample topography figure after the immersion test that the embodiment of the present invention 2 is As-extruded Mg-2Al-2Ca-3Zn.
4 embodiment of the present invention 2 of attached drawing is the polarization curve after the electrochemical test of As-extruded Mg-2Al-2Ca-3Zn.
5 embodiment of the present invention 3 of attached drawing is that the Temperature-time of the burning point test of As-extruded Mg-2Al-2Ca-3Zn and AM80 is bent
Line.
Scheme the SEM that a is as cast condition Mg-2Ca-2Al-3Zn in attached drawing 1 to scheme；Fig. 1 b is the EDS figure for scheming A point in a, and Fig. 1 c is figure a
The EDS of middle B point schemes, from attached drawing 1 as can be seen that microstructure the second phase overwhelming majority of Mg-2Ca-2Al-3Zn alloy is
Al2Ca, while also some MgZn phases.Al2Ca has C15 structure and is stable, and Mg in equilibrium state2Ca is then not so good as Al2Ca
It is so stable.573K at a temperature of, (Mg, Al)2Ca can be to Al2Ca is changed；In addition, the alloy is using direct water-cooling half
Continuously casting, cooling velocity bigger (102DEG C/s), promote Al2Ca is preferentially precipitated, it is suppressed that Mg2Ca and (Mg, Al)2Ca analysis
Out, and promote Mg2Ca+(Mg,Al)2Ca is to Al2Ca transformation.(black bar is Al in figure2Ca particle, white are alloy-based
Body).
From attached drawing 2 as can be seen that as cast condition Mg-2Ca-2Al-3Zn alloy Al after squeezing2Ca is sufficiently crushed, and is not occurred
Phase transformation and melting, are uniformly distributed along the direction of extrusion.Crystal grain becomes fine uniform after extruding, and the smallest crystallite dimension can achieve
1μm。
Fig. 3 a is the shape appearance figure after the soak test of AZ31, and Fig. 3 b is that embodiment 2 is As-extruded Mg-2Al-2Ca-3Zn
Shape appearance figure after immersion test.From attached drawing 3 as can be seen that after impregnating under the same conditions, Mg-2Ca-2Al-3Zn surface topography
It is better than AZ31, does not occur apparent etch pit, corrosive nature is good.
Fig. 4 a is the polarization curve that embodiment 2 is As-extruded Mg-2Al-2Ca-3Zn, and Fig. 4 b is the polarization curve of AZ31
Figure；From attached drawing 4 as can be seen that electrochemical test, Mg-2Ca-2Al-3Zn corrosion potential are higher than AZ31, corruption under the same conditions
It loses current density and is lower than AZ31, illustrate that Mg-2Ca-2Al-3Zn corrosion resistance is more preferable.
From attached drawing 5 as can be seen that Mg-2Ca-2Al-3Zn burning point be 890 DEG C, significantly larger than the 566 of AZ80 DEG C, AZ91's
590 DEG C, 644 DEG C of WE43.Excellent fireproof performance can satisfy the requirement of specified conditions, such as aerospace field.
Specific embodiment:
The embodiment of the present invention uses following preparation method and detection means:
Raw material be pure magnesium ingot, fine aluminium ingot, magnesium calcium intermediate alloy and zinc ingot metal, use semi-continuous casting obtain diameter for
The Mg-Ca-Al-Zn ingot casting of the high Ca/Al ratio of 170mm.
Squeeze test carries out on XJ1250 type horizontal extruder, and magnesium alloy ingot vehicle is removed appearance surface oxidized skin, obtainsThe spindle of mm × 250mm, spindle to be extruded Homogenization Treatments 12h in 400 DEG C of electric furnaces, is then being preheated to 350-380
DEG C extrusion cylinder in squeeze, obtain diameter 40mm bar, extrusion speed 0.5-2.5m/min, extrusion ratio 15-25.
