CN101781728B - Magnesium-tin-based alloy and preparation method thereof - Google Patents
Magnesium-tin-based alloy and preparation method thereof Download PDFInfo
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- CN101781728B CN101781728B CN2010101246053A CN201010124605A CN101781728B CN 101781728 B CN101781728 B CN 101781728B CN 2010101246053 A CN2010101246053 A CN 2010101246053A CN 201010124605 A CN201010124605 A CN 201010124605A CN 101781728 B CN101781728 B CN 101781728B
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 82
- 239000000956 alloy Substances 0.000 title claims abstract description 82
- RRXGIIMOBNNXDK-UHFFFAOYSA-N [Mg].[Sn] Chemical compound [Mg].[Sn] RRXGIIMOBNNXDK-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011777 magnesium Substances 0.000 claims abstract description 22
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004332 silver Substances 0.000 claims abstract description 14
- 229910052709 silver Inorganic materials 0.000 claims abstract description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052718 tin Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005728 strengthening Methods 0.000 claims abstract description 10
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000007669 thermal treatment Methods 0.000 claims description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- 239000011135 tin Substances 0.000 claims description 11
- 238000010791 quenching Methods 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 238000003723 Smelting Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 238000004062 sedimentation Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229910000861 Mg alloy Inorganic materials 0.000 description 7
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 229910001051 Magnalium Inorganic materials 0.000 description 4
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910019074 Mg-Sn Inorganic materials 0.000 description 1
- 229910019382 Mg—Sn Inorganic materials 0.000 description 1
- 229910020994 Sn-Zn Inorganic materials 0.000 description 1
- 229910009069 Sn—Zn Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910001234 light alloy Inorganic materials 0.000 description 1
- -1 magnesium rare earth Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
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Abstract
The invention relates to a magnesium-tin-based alloy and a preparation method thereof, which belong to the technical field of the metal structural material and the preparation. The magnesium-tin-based alloy comprises the following components by weight percent: 6 to 8 percent of tin, 2 to 3 percent of zinc, 0.2 to 0.5 percent of manganese, 0.1 to 0.5 percent of silver and rest magnesium. The preparation method comprises the following steps that: the components are sequentially arranged inside a crucible to be heated, mixed and settled into alloy liquid, and the alloy liquid is poured into a cold mould to form a magnesium-tin-based alloy ingot; the magnesium-tin-based alloy ingot is arranged into a resistance furnace to be heated at an air atmosphere and to be quenched with cold water to obtain the homogenized magnesium-tin-based alloy; and finally the homogenized magnesium-tin-based alloy is arranged inside a conventional resistance furnace to be undertaken the timely heat treatment at the air atmosphere and to be quenched with cold water to obtain the timely-reinforced magnesium-tin-based alloy. The method has simple smelting process, the sedimentation strengthening can be performed through the heat treatment, the timely peak value can be reached within a short time, the hardness value is above 80HV, the structure at high temperature is stable, the additive amount of the silver is less, the cost is within the available range, and the magnesium-tin-based alloy has commercial potential.
Description
Technical field
The invention belongs to structural metallic materials and preparing technical field, particularly a kind of novel magnesium-tin-based alloy and smelting and thermal treatment process that does not contain rare earth.
Background technology
Magnesium alloy is a kind of novel light alloy, and comparing it with titanium alloy with aluminium alloy, to have density lower, advantage such as damping capacity is better, and castability is more superior.The development of high-performance magnesium-alloy is the focus of various countries' metal material field in recent years.Magnalium system is the most frequently used magnesium alloy system, but the use temperature of existing magnalium generally is lower than 150 ℃, can not satisfy the requirement of many members.The commercial magnesium alloy that can improve hot strength and creep property at present mainly all is to be main alloy element with the rare earth element, and consumption 〉=7% of most of magnesium rare earth based alloy middle-weight rare earths elements, but the structure stability problem remains the important factor that limits these alloy use temperatures, and price has then restricted these alloys popularizing on the product for civilian use.In not containing the high strength at high temperature magnesium alloy design of components of rare earth element, existing work mainly is divided into three directions: 1, and be to add trace element in the alloy at the magnalium that obtains widespread use; 2, be main alloy element with calcium, silicon etc.; 3, be main alloy element with tin.Magnalium base system alloy can obtain performance change in various degree with the difference of trace element, but the relative needed index of practical application does not have the improvement of essence; Magnesium calcium base system and magnesium are silica-based to be that stable eutectic phase plays strengthening effect on the alloy dependence crystal boundary, but these crystal boundary eutectics are often thicker, and matrix inside can not get the strengthening phase of small and dispersed.At present main magnesium-tin-based alloy mostly is ternary alloy, wherein better performances and what have commercial potentiality is Mg-Sn-Zn ternary magnesium-tin-based alloy.This series magnesium-tin-based alloy has certain ageing strengthening effect, but the time that reaches the timeliness peak value is longer.Alloy is 200-250 ℃ of timeliness, and the timeliness peak value arrives the required time of timeliness peak value between 70h～100h between 70～75HV, and this is unfavorable for industrial production.Therefore, the work that improves magnesium-tin-based alloy is necessary.
