CN105154733B - A kind of non-rare earth cast magnesium alloy and preparation method thereof - Google Patents
A kind of non-rare earth cast magnesium alloy and preparation method thereof Download PDFInfo
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Abstract
The present invention is a kind of non-rare earth cast magnesium alloy, and the alloy is Mg Bi Zr Zn alloys, and the percentage by weight of its component is：0.5~8wt% of Bi；0.35~1.0wt% of Zr；0.1~2.0wt% of Zn, surplus is Mg.The present invention is that Zr elements significant Grain Refinement Effect in Mg Bi alloy systems is found that on the basis of Mg Bi, so as to improve the intensity and plasticity of alloy.It is aided with a small amount of Zn-ef ficiency to improve the intensity of alloy, so that high-strength cast magnesium alloy is developed in the alloy series, the 155MPa of yield strength 140, the 285MPa of tensile strength 245, elongation percentage is 6.5% or so.
Description
Technical field
The present invention relates to a kind of magnesium alloy and preparation method thereof, more particularly to a kind of inexpensive non-rare-earth type cast magnesium alloy
And preparation method thereof, belong to class of metal materials and field of metallurgy；The novel magnesium alloy can be used as potential heat resistance magnesium alloy and life
Thing Medical magnesium alloy material.
Background technology
Magnesium alloy is most light structural metallic materials, and high with specific strength height, specific stiffness, capability of electromagnetic shielding is good, casting
Function admirable, easy machining and many advantages, such as be easily recycled has obtained increasingly extensive application.In existing magnesium
In the application of alloy, the ratio shared by cast magnesium alloy reaches more than 90%, is mainly used in automobile, aircraft, 3C Product and military affairs
In field with meet loss of weight, inhale make an uproar, the requirement of damping and radiation proof.In the automotive industry, fuel oil will be improved by reducing automotive dead weight
Utilization rate, and low exhaust gas emission drops.The 60% fuel used deadweight for being consumed in automobile of automobile, automobile is per loss of weight 10%, oil consumption
8-10% will be reduced.Simultaneously automotive light weight technology can increase the carrying capacity and payload of vehicle, can also improve brake and
Acceleration, significantly improves the noise and oscillation phenomenon of vehicle.The larger commercial cast magnesium alloy of usage amount include AZ91D,
AM50, AM60B, AS41 and AE42 etc., but the intensity of magnesium alloy is not high, and this causes the part as stressed member using magnesium alloy
Have to increase wall thickness, which increase cost, and light-weighted advantage is weakened, so as to constrain further pushing away for magnesium alloy
Wide application；In addition, the performance of the magnesium alloy parts of high Al content at high temperature is decreased obviously, Long-term service temperature can not surpass
Cross 120 DEG C.Therefore solved the above problems in the urgent need to developing low-cost high-strength magnesium alloy.
By introducing substantial amounts of hardening constituent in the magnesium alloy, while crystal grain thinning, it is possible to achieve the reinforcing of magnesium alloy with
Toughening, develops the magnesium alloy with higher-strength.In the prior art, CN102978497A discloses a kind of high-toughness casting magnesium
Alloy, the percentage by weight of its constituent is respectively：Zn 6.0~8.0%, 0.5~1.5wt% of Al, Cu 0.5~
1.0%th, Mn 0.3~0.7%, remaining is magnesium and a small amount of inevitable impurity element, the alloy after solid solution and Ageing Treatment
Tensile strength is not less than 305MPa, and yield strength is not less than 205MPa, and elongation percentage is not less than 10%, with excellent resultant force
Learn performance.But the alloy contains the higher simple metal metal of the fusing points such as Cu and makees raw material, and to coordinate (small not less than 24 for a long time
When) solution treatment and two-stage time effect processing, preparation technology is complicated.CN102534330A discloses a kind of high-strength casting magnesium and closed
Gold, the percetage by weight of the component of the alloy is Gd 8~14%, Y 1~5%, Al 0.6~2%, and remaining is magnesium and can not kept away
The impurity element exempted from, after solid solution and Ageing Treatment, the tensile strength of the alloy is between 300~355MPa, yield strength
Between 210~255MPa, elongation percentage is between 2~8%, and with higher intensity, but elongation percentage is relatively low, and is needed in the alloy
The rare earth element costly such as substantial amounts of Gd, Y is added, the cost of alloy is directly increased, and adds the density of alloy,
Also result in cast form degradation.CN1752251 discloses a kind of high-strength magnesium alloy and preparation method thereof, and it is constituted into
Point percentage by weight be respectively：2.5~3.6wt% of Nd, 0.35~0.8wt% of Zr, Zn contents are not more than 0.4wt%, Ca
Content is not more than 0.5wt%, and remaining is magnesium and inevitable impurity.The alloy is after solid solution and Ageing Treatment, with higher
Mechanical property, 280~320MPa of tensile strength, 140~155MPa of yield strength, elongation percentage 5~12%, and same in alloy
Sample contains more noble element (2.5~3.6wt% of Nd), improves the cost of alloy, and have pollution to environment.These
The higher magnesium alloy of cost is difficult to high-volume commercial applications.