Extruded Magnesium Alloy is sampled, is corroded after grinding and buffing with the corrosive agent prepared, corrosive agent ingredient is
10mL acetic acid+4.2g picric acid+10mL distilled water+70mL ethyl alcohol, is then observed under metallographic microscope and scanning electron microscope micro-
Tissue.
Using 3382 universal testing machine of Instron carry out tensile property test, tensile sample be cross section 2mm ×
6mm, the sheet specimens of gauge length 15mm, test rate of extension are 0.5mm/min.
Burning point test is carried out to the Mg-2Ca-2Al-3Zn ingot casting for being processed into side length 10mm using crucible electrical resistance furnace, while right
AZ80 magnesium alloy carries out burning point test to compare.
Mg-2Ca-2Al-3Zn sample is subjected to total immersion test at 30 DEG C in 3.5%NaCl solution, while to AZ31 magnesium
Alloy does same test to compare.Electrochemical test carries out in 5%NaCl solution at 30 DEG C, carries out before polarization curve test
The open circuit potential of 10min is tested, to guarantee to reach stable state.
Mg-2Al-2Ca-3Zn ingredient and density are as follows in the embodiment of the present invention:
| Al (wt.%) | Ca (wt.%) | Zn (wt.%) | Mn (wt.%) | Density (gcm-3) |
| 2.47 | 2.3 | 2.98 | 0.57 | 1.74 |
Embodiment 1
The room temperature tensile properties of As-extruded Mg-2Ca-2Al-3Zn alloy are as shown in table 1, the microscopic structure of sample such as Fig. 1
Shown, As-extruded fine microstructures are uniform, wherein Al2Ca and Ca2Mg6Zn3It is extruded sufficiently broken, the distribution change on magnesium matrix
It obtains uniformly, to improve tensile property.It is organized finer and close the defects of the lockhole shrinkage porosite of organization internal by soldering after hot extrusion
Continuously.Crystal grain is elongated, to increase the surface area of crystal boundary, improves resistance of deformation.Meanwhile being solid-solubilized in the portion in magnesium matrix
The elements such as Zn are divided to be capable of forming KESHI gas mass, pinning dislocation plays the role of solution strengthening.The extrusion process parameters of the present embodiment
For extrusion ratio 16,420 DEG C of temperature, extruding rate 0.5-2.5m/min are squeezed, since extrusion ratio is 16, is arrived if increasing extrusion ratio
20-40, then above-mentioned performance can also greatly improve.
There is the transformation of the second phase at different temperatures due to being added after alloy element Zn, heat treatment can be passed through
Strengthen.Mg-2Ca-2Al-3Zn is dissolved 12h at 420 DEG C, and then hardness increases 20% after 250 DEG C of timeliness 18h, surrender
Intensity can also further increase.
The room temperature tensile properties of 1 As-extruded Mg-2Ca-2Al-3Zn alloy of table
| Yield strength (MPa) | Tensile strength (MPa) | Elongation percentage (%) | |
| Mg-2Al-2Ca-3Zn | 300 | 350 | 10.0 |
The content for further adjusting Zn, is prepared for Mg-3Ca-3Al-5Zn alloy (ingredient are as follows: Mg-2.55Ca-2.65Al-
4.97Zn-0.57Mn), it is squeezed using 400 DEG C, extrusion ratio obtains the performance such as table 2 for 16.