Summary of the invention
The objective of the invention is for overcoming the weak point of prior art, a kind of novel magnesium-tin-based alloy and preparation method thereof is provided, by improvement component and thermal treatment process, it is obvious to make it have the ageing strengthening effect, the timeliness peak value occurs very fast, and overaging is slow, and structure stability is characteristics preferably, to increase the alloy system of magnesium alloy, optimize its performance.
A kind of magnesium-tin-based alloy provided by the invention is characterized in that, the component of this magnesium-tin-based alloy is elementary composition by magnesium, tin, zinc, manganese and five kinds of silver; The mass percent of each component concentration is:
Tin (Sn): 6～8%
Zinc (Zn): 2～3%
Manganese (Mn): 0.2～0.5%
Silver (Ag): 0.1～0.5%
All the other are magnesium (Mg).
The preparation method of above-mentioned magnesium-tin-based alloy provided by the invention comprises smelting, homogenizing thermal treatment, timeliness thermal treatment; It is characterized in that, may further comprise the steps:
Step 1: preparation magnesium-tin-based alloy blank
Prepare burden by following component and mass percentage content: 6～8% tin, 2～3% zinc, 0.2～0.5% manganese, 0.1～0.5% silver medal, all the other are magnesium; The purity of each component is put into magnesium, tin, zinc successively all above 99.99% in the raw material in crucible, manganese, silver is heated to 700～720 ℃, stirred 8-10 minute, and left standstill 6-10 minute one-tenth alloy liquid, alloy liquid is poured into casting with forming the magnesium-tin-based alloy blank in the cold mould;
Step 2: homogenizing thermal treatment
The magnesium-tin-based alloy blank is put into conventional resistance furnace, heat under air atmosphere, Heating temperature is 440-450 ℃, and soaking time is 27-30 hour, and cold-water quench obtains the magnesium-tin-based alloy of homogenizing;
Step 3: timeliness thermal treatment
The magnesium-tin-based alloy of homogenizing is carried out timeliness thermal treatment under the air atmosphere in conventional resistance furnace, Heating temperature is 200-220 ℃, and soaking time is 25～30 hours, and cold-water quench obtains the magnesium-tin-based alloy of ageing strengthening.
The present invention compared with prior art has following advantage:
1, this magnesium alloy that proposes of the present invention be characterised in that integrated survey Mg-Sn, Mg-Zn, Mg-Mn isofacies map, and possible intermetallic compound, adopt cheap main alloying element, do not contain rare earth element, only need to add the silver element of trace, all the other main alloy element are more cheap non-rare earth, and the cost of material is in acceptable scope.
2, magnesium-tin-based alloy of the present invention possesses the potentiality that high strength at high temperature is used, and the timeliness peak value surpasses 80HV, is higher than other serial magnesium-tin-based alloys.
3, the prepared magnesium-tin-based alloy of the present invention, the time that the timeliness peak value arrives is 25-30 hour, far below other serial magnesium-tin-based alloys, has saved the energy consumption that needed time of thermal treatment and thermal treatment need to a great extent.
4, the prepared magnesium-tin-based alloy of the present invention is in timeliness more than 200 ℃, and the alloy microhardness value is stable remaining on about 70HV after 55 hours, and the high temperature stability performance of material structure is fine.
5, the magnesium-tin-based alloy of the present invention's design can be heat-treated by conventional resistance furnace, need not gas shields such as argon gas in the heat treatment process, need not additionally to increase specific installation, can save equipment cost when using in enterprise.
Embodiment
The purpose of this invention is to provide a kind of have stable high-temperature performance and the time validity response magnesium-tin-based alloy faster.