Therefore, by developing non-rare earth cast magnesium alloy, and then low-cost high-strength magnesium alloy is obtained, advantageously reduces magnesium
The cost of alloy, promotes application of the magnesium alloy on the parts of the products such as automobile, with important economy and social effect.
The content of the invention
The purpose of the present invention is a variety of high rare earth elements of use or high price conjunction existed for existing high-strength cast magnesium alloy
Gold element causes cost too high, and density is higher, and causes alloy casting character to be deteriorated so that being difficult to be commercialized popularization and application
The problems such as there is provided new non-rare earth cast magnesium alloy of one kind and preparation method thereof, the magnesium alloy is a kind of new Mg-Bi-Zr-
Zn magnesium alloys, are added Zr elements in the form of Mg-Zr intermediate alloys in fusion process, Zr elements is relatively easily added
Into alloy, so that refining effect strong in Mg-Bi systems alloy, makes magnesium alloy have excellent comprehensive mechanical property, together
When raw material and low processing cost, easily realize and produce in enormous quantities.
The technical scheme is that：
A kind of new non-rare earth cast magnesium alloy, is Mg-Bi-Zr-Zn alloys, the percentage by weight of its component is：Bi
0.5~8wt%；0.35~1.0wt% of Zr；0.1~2.0wt% of Zn, surplus is Mg.
The preparation method of described new non-rare earth cast magnesium alloy, comprises the following steps：
1) dispensing：Using pure Mg ingots, pure bismuth block, pure spelter and Mg-Zr intermediate alloys as raw material, by described magnesium alloy composition
Carry out dispensing；
2) melting：Pure Mg ingots are put into the crucible of smelting furnace, 700~730 DEG C of furnace temperature is set and keeps, treat that it melts
Afterwards, the pure bismuth block, pure spelter and the Mg-Zr intermediate alloys that are preheating to 200~250 DEG C are added in magnesium melt respectively；Then rise
High 10~20 DEG C of smelting temperature, and 10~15 minutes are incubated, then stir 2~5 minutes；
3) pour into a mould：Furnace temperature is turned down 10~30 DEG C to pouring temperature, after being incubated 8~10 minutes, magnesium alloy fused mass poured into a mould
Into corresponding mould, using gravitational casting or pressure casting processes, described new non-rare earth cast magnesium alloy is made；Its
In, from melting to cast during the entire process of in CO2/SF6Mixed gas protected lower progress；
Described Mg-Zr intermediate alloys are preferably Mg-20Zr intermediate alloys.
Described CO2/SF6Mixed gas composition is preferably volume ratio CO2:SF6=100:1.
The preparation method of above-mentioned novel magnesium alloy, raw material used and equipment are obtained by known approach, used
Operating procedure be that those skilled in the art can grasp.