The room temperature tensile properties of 2 As-extruded Mg-3Ca-3Al-5Zn alloy of table
| Yield strength (MPa) | Tensile strength (MPa) | Elongation percentage (%) | |
| Mg-3Al-3Ca-5Zn | 340 | 360 | 9.0 |
Its yield strength of Mg-Ca-Al-Zn alloy of the invention is 300-340MPa, tensile strength 350- as known from Table 1
360MPa and elongation percentage still has 9-10%, can preferably be used for structural material, specific strength is also higher.Elongation percentage so makes
It obtains it and possesses preferable machining deformation ability
Embodiment 2
Table 2 is total immersion test result of the Mg-2Ca-2Al-3Zn and AZ31 at 30 DEG C in 3.5%NaCl solution.It can see
Mg-2Al-2Ca-3Zn corrosion rate is about that AZ31 is less than AZ31 out, is even better than added to the WE43 of rare earth element.Its reason
Mainly a large amount of Al2The formation of Ca phase inhibits β-Mg17Al12It is mutually formed, the α-Mg and β-that the reallocation of Al element avoids
Mg17Al12Galvanic corrosion between phase increases the corrosion potential of magnesium alloy, and corrosion electric current density reduces, to hinder
The corrosion of magnesium alloy.From attached drawing 4 as can be seen that the corrosion electric current density of Mg-2Al-2Ca-3Zn is less than AZ31, illustrate Mg-2Al-
2Ca-3Zn corrosion resistance is more preferable.Meanwhile in anode part, electric current increases sharply with the increase of voltage, and alloy is not blunt
Change, this shows that corrosion product is weaker to alloy protective effect.This is because corrosion product Mg (OH)2And Cl-1Reaction forwarding is can
Dissolubility magnesium chloride.
The total immersion test result of table 2 Mg-Ca-Al alloy and AZ31 and WE43
| Alloy | Corrosion rate (gcm-2·d-1) |
| Mg-2Al-2Ca-3Zn | 9.6 |
| AZ31 | 18.7 |
| WE43 | 12.1 |
Embodiment 3
Table 3 is that compared Mg-2Ca-2Al-3Zn, the burning point of AZ80, AZ91 and WE43, it is clear that Mg-2Ca-2Al-
3Zn burning point is higher by existing commercial magnesium alloy significantly, is even more than added to the WE43 of rare earth.This will be advantageous to magnesium alloy and exist
The use in fire-retardant and specific environment in melting, has widened the application of magnesium alloy.Its reason is mainly the addition of Ca can be with
The compactness for increasing Mg alloy surface oxidation film, in the case where molten metal receives disturbance, oxidation film containing Ca has preferably certainly
Repairing regenerating ability.Contain a large amount of high-melting-point stable phase Al in tissue simultaneously2Ca (1079 DEG C of fusing point) hinders the burning of magnesium,
Improve flame retardant property.With the increase of Ca and Al content in Mg-XCa-YAl-ZZn, flame retardant property can be further increased.
The burning point of table 3 Mg-2Ca-2Al-3Zn and remaining common magnesium alloy
| Alloy | Burning point (DEG C) |
| Mg-2Ca-2Al-3Zn | 890 |
| AZ80 | 566 |
| AZ91 | 590 |
| WE43 | 644 |
By the data of above embodiments it can be seen that Mg-xCa-yAl-3Zn alloy prepared by the present invention have it is good
Mechanical property, higher elevated temperature strength, excellent flame retardant property and corrosion resistance, it is perishable, easy to overcome existing magnesium alloy
It burns, be difficult to the defects of hot-working, be conducive to the practical application of magnesium alloy.
Claims (6)
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| CN105132769A (en) * | 2015-09-11 | 2015-12-09 | 湖南大学 | Low-Al low-Ca and high-Ca/Al-ratio Mg-Ca-Al alloy and preparing method of low-Al low-Ca and high-Ca/Al-ratio Mg-Ca-Al alloy |
| CN105143483A (en) * | 2013-03-14 | 2015-12-09 | 德普伊新特斯产品公司 | Magnesium alloy with adjustable degradation rate |
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| CN104532093A (en) * | 2015-01-14 | 2015-04-22 | 湖南大学 | Mg-Ca-Al alloy and preparation method |
| CN105132769A (en) * | 2015-09-11 | 2015-12-09 | 湖南大学 | Low-Al low-Ca and high-Ca/Al-ratio Mg-Ca-Al alloy and preparing method of low-Al low-Ca and high-Ca/Al-ratio Mg-Ca-Al alloy |
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