The present invention will be further described by following embodiment:
Embodiment 1:
Step 1: preparation magnesium-tin-based alloy blank
(1) by following component and mass percentage content batching: 6% tin, 2% zinc, 0.2% manganese, 0.1% silver medal, all the other are magnesium; The purity of raw material is 99.999%, and crucible and mold and pattern for casting tool adopt low-carbon steel material.The crucible target temperature is decided to be 700 ℃; Then described various batchings are placed on and are preheated to 160 ℃ in the baking oven, the RJ-2 insulating covering agent that will account for prepared magnesium-tin-based alloy gross weight 2wt% is simultaneously put into baking oven and is toasted; Casting is preheated to 300 ℃ with mould in other box-type furnace;
(2) when crucible is warming up to 300 ℃, feed CO
2Gas carries out gas displacement to crucible, add about 1/2 the insulating covering agent that has toasted then in crucible bottom, again after the pure magnesium batching that preheating is good put into crucible;
(3) magnesium batching fusing and etc. after crucible temperature is stabilized in 700 ℃, add other various batchings of preheating from high to low successively according to fusing point, melt carried out stir about 8 minutes then; In this process, take the circumstances into consideration to add the remaining insulating covering agent that has toasted, do not fire with the surface and be as the criterion;
(4) after crucible temperature was stabilized in 700 ℃, melt left standstill 6 minutes, and per-cent by volume is at 99.5% air (or CO
2)+1%SF
6Draw slag under mixed gas protected;
(5) draw slag and finish after, keep crucible temperature and be stabilized in 700 ℃, per-cent by volume is at 99.5% air (or CO
2)+1%SF
6Be cast into the magnesium-tin-based alloy blank under mixed gas protected;
Step 2: homogenizing thermal treatment
The magnesium-tin-based alloy blank is put into conventional resistance furnace, heat under air atmosphere, Heating temperature is 440 ℃, and soaking time is 27 hours, and cold-water quench obtains the magnesium-tin-based alloy of homogenizing;
Step 3: timeliness thermal treatment
The magnesium-tin-based alloy of homogenizing is carried out timeliness thermal treatment under the air atmosphere in conventional resistance furnace, the temperature of using in the ag(e)ing process is 200 ℃, and soaking time is 30 hours, and cold-water quench obtains the magnesium-tin-based alloy of ageing strengthening.
Embodiment 2:
Step 1: preparation magnesium-tin-based alloy blank
(1) by following component and mass percentage content batching: 7% tin, 2.5% zinc, 0.3% manganese, 0.3% silver medal, all the other are magnesium.The purity of raw material is 99.999%, and crucible and mold and pattern for casting tool adopt low-carbon steel material.Deciding the crucible target temperature is 710 ℃, described various batchings is placed on is preheated to 160 ℃ in the baking oven then, and the RJ-2 insulating covering agent that will account for prepared magnesium-tin-based alloy gross weight 2wt% is simultaneously put into baking oven and toasted; Casting is preheated to 300 ℃ with mould in other box-type furnace;
(2) when crucible is warming up to 300 ℃, feed CO
2Gas carries out gas displacement to crucible, add about 1/2 the insulating covering agent that has toasted then in crucible bottom, again after the pure magnesium batching that preheating is good put into crucible;
(3) magnesium batching fusing and etc. after crucible temperature is stabilized in 710 ℃, add other various batchings of preheating from high to low successively according to fusing point, melt carried out stir about 9 minutes then; In this process, take the circumstances into consideration to add the remaining insulating covering agent that has toasted, do not fire with the surface and be as the criterion.
(4) after crucible temperature was stabilized in 710 ℃, melt left standstill 8 minutes, and per-cent by volume is at 99.5% air (or CO
2)+1%SF
6Draw slag under mixed gas protected;
(5) draw slag and finish after, keep crucible temperature and be stabilized in 710 ℃, per-cent by volume is at 99.5% air (or CO
2)+1%SF
6Be cast into the magnesium-tin-based alloy blank under mixed gas protected.
Step 2: homogenizing thermal treatment
The magnesium-tin-based alloy blank is put into conventional resistance furnace, heat under air atmosphere, Heating temperature is 445 ℃, and soaking time is 28 hours, and cold-water quench obtains the magnesium-tin-based alloy of homogenizing.
Step 3: timeliness thermal treatment
The magnesium-tin-based alloy of homogenizing is carried out timeliness thermal treatment under the air atmosphere in conventional resistance furnace, the temperature of using in the ag(e)ing process is 210 ℃, and soaking time is 27 hours, and cold-water quench obtains the magnesium-tin-based alloy of ageing strengthening.