The present invention substantive distinguishing features be：
The magnesium alloy of the present invention is using Bi as main alloying elements, and Bi can have high-melting-point with the magnesium in-situ preparation in alloy
Mg3Bi2Phase (fusing point is 823 DEG C), its higher heat endurance can compare favourably with the heat endurance of Mg-RE phase, and price is low
It is honest and clean, Mg3Bi2Mutually can effectively pin crystal boundary movement, hinder dislocation motion, and then improve alloy mechanical property.Using Zr elements
As grain refiner, Zr crystal structure is similar to Mg, can play a part of heterogeneous forming core in alloy graining, so that
Greatly crystal grain thinning, while improving alloy property, improves the processing performance of alloy, Zr content is 0.35~1.0%.Close
A small amount of Zn is additionally added in gold, certain solution strengthening effect can be played, while adjusting alloy casting character, alloy is improved and receives
Contracting tendency.
Beneficial effects of the present invention are
1) present invention is the cast magnesium alloy of the alloy system based on Mg-Bi, is brand-new cast magnesium alloy series, is closing
Substantial amounts of Mg is formed in gold3Bi2It is used as the hardening constituent of alloy.It is found that Zr elements show in Mg-Bi alloy systems on this basis
The Grain Refinement Effect of work, so as to improve the intensity and plasticity of alloy.It is aided with a small amount of Zn-ef ficiency to improve the intensity of alloy, from
And high-strength cast magnesium alloy is developed in the alloy series, yield strength 140-155MPa, tensile strength 245-285MPa prolong
Rate is stretched more than 6.5%.
2) in the present invention Mg-Bi-Zr-Zn alloys preparation method, by metal Bi (fusing points 271 in the raw material that is used
DEG C) and Zn, and and Mg-Zr intermediate alloys fusing point all than relatively low, melting is easy, saves the energy.Due to hardening constituent in alloy
Mg3Bi2It is mutually generated in-situ, so existing magnesium alloy smelting and Equipment for Heating Processing can be all processed to it, without extra
Improve, the requirement to production equipment is low.(equipment is simple, and production efficiency is high)
3) present invention develops alloy with the prospect as heat resistance magnesium alloy.Hardening constituent (Mg in alloy3Bi2Phase) it is molten
Point is higher (fusing point be 823 DEG C), can be compared favourably with the high-temperature-phase of magnesium rare earth formation, during high temperature, due to better heat stability, its
Invigoration effect remains to keep, so as to improve the heat resistance of alloy.
4) magnesium alloy of the present invention is with low cost.It is steady for in-situ preparation hyperpyrexia due to without precious metals such as rare earths
Qualitatively Mg3Bi2The metal Bi of phase is cheap, cost of alloy low (general 1000 to the 5000 yuan of per kilograms of rare earth, and this patent
Metal Bi per kilograms used are only with 200 yuan or so)；It can be widely applied to the casting parts of the products for civilian use such as automobile.
5) the main alloy element Bi elements of this alloy do not have toxic action to environment and human body, belong to environment-friendly section bar
Material, also holds promise as bio-medical material application.
6) as cast condition blank alloy of the invention, because die type becomes the visibly homogeneous equi-axed crystal of size, just
In plastotype processing, it can be used for the plastic workings, the higher material of production performance such as extruding.
Brief description of the drawings
In order that the object, technical solutions and advantages of the present invention are clearer, below in conjunction with accompanying drawing the present invention is done into
The description of one step.
Fig. 1 is to obtain the microscopic structure of alloy in embodiment 1
Fig. 2 is to obtain the microscopic structure of alloy in embodiment 2
Fig. 3 is as cast condition Mg microscopic structure
Fig. 4 is to obtain the microscopic structure of alloy in comparative example 1
Fig. 5 is to obtain the SEM photograph of alloy tensile fracture in embodiment 2
Obtain obtaining the tensile stress strain curve of alloy at room temperature in alloy and comparative example 1 in Fig. 6 embodiments 1,2,3
Embodiment
(technical scheme) of the invention is described further with embodiment below, following examples are in this hair
It is lower premised on bright technical scheme to be implemented, give detailed embodiment and specific operating process, but the guarantor of the present invention
Shield scope is not limited to following embodiments.
