CN103290264B - A kind of containing strontium cast zinc alloy and preparation method thereof - Google Patents
A kind of containing strontium cast zinc alloy and preparation method thereof Download PDFInfo
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Abstract
A kind of cast zinc alloy containing strontium and preparation method thereof, the component of alloy following weight percent: the inevitable impurity element summation such as Al3.5-4.8%, Mg0.02-0.08%, Sr0.03-0.14%, Pb, Cd, Fe, Sn is less than 0.02%, and surplus is Zn.Its preparation method is: first Zn-Al master alloy is put into smelting furnace, be warming up to 550 DEG C, add Al-Mg master alloy, pure Zn ingot and Al-Sr master alloy more successively, be warming up to 650-660 DEG C, after metal melts completely, stirring, refining, to skim, be cooled to 500-550 DEG C, leave standstill, skim, cast.The present invention effectively can improve plasticity, the toughness of zinc alloy, improves the over-all properties of cast zinc alloy.This alloy production technical process is simple, and effective refinement zinc alloy as cast condition dendrite, shortens the sheet interlayer spacing of the lamellar microstructure of dendrite net intercellular, decrease the volume fraction of brittlement phase, improve the mechanical property of alloy.
Description
Technical field
The present invention relates to a kind of containing strontium cast zinc alloy and preparation method thereof, belong to technical field of metal material preparation.
Background technology
Cast zinc alloy has that fusing point is low, melting power consumption less, high, the low cost of manufacture of mobility and good moldability, production efficiency, the advantages such as surface treatment widely can be implemented.The die casting of thin-walled, complex-shaped, precision size can be obtained.Along with developing rapidly of the industries such as Domestic Automotive Industry, real estate and household electrical appliances, the demand of China to cast zinc alloy increases fast.Therefore cast zinc alloy is applied to every field just more and more widely, and brings significant economic benefit.But traditional cast zinc alloy ubiquity dendritic structure is flourishing, the problems such as poor mechanical property, greatly reduce its product work-ing life.
Microalloying is one of effective way improving casting alloy microstructure and property, by add alloying element can effectively thinning microstructure, purify impurity, carry heavy alloyed comprehensive mechanical property.The domestic research adding Sr element microalloying has got certain achievement, as University Of Chongqing the people such as Liu Xiangguo and Peng Xiaodong " rare metal " the 28th volume the 4th phase " present Research of Preparation of Metallic Strontium and alloy thereof and application " literary composition in propose Al-Sr alloy be a kind of novel efficient grain-refining agent, be mainly used in the object reaching crystal grain thinning in the alloys such as Al, Mg; The refinement mechanism of the Sr element added in the magnesium alloy is that Sr can form Sr film at crystal boundary edge, inhibits the propelling of solid-liquid interface, thus crystal grain thinning.The Pan Zengyuan of Shanghai mechanical technology institute have studied and adds micro-Sr element in Al-Si alloy, show that adding of Sr can promote new heterogeneous nuclei, suppresses grain growing, the conclusion of refined eutectic structure; In Al-Si alloy, add Sr element, system interface energy can be reduced, weaken the combination of Si-Si atomic group, and promote the combination of Al-Al atomic group, Al phase is preferentially separated out, facilitate more nucleus and formed, make grain refining.But, according to the heterogeneous forming core classical theory of crystal, only have when the mismatch that two-phase lattice is asked less (in about 10% scope), just there is good nucleation ability.And Sr atomic radius is 0.200nm, Zn atomic radius is 0.133nm, and both Atomic radiuses differences are 33.5%, and lattice equations is comparatively large, is unfavorable for effective forming core core of serving as η-Zn phase.Therefore, not yet find so far in cast zinc alloy, to add micro-Sr to improve the open report of alloy structure and raising alloy mechanical property.
Summary of the invention
The object of this invention is to provide one can effective refining alloy tissue, improves alloy comprehensive mechanical property, reduces production cost, produce cast zinc alloy containing Sr of the zinc alloy product of high-quality and preparation method thereof.
Above-mentioned purpose of the present invention reaches by the following technical programs.
Containing a cast zinc alloy of Sr, be made up of following component by weight percentage:
Al：3.5-4.8%；
Mg：0.02-0.08%；
Sr：0.03-0.14%；
Pb, Cd, Fe, Sn impurity element total content is less than 0.02%; Surplus is Zn.