Embodiment 3:
Step 1: preparation magnesium-tin-based alloy blank
(1) by following component and mass percentage content batching: 8% tin, 3% zinc, 0.5% manganese, 0.5% silver medal, all the other are magnesium.The purity of raw material is 99.999%, and crucible and mold and pattern for casting tool adopt low-carbon steel material.Deciding the crucible target temperature is 720 ℃, begins heating.Then various batchings are placed on and are preheated to 160 ℃ in the baking oven, the RJ-2 insulating covering agent that will account for prepared magnesium-tin-based alloy gross weight 2wt% is simultaneously put into baking oven and is toasted; Casting is preheated to 300 ℃ with mould in other box-type furnace.
(2) when crucible is warming up to 300 ℃, feed CO
2Gas carries out gas displacement to crucible, add about 1/2 the insulating covering agent that has toasted then in crucible bottom, again after the pure magnesium batching that preheating is good put into crucible.
(3) magnesium batching fusing and etc. after crucible temperature is stabilized in 720 ℃, add the various batchings of preheating from high to low successively according to fusing point, melt carried out stir about 10 minutes then; In this process, take the circumstances into consideration to add the remaining insulating covering agent that has toasted, do not fire with the surface and be as the criterion.
(4) after crucible temperature was stabilized in 720 ℃, melt left standstill 10 minutes, and per-cent by volume is at 99.5% air (or CO
2)+1%SF
6Draw slag under mixed gas protected;
(5) draw slag and finish after, keep crucible temperature and be stabilized in 720 ℃, per-cent by volume is at 99.5% air (or CO
2)+1%SF
6Be cast into the magnesium-tin-based alloy blank under mixed gas protected.
Step 2: homogenizing thermal treatment
The magnesium-tin-based alloy blank is put into conventional resistance furnace, heat under air atmosphere, Heating temperature is 450 ℃, and soaking time is 30 hours, and cold-water quench obtains the magnesium-tin-based alloy of homogenizing.
Step 3: timeliness thermal treatment
The magnesium-tin-based alloy of homogenizing is carried out timeliness thermal treatment under the air atmosphere in conventional resistance furnace, the temperature of using in the ag(e)ing process is 220 ℃, and soaking time is 25 hours, and cold-water quench obtains the magnesium-tin-based alloy of ageing strengthening.
Claims (2)
1. a magnesium-tin-based alloy is characterized in that, the component of this magnesium-tin-based alloy is elementary composition by magnesium, tin, zinc, manganese and five kinds of silver, and the mass percentage content of each component concentration is:
Tin (Sn): 6～8%
Zinc (Zn): 2～3%
Manganese (Mn): 0.2～0.5%
Silver (Ag): 0.1～0.5%
All the other are magnesium (Mg).
2. the preparation method of a magnesium-tin-based alloy comprises preparation magnesium-tin-based alloy blank, homogenizing thermal treatment, timeliness thermal treatment; It is characterized in that, may further comprise the steps:
Step 1: preparation magnesium-tin-based alloy blank
Prepare burden by following component and mass percentage content: 6～8% tin, 2～3% zinc, 0.2～0.5% manganese, 0.1～0.5% silver medal, all the other are magnesium; The purity of each component is put into magnesium, tin, zinc successively all above 99.99% in the raw material in crucible, manganese, silver is heated to 700～720 ℃, stirred 8-10 minute, and left standstill 6-10 minute one-tenth alloy liquid, alloy liquid is poured into casting with forming the magnesium-tin-based alloy blank in the cold mould;
Step 2: homogenizing thermal treatment
The magnesium-tin-based alloy blank is put into conventional resistance furnace, heat under air atmosphere, Heating temperature is 440-450 ℃, and soaking time is 27-30 hour, and cold-water quench obtains the magnesium-tin-based alloy of homogenizing;
Step 3: timeliness thermal treatment
The magnesium-tin-based alloy of homogenizing is carried out timeliness thermal treatment under the air atmosphere in conventional resistance furnace, Heating temperature is 200-220 ℃, and soaking time is 25～30 hours, and cold-water quench obtains the magnesium-tin-based alloy of ageing strengthening.
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| CN102358929B (en) * | 2011-10-19 | 2013-04-03 | 清华大学 | Heatproof magnesium sannum silver alloy and preparation method thereof |
| CN109182860A (en) | 2018-11-08 | 2019-01-11 | 中信戴卡股份有限公司 | A kind of magnesium alloy with high strength and ductility and preparation method |
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| CN100469929C (en) * | 2006-12-29 | 2009-03-18 | 清华大学 | Magnesium alloy and its preparation method |
| CN101323924B (en) * | 2008-07-24 | 2010-04-21 | 上海交通大学 | Ag-containing cast magnesium alloy and method for preparing the same |
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