Choose three kinds of alloying component Mg-3.8Bi-0.7Zr-1.0Zn (wt%) (alloy 1), Mg-6.0Bi-0.7Zr-
1.0Zn (wt%) (alloy 2), Mg-7.0Bi-0.7Zr-1.0Zn (wt%) (alloy 3) are used as exemplary.
According to technical scheme, choose pure Mg (99.8wt%), pure Bi (99wt%), pure Zn (99.9wt%) and
Mg-20Zr (the actually detected contents of Zr are 20.01wt%) intermediate alloy is raw material, through dispensing, melting, melt treatment and cast,
High strength and low cost magnesium alloy is made, and gained alloy mechanical property and microstructure are tested and analyzed.
Embodiment 1
1. raw material is weighed by alloy Mg-3.8Bi-0.7Zr-1.0Zn (wt%) mass percent：Pure Bi, pure Zn, Mg-
20Ca, remaining be Mg (every 1000 grams of subject alloys can be prepared by 35 grams of Mg-20Zr, 10g grams of Zn, 38 grams of Bi and 917 gram of Mg and
Into)；And carry out raw material surface treatment (as removed dirt, oxide skin etc.).
2. smelting furnace is cleaned out first and is heated to 450 DEG C, the magnesium ingot for being preheating to 200 DEG C is put into the earthenware of smelting furnace
In crucible, 720 DEG C of furnace temperature, slow heating are set, heating rate is 20~40 DEG C/min, reaches and is kept after design temperature.
3. after after pure magnesium ingot all fusing, addition is preheated to 200 DEG C or so of pure bismuth, pure zinc and Mg-20Zr intermediate alloys.
4. furnace temperature is risen to 740 DEG C, after being incubated 10~15 minutes, stirs 2~5 minutes, all alloying elements is uniformly divided
Cloth (this temperature is in order that Zr elements can be circulated sufficiently in alloy molten solution) in magnesium alloy fused mass.
5. furnace temperature is adjusted to 720 DEG C after, 8~10 minutes is incubated, skims dross on surface of fusant, be then poured into mould
In, after cooled and solidified, magnesium alloy needed for being made.In CO during the entire process of from melting to cast2/SF6Under mixed gas protected
Carry out, CO2:SF6Volume ratio is 100:1.
Sampled from gained alloy, be processed into coupon, carry out tensile tests at room, the tensile strength for measuring gained alloy reaches
To 245MPa, yield strength reaches 140MPa, elongation percentage 6.9%.
Embodiment 2
1. raw material is weighed by alloy Mg-6.0Bi-0.7Zr-1.0Zn (wt%) mass percent：Pure Bi, pure Zn, Mg-
20Ca, remaining is Mg；And carry out raw material surface treatment (as removed dirt, oxide skin etc.).
2. smelting furnace is cleaned out first and is heated to 450 DEG C, the magnesium ingot for being preheating to 200 DEG C is put into the earthenware of smelting furnace
In crucible, 720 DEG C of furnace temperature, slow heating are set, heating rate is 20~40 DEG C/min.Reach and kept after design temperature.
3. after after pure magnesium ingot all fusing, addition is preheated to 200 DEG C or so of pure bismuth, pure zinc and Mg-20Zr intermediate alloys.
4. furnace temperature is risen to 740 DEG C, after being incubated 10~15 minutes, stirs 2~5 minutes, all alloying elements is uniformly divided
Cloth (this temperature is in order that Zr elements can be circulated sufficiently in alloy molten solution) in magnesium alloy fused mass.
5. furnace temperature is adjusted to 720 DEG C after, 8~10 minutes is incubated, skims dross on surface of fusant, be then poured into mould
In, after cooled and solidified, magnesium alloy needed for being made.In CO during the entire process of from melting to cast2/SF6Under mixed gas protected
Carry out, CO2:SF6Volume ratio is 100:1.
Sampled from gained alloy, be processed into coupon, carry out tensile tests at room, the tensile strength for measuring gained alloy reaches
To 272MPa, yield strength reaches 148MPa, elongation percentage 6.8%.