η-Zn the phase of this zinc alloy microtexture primarily of primary dendrite shape and the eutectic structure α-Al phase+η-Zn phase composite of sheet, the volume content of lamellar eutectic tissue is 40% ~ 75%, and all the other are the bulk dendrite η-Zn phase of fragility.
A kind of preparation method containing Sr cast zinc alloy of the present invention, comprises the steps:
The first step: batching
The component proportion containing Sr cast zinc alloy according to design takes each component, and wherein: Mg, Sr add with the form of Al-Sr, Al-Mg master alloy, Al adds with the form of Zn-Al master alloy, and Zn adds with the form of pure Zn ingot;
Second step: first Zn-Al master alloy is put into smelting furnace, be warming up to 550 DEG C of fusings, add Al-Mg master alloy, pure Zn ingot and Al-Sr master alloy more successively, be warming up to 650-660 DEG C, after metal melts completely, stirring, refining, to skim, be cooled to 500-550 DEG C subsequently, leave standstill, skim, cast, obtain containing Sr cast zinc alloy.
The present invention is a kind of containing in the preparation method of strontium cast zinc alloy, the purity of described pure Zn ingot is greater than 99.97%, after adding Al, Mg, Sr master alloy, controlling each element mass percent of alloy solution is: Al3.5-4.3%, Mg0.02-0.06%, Sr0.03-0.14%, Pb, the inevitable impurity element total content of Cd, Fe, Sn are less than 0.02%, and surplus is Zn.
Of the present invention containing in the preparation method of Sr cast zinc alloy, described Zn-Al master alloy is Zn-5wt.%Al, and described Al-Sr master alloy is Al-10wt.%Sr, and described Al-Mg master alloy is Al-11.07wt.%Mg.
Ultimate principle of the present invention sketch under:
In zinc alloy, because the mismatch of Sr and Zn atom is large, can not provide effective forming core core, therefore, this area it has been generally acknowledged that can not carry out refinement zinc alloy crystal grain with Sr.But the present inventor is by long-term research, experiment, observation, find that Sr completely can refinement zinc alloy crystal grain, effectively can reduce the η-Zn phase nascent with refinement bulk; Analyzing its Refining Mechanism may be: Sr can provide forming core particle for the formation of the α-Al phase in zinc alloy in zinc alloy, abundant to α-Al phase forming core while, inhibit large block growth conversely, instead of directly by Sr unit usually refinement η-Zn phase.After adding Al-Sr master alloy, in alloy, solution composition rises and falls, cause the enrichment of Al, eutectic composition point deflection Fu Xinqu, alloying constituent is transformed into hypereutectic (see figure 1) by hypoeutectic in some region, therefore the Primary α-Al Phase in zinc alloy increases, and nascent η-Zn reduces mutually and obtains refinement, improves mechanical property.The present invention suppresses bulk dendrite η-Zn phase by improving Primary α-Al Phase.η-the Zn of bulk is close-packed hexagonal structure mutually, for brittlement phase, be unfavorable for the plasticity and toughness of alloy, and Primary α-Al Phase is a kind of face-centred cubic structure phase, improve the ratio of Primary α-Al Phase and bulk dendrite η-Zn phase, effectively can improve plasticity, the toughness of zinc alloy, improve the over-all properties of cast zinc alloy.This alloy preparation technology flow process is simple, and effective refinement zinc alloy as cast condition dendrite, shortens the sheet interlayer spacing of the lamellar microstructure of dendrite net intercellular, decrease the volume fraction of brittlement phase, improve the mechanical property of alloy.In addition, according to Hume-Rothery criterion, the Atomic radiuses difference being conducive to being formed sosoloid will lower than 15%, the Atomic radiuses difference of Sr atomic radius to be 0.200nm, Zn atomic radius be 0.133nm, Sr and Zn is 33.5%, the solid solution of Sr will produce very large distortional strain energy, and Sr and Zn has spontaneous generation SrZn
13trend, when Sr content increases to a certain degree, dendrite net intercellular separate out SrZn
13deng intermetallic compound, have stronger pinning effect to crystal boundary, the bulk strength of material rises.
Advantage of the present invention is: after Addition ofelements Sr, the obvious refinement of as cast condition bulk dendrite of zinc alloy and minimizing, the sheet interlayer spacing of the lamellar microstructure of dendrite net intercellular shortens, the a large amount of sheet eutectic structure formed, what be conducive to puies forward heavy alloyed mechanical property, and wherein hardness maximumly improves 9.5%, tensile strength improves 17.2%, unit elongation improves 58.3%, impelling strength is maximum improves 138.2%.
In sum, preparation technology's flow process of the present invention is simple, can effective refinement zinc alloy as cast condition dendrite, shorten the sheet interlayer spacing of the lamellar microstructure of dendrite net intercellular, decrease the volume fraction of brittlement phase, improve alloy comprehensive mechanical property, reduce production cost, produce the zinc alloy product of high-quality, be suitable for industrial applications.
Accompanying drawing explanation
Fig. 1: adding Al-Sr master alloy affects schematic diagram to two component eutectic point;
Fig. 2 a is the zinc alloy as-cast structure photo not adding Sr element;
The zinc alloy as-cast structure photo of Fig. 2 b to be Sr element addition be 0.03wt.%;
The zinc alloy as-cast structure photo of Fig. 2 c to be Sr element addition be 0.06wt.%;
The zinc alloy as-cast structure photo of Fig. 2 d to be Sr element addition be 0.1wt.%;
The zinc alloy as-cast structure photo of Fig. 2 e to be Sr element addition be 0.14wt.%;
Fig. 3: the tissue topography figure of the embodiment of the present invention 3
Accompanying drawing 4 is the energy spectrogram of A point in accompanying drawing 3.
Can know from accompanying drawing 1: add Al-Sr master alloy zinc alloy prepared by the present invention after, in alloy, solution composition rises and falls, and causes the enrichment of Al, eutectic composition point deflection Fu Xinqu.
As can be seen from accompanying drawing 2a-accompanying drawing 2e: along with the increase of Sr content, bulk dendrite η-Zn phase size reduces, and volume fraction reduces, and when Sr content is 1.0wt.%, size and the volume fraction of η-Zn phase reach minimum.
As can be seen from accompanying drawing 3, accompanying drawing 4: when Sr content is 1.0wt.%, SrZn can be separated out at dendrite net intercellular
13deng intermetallic compound.
Embodiment
Following examples are provided in conjunction with method of the present invention:
Embodiments of the invention are the Sr adding different content in cast zinc alloy batching, and its composition is as shown in table 1.Alloy shown in the embodiment of the present invention decreases the volume fraction of brittlement phase, effective refinement zinc alloy as cast condition dendrite, shorten the sheet interlayer spacing (as shown in Figure 2) of the lamellar microstructure of dendrite net intercellular, have good mechanical property, its mechanical property has all exceeded the cast zinc alloy (as shown in table 2) shown in comparative example 1 not adding Sr element.Specific embodiment is described as follows:
Comparative example 1:
With purity be greater than 99.97% pure Zn ingot, Zn-5wt.%Al master alloy, Al-11.07wt.%Mg master alloy and Al-10wt.%Sr master alloy be for raw material, first Zn-Al master alloy is put into smelting furnace, be warming up to 550 DEG C, add Al-Mg master alloy and pure Zn ingot more successively, be warming up to 650-660 DEG C, after metal melts completely, uniform stirring, with the NH of batching gross weight 0.3%
4cl refining agent alloy liquid carries out refining, skims, and is cooled to 500-550 DEG C, skims after leaving standstill 10min, casting.The component of alloy and weight percent thereof are: 3.5%Al, 0.022%Mg, and all the other are Zn.The microstructure of ingot casting, as shown in Fig. 1 (a), does not add Sr element and significantly can find out that tissue is formed primarily of thick white dendrite, dendrite net intercellular and dendrite border are dispersed with more black particle and lamellar microstructure.
Embodiment 1:
Sr is added by 0.03% of zinc alloy total mass, with purity be greater than 99.97% pure Zn ingot, Zn-5%Al master alloy, Al-10%Sr master alloy, Al-11.07%Mg master alloy is for raw material, first Zn-Al master alloy is put into smelting furnace, be warming up to 550 DEG C, add Al-Mg master alloy, pure Zn ingot and Al-Sr master alloy more successively, be warming up to 650-660 DEG C, after metal melts completely, uniform stirring, with the NH of batching gross weight 0.3%
4cl refining agent alloy liquid carries out refining, skims, and is cooled to 500-550 DEG C, skims after leaving standstill 10min, casting.The component of alloy and weight percent thereof are: 3.5%Al, 0.039%Mg, 0.03%Sr, and all the other are Zn.Add the alloy structure after Sr element as shown in Fig. 1 (b), relative contrast's embodiment 1, white dendrite size reduces to some extent.Its mechanical property is as embodiment 1 alloy in table 2, and hardness raising 5.4%, tensile strength raising 7.4%, unit elongation raising 8.3%, impelling strength improve 34.5%.