Embodiment 3
1. raw material is weighed by alloy Mg-7.0Bi-0.7Zr-1.0Zn (wt%) mass percent：Pure Bi, pure Zn, Mg-
20Ca, remaining is Mg；And carry out raw material surface treatment (as removed dirt, oxide skin etc.).
2. smelting furnace is cleaned out first and is heated to 450 DEG C, the magnesium ingot for being preheating to 200 DEG C is put into the earthenware of smelting furnace
In crucible, 720 DEG C of furnace temperature, slow heating are set, heating rate is 20~40 DEG C/min, reaches and is kept after design temperature.
3. after after pure magnesium ingot all fusing, addition is preheated to 200 DEG C or so of pure bismuth, pure zinc and Mg-20Zr intermediate alloys.
4. furnace temperature is risen to 740 DEG C, after being incubated 10~15 minutes, stirs 2~5 minutes, all alloying elements is uniformly divided
Cloth is in magnesium alloy fused mass.
5. furnace temperature is adjusted to 720 DEG C after, 8~10 minutes is incubated, skims dross on surface of fusant, be then poured into mould
In, after cooled and solidified, magnesium alloy needed for being made.In CO during the entire process of from melting to cast2/SF6Under mixed gas protected
Carry out, CO2:SF6Volume ratio is 100:1.
Sampled from gained alloy, be processed into coupon, carry out tensile tests at room, the tensile strength for measuring gained alloy reaches
To 285MPa, yield strength reaches 155MPa, elongation percentage 6.6%.
Comparative example 1
1. raw material is weighed by alloy Mg-6.0Bi-0.7Zr-1.0Zn (wt%) mass percent：Pure Bi, pure Zn, pure Zr
(99.99wt%), remaining is Mg；And carry out raw material surface treatment (as removed dirt, oxide skin etc.).
2. smelting furnace is cleaned out first and is heated to 450 DEG C, the magnesium ingot for being preheating to 200 DEG C is put into the earthenware of smelting furnace
In crucible, 720 DEG C of furnace temperature, slow heating are set, heating rate is 20~40 DEG C/min.Reach and kept after design temperature.
3. after after pure magnesium ingot all fusing, addition is preheated to 200 DEG C or so of pure bismuth, pure zinc and pure Zr (99.99wt%).
4. furnace temperature is risen to 740 DEG C, after being incubated 10~15 minutes, stirred 2~5 minutes.
5. furnace temperature is adjusted to 720 DEG C after, 8~10 minutes is incubated, skims dross on surface of fusant, be then poured into mould
In, after cooled and solidified, the magnesium alloy of comparative example 1 is made.In CO during the entire process of from melting to cast2/SF6Mixed gas is protected
Shield is lower to be carried out, CO2:SF6Volume ratio is 100:1.
Sampled from gained alloy, be processed into coupon, carry out tensile tests at room, the tensile strength for measuring gained alloy reaches
To 102MPa, yield strength reaches 58MPa, elongation percentage 1.3%.
Microscopic structure and mechanical property comparative analysis：
Fig. 1 is the microscopic structure of gained alloy in embodiment 1, there it can be seen that alloy is all by uniform equiax crystal
Grain composition；Fig. 2 is the microscopic structure of gained alloy in embodiment 2, there it can be seen that alloy is all by uniform equi-axed crystal
Composition；Fig. 3 is the as cast condition Mg obtained under experiment condition same as Example 1 microscopic structure, it can be seen that pure magnesium
As-cast grain is very thick, and most of is column crystal.Fig. 4 is the microscopic structure in the gained alloy of comparative example 1, it can be seen that
Mainly it is made up of in alloy isometric dendrite and the two kinds of crystal grain of column crystal, contrasts the as-cast structure of pure magnesium, it can be seen that
The crystal grain of the gained alloy of comparative example 1 has been refined, but the crystal grain of the isometric dendrite in alloy is still thicker.Contrast is implemented
Example 1,2 and comparative example 1, it can be seen that the alloy of gained is all made up of uniform equi-axed crystal in embodiment 1,2, and is waited
The die type of axialite is changed into born of the same parents' shape of gained alloy etc. in embodiment 1,2 from the isometric dendrite of the gained alloy of comparative example 1
Axialite.It can be seen that Zr elements can produce ferocious thinning effect when being added in intermediate alloy form in Mg-Bi alloys, so as to
With from largely improve alloy intensity and plasticity, and when Zr elements in the form of pure Zr in alloying process add
When, satisfied thinning effect is hardly resulted in, this illustrates to add Zr elements, alloying efficiency in the form of Mg-Zr intermediate alloys
It is higher.Fig. 5 is the scanned photograph of the stretching fracture of gained alloy in embodiment 2, from fracture apperance as can be seen that the crystalline substance of the alloy
Grain is visibly homogeneous tiny, and it is a kind of fine grain cast magnesium alloy that Mg-Bi-Zr-Zn alloys have been confirmed again.