Embodiment 2:
Sr is added by 0.06% of zinc alloy total mass, with purity be greater than 99.97% pure Zn ingot, Zn-5%Al master alloy, Al-10%Sr master alloy, Al-11.07%Mg master alloy is for raw material, first Zn-Al master alloy is put into smelting furnace, be warming up to 550 DEG C, add Al-Mg master alloy, pure Zn ingot and Al-Sr master alloy more successively, be warming up to 650-660 DEG C, after metal melts completely, uniform stirring, with the NH of batching gross weight 0.3%
4cl refining agent alloy liquid carries out refining, skims, and is cooled to 500-550 DEG C, skims after leaving standstill 10min, casting.The component of alloy and weight percent thereof are: 3.8%Al, 0.079%Mg, 0.06%Sr, and all the other are Zn.Add the alloy structure after Sr element as shown in Fig. 1 (c), white dendrite size obviously reduces, in the shaft-like distribution such as near in the base.Its mechanical property gold as 2-in-1 in the embodiment in table 2, hardness raising 6.2%, tensile strength raising 8.9%, unit elongation raising 18.1%, impelling strength improve 138.2%.
Embodiment 3:
Sr is added by 0.10% of zinc alloy total mass, with purity be greater than 99.97% pure Zn ingot, Zn-5%Al master alloy, Al-10%Sr master alloy, Al-11.07%Mg master alloy is for raw material, first Zn-Al master alloy is put into smelting furnace, be warming up to 550 DEG C, add Al-Mg master alloy, pure Zn ingot and Al-Sr master alloy more successively, be warming up to 650-660 DEG C, after metal melts completely, uniform stirring, with the NH of batching gross weight 0.3%
4cl refining agent alloy liquid carries out refining, skims, and is cooled to 500-550 DEG C, skims after leaving standstill 10min, casting.The component of alloy and weight percent thereof are: 4.3%Al, 0.049%Mg, 0.10%Sr, and all the other are Zn.Add the alloy structure after Sr element as shown in Figure 1 (d) shows, the size of white phase reduces further, containing Sr second-phase power spectrum as shown in Figure 3, be about 12:1 ~ 16:1 containing the ratio of Zn, Sr in Sr particle, can infer that particle may be SrZn thus
13.Its mechanical property is as embodiment 3 alloy in table 2, and hardness raising 9.5%, tensile strength raising 17.2%, unit elongation raising 58.3%, impelling strength improve 103.7%.
Embodiment 4:
Sr is added by 0.14% of zinc alloy total mass, with purity be greater than 99.97% pure Zn ingot, Zn-5%Al master alloy, Al-10%Sr master alloy, Al-11.07%Mg master alloy is for raw material, first Zn-Al master alloy is put into smelting furnace, be warming up to 550 DEG C, add Al-Mg master alloy, pure Zn ingot and Al-Sr master alloy more successively, be warming up to 650-660 DEG C, after metal melts completely, uniform stirring, with the NH of batching gross weight 0.3%
4cl refining agent alloy liquid carries out refining, skims, and is cooled to 500-550 DEG C, skims after leaving standstill 10min, casting.The component of alloy and weight percent thereof are: 4.8%Al, 0.053%Mg, 0.14%Sr, and all the other are Zn.Add the size of the alloy structure white phase as Suo Shi Fig. 1 (e) after Sr element without considerable change., embodiment 4 alloy in its mechanical property man table 2, hardness raising 5.4%, tensile strength raising 10.8%, unit elongation raising 27.8%, impelling strength improve 80.8%.
The main chemical compositions (wt.%) of table 1 cast alloy of the present invention
| Alloy | Al | Mg | Sr | Zn |
| Comparative example 1 | 3.5 | 0.022 | 0 | Surplus |
| Embodiment 1 | 3.5 | 0.039 | 0.03 | Surplus |
| Embodiment 2 | 3.8 | 0.076 | 0.06 | Surplus |
| Embodiment 3 | 4.3 | 0.049 | 0.1 | Surplus |
| Embodiment 4 | 4.8 | 0.053 | 0.14 | Surplus |
The mechanical property of table 2 embodiment and comparative example
Claims (4)
1., containing a cast zinc alloy of Sr, it is characterized in that comprising following component forms by weight percentage:
Al：3.5-4.8％；
Mg：0.02-0.08％；
Sr：0.03-0.14％；
Pb, Cd, Fe, Sn impurity element total content is less than 0.02%; Surplus is Zn;
η-Zn the phase of described cast zinc alloy microtexture primarily of primary dendrite shape and the eutectic structure α-Al phase+η-Zn phase composite of sheet, the volume content of lamellar eutectic tissue is 40% ~ 75%, and all the other are the bulk dendrite η-Zn phase of fragility.
2. a kind of preparation method containing Sr cast zinc alloy according to claim 1, is characterized in that, comprise the following steps:
The first step: batching
The component proportion containing Sr cast zinc alloy according to design takes each component, and wherein: Mg, Sr add with the form of Al-Sr, Al-Mg master alloy, Al adds with the form of Zn-Al master alloy, and Zn adds with the form of pure Zn ingot;
Second step: first Zn-Al master alloy is put into smelting furnace, be warming up to 550 DEG C of fusings, add Al-Mg master alloy, pure Zn ingot and Al-Sr master alloy more successively, be warming up to 650-660 DEG C, after metal melts completely, stirring, refining, to skim, be cooled to 500-550 DEG C subsequently, leave standstill, skim, cast, obtain containing Sr cast zinc alloy.
3. a kind of preparation method containing Sr cast zinc alloy material according to claim 2, it is characterized in that: the purity of described Zn ingot is greater than 99.97%, the master alloy of Al, Mg, Sr is added in melt, the mass percent controlling each element in alloy molten solution is: Al3.5-4.8%, Mg0.02-0.08%, Sr0.03 ~ 0.14%, the inevitable impurity element total content of Pb, Cd, Fe, Sn is less than 0.02%, and surplus is Zn.
4. a kind of preparation method containing Sr cast zinc alloy material according to claim 2, it is characterized in that: described Zn-Al master alloy is Zn-5wt.%Al, described Al-Sr master alloy is Al-10wt.%Sr, and described Al-Mg master alloy is Al-11.07wt.%Mg.
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| CN103993193B (en) * | 2014-05-07 | 2016-06-08 | 常州大学 | A kind of zinc die casting alloys low melting point is containing strontium long-acting alterant and Modification Manners thereof |
| CN104195368B (en) * | 2014-08-21 | 2016-09-21 | 北京大学 | A kind of Zn-Sr system kirsite and preparation method and application |
| CN105132746B (en) * | 2015-09-29 | 2017-10-10 | 南安市鑫灿品牌运营有限公司 | A kind of low creep kirsite |
| CN105132748B (en) * | 2015-09-29 | 2017-07-21 | 广州市奇诺五金有限公司 | A kind of metamorphism treatment method of kirsite |
| CN106906381A (en) * | 2015-12-23 | 2017-06-30 | 上海微创医疗器械（集团）有限公司 | A kind of alloy material and its application |
| CN106435272B (en) * | 2015-12-25 | 2018-08-28 | 常州大学 | A kind of preparation method of Zn-Sr alloys |
| CN105714151A (en) * | 2016-02-29 | 2016-06-29 | 常州大学 | Zn-Al-Sr alloy and preparation method thereof |
| CN108315595A (en) * | 2018-04-20 | 2018-07-24 | 厦门格欧博新材料科技有限公司 | It is a kind of to may be cast as and deformable Environment-friendlyzinc zinc alloy |
| JP7322611B2 (en) * | 2019-09-10 | 2023-08-08 | ニデック株式会社 | Zinc alloy and its manufacturing method |
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| CN1091475A (en) * | 1993-02-12 | 1994-08-31 | 曾宏洁 | Super-high-strength antiwear zinc alloy |
| CN102766782A (en) * | 2012-07-28 | 2012-11-07 | 四会市丰亿鑫金属熔铸有限公司 | Environment-friendly zinc alloy |
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| JP2004019000A (en) * | 2002-06-20 | 2004-01-22 | Sumitomo Metal Ind Ltd | HOT-DIP Zn-Al PLATED STEEL SHEET SUPERIOR IN APPEARANCE, WORKABILITY AND CORROSION RESISTANCE, AND MANUFACTURING METHOD THEREFOR |
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| CN1091475A (en) * | 1993-02-12 | 1994-08-31 | 曾宏洁 | Super-high-strength antiwear zinc alloy |
| CN102766782A (en) * | 2012-07-28 | 2012-11-07 | 四会市丰亿鑫金属熔铸有限公司 | Environment-friendly zinc alloy |
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