Fig. 6 is the stress strain curve of embodiment 1,2,3 and the gained alloy of comparative example 1.The mechanical property of embodiment 1,2,3, bends
Intensity 140-155MPa, tensile strength 245-285MPa are taken, elongation percentage is more than 6.5%, than the mechanical property of the alloy of comparative example 1
Can, tensile strength reaches 102MPa, and yield strength reaches 58MPa, and elongation percentage 1.3% has fairly obvious raising.Closed with reference to each
The microstructure and common metal material reinforcement rule of gold, it may be speculated that this is that mainly intercrystalline strengthening and second-phase strength is comprehensive
The result of cooperation.On the other hand, with the rise of Bi contents, the intensity of embodiment 1,2,3 gradually rises, under elongation percentage slightly has
Drop, this is mainly in Mg3Bi2Phase amount increases with the rise of Bi contents, and this aspect can improve the intensity of alloy, a side
Low-alloyed plasticity can drop in face again.
Unaccomplished matter of the present invention is known technology.
Claims (3)
1. a kind of non-rare earth cast magnesium alloy, it is characterized in that the alloy is Mg-Bi-Zr-Zn alloys, the percentage by weight of its component
For：Bi 3.8~8 wt%；Zr 0.35~1.0 wt%；The wt% of Zn 0.1 ~ 2.0, surplus is Mg；
Described non-rare earth cast magnesium alloy is made by following methods, is comprised the following steps：
1) dispensing：Using pure Mg ingots, pure bismuth block, pure spelter and Mg-Zr intermediate alloys as raw material, enter by described magnesium alloy composition
Row dispensing；
2) melting：Pure Mg ingots are put into the crucible of smelting furnace, 700 ~ 730 DEG C of furnace temperature is set and keeps, after after its thawing, are divided
The pure bismuth block, pure spelter and the Mg-Zr intermediate alloys that are preheating to 200 ~ 250 DEG C are not added in magnesium melt；Then melting is raised
10 ~ 20 DEG C of temperature, and 10~15 minutes are incubated, then stir 2~5 minutes；
3) pour into a mould：Furnace temperature is turned down 10 ~ 30 DEG C to pouring temperature afterwards, after being incubated 8 ~ 10 minutes, magnesium alloy fused mass be poured into
In corresponding mould, using gravitational casting or pressure casting processes, described non-rare earth cast magnesium alloy is made；Wherein, from molten
Refine during the entire process of cast in CO2/SF6Mixed gas protected lower progress.
2. non-rare earth cast magnesium alloy as claimed in claim 1, it is characterized in that described Mg-Zr intermediate alloys are Mg-20Zr
Intermediate alloy.
3. non-rare earth cast magnesium alloy as claimed in claim 1, it is characterized in that described CO2/SF6Mixed gas composition is body
Product compares CO2:SF6=100:1.
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| CN109280826B (en) * | 2018-10-17 | 2020-08-07 | 合肥诺瓦新材料科技有限公司 | Nano-structure-containing non-rare earth high-strength magnesium alloy material and preparation method thereof |
| CN109234592B (en) * | 2018-11-19 | 2020-07-14 | 河北工业大学 | Low-temperature rolled high-strength-toughness wrought magnesium alloy and preparation method thereof |
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