CN101880841B - Amorphous/nanocrystalline titanium matrix composite fiber alloy and preparation method thereof - Google Patents
Amorphous/nanocrystalline titanium matrix composite fiber alloy and preparation method thereof Download PDFInfo
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- CN101880841B CN101880841B CN2010102202480A CN201010220248A CN101880841B CN 101880841 B CN101880841 B CN 101880841B CN 2010102202480 A CN2010102202480 A CN 2010102202480A CN 201010220248 A CN201010220248 A CN 201010220248A CN 101880841 B CN101880841 B CN 101880841B
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- 239000000956 alloy Substances 0.000 title claims abstract description 52
- 239000010936 titanium Substances 0.000 title claims abstract description 51
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 40
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 39
- 239000000835 fiber Substances 0.000 title claims abstract description 34
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000011159 matrix material Substances 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- 229910052712 strontium Inorganic materials 0.000 claims description 12
- 229910052718 tin Inorganic materials 0.000 claims description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims description 11
- 229910052727 yttrium Inorganic materials 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 4
- 150000003608 titanium Chemical class 0.000 claims description 4
- 230000004927 fusion Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000009827 uniform distribution Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- 229910052772 Samarium Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000005300 metallic glass Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
The invention provides amorphous/nanocrystalline titanium matrix composite fiber alloy and a preparation method thereof. The alloy has superior strength and toughness. The preparation method has simple technology and low production cost and is suitable for industrial production. The alloy material utilizes titanium alloy as a matrix, nanometer-scale grains are uniformly distributed on thematrix, the nanometer-scale grains account for 20 to 50% of the composite material by volume, and the size of the nanometer-scale grain is from 50 nm to 100 nm. The composite material comprises the following chemical components in percentages by weigh: 25% to 30% of Al, 5% to 10% of Cu, 1% to 5% of Sr, 0.05% to 0.09% of Sn, 0.003% to 0.09% of Sm, 0.5% to 1.0% of Y, 0.5% to 2% of La and balance of Ti.
Description
One, technical field
The invention belongs to metal material field, relate to a kind of amorphous/nanocrystalline titanium matrix composite fiber alloy and preparation method.
Two, background technology
In the metal current field of materials, the effect of fiber alloy has more and more received attention.
CN200510043199.7 number application is on the basis of comprehensive pair rolling and fixed die drawing method for processing advantage; Utilization have before and after two groups of four rollers of roll-type mould of certain die cavity vertically with four groups of planche cross combination or eight rollers before and after intersect vertically to make up and carry out the roller die wire-drawing technology that titanium or titanium alloy silk material is processed with planche cross; Through selecting suitable titanium or titanium alloy wire material hot-work or cold working production technique, can carry out the processing of circular section or on-circular cross-section (abnormal shape) titanium or titanium alloy silk material.Wang Haibo has been discussed titanium or titanium alloy silk material preparation technology's present Research in 2008 the 37th the 14th phases of volume of heat processing technique magazine.Titanium alloy wire realizes that through Hubbing method its technological process of production is: raw material-ingot casting-melting-forging-rolling-drawing-thermal treatment-check-finished product.It is thus clear that the program that titanium alloy wire prepares process is many and complicated, and can't form the fiber with amorphous/nanocrystalline tissue.
CN01128161.8 number application provides one type of multicomponent titanium base alloy that can form amorphous structure, and the expression formula of alloying constituent is: Ti
aM
b(Cu
xNi
1-x)
cR
dZ
e(a, b, c, d, e are atomic percent, x is an atomic fraction).M is at least a among element M g, Ca, Mn, Nb, Fe, V, Mo, the Zr, and R is at least a among element al, Ag, Co, Fe, Pd, the Zn, and Z is at least a among element B, Ge, Si, C, the Sn.a＝37～77％，b＝0～27％，c＝20～50％，d＝0～17％，e＝1～15％，a+b+c+d+e＝100％。x＝0.35～0.75。
CN200610011458.2 number application provides a kind of titanium base block amorphous attitude alloy, and its chemical ingredients (atom number %) is: TE
1(a) TL
1(b) TE
2(c) TL
2(d).Wherein, TE
1=Ti; TL
1=Cu; TE
2=Zr; TL
2=Fe, Co, Pd, Pt, Ir; 45≤a≤50,45≤b≤47.5,2.5≤c≤7.5,1.5≤d≤5.
CN200810084806.8 has supplied a kind of titanium-based amorphous alloy, and wherein, the composition of this titanium-based amorphous alloy is shown in following general formula: Ti
aCu
bSn
cTL
dWherein, TL is one or more among Fe, Co, Mn, Ru, Ag, Pd, the Pt, and a, b, c, d are atomic percent, 40≤a≤60,30≤b≤50,0≤c≤6,2≤d≤8, and a, b, c, d sum are 100.
CN200910084902.7 number application; A kind of titanium base block amorphous alloy that can improve intensity and plasticity is simultaneously disclosed; It is a kind of non-crystaline amorphous metal that contains titanium Ti, copper Cu, zirconium Zr, nickel and five kinds of elements of tin Sn, and this non-crystaline amorphous metal nominal composition is [Ti44.10Cu37.04Zr9.80Ni7.06Sn2.00 (at%)].These materials all can't directly form amorphous/nanocrystalline and organize the titanium fiber alloy.
Three, summary of the invention
Technical problem: the objective of the invention is provides a kind of lightweight amorphous/nanocrystalline titanium base fiber alloy to above-mentioned technological deficiency, and it has superior intensity and toughness.
A kind of amorphous/nanocrystalline titanium matrix composite fiber alloy, this alloy material are matrix with the titanium alloy, are uniform-distribution with nanometer-size die on the matrix, and it is 20-50% that this nanometer-size die accounts for matrix material volume per-cent, and nanometer-size die is of a size of 50nm-100nm; The weight percentage of this alloy material chemical composition is: Al is 25%～30%, and Cu is 5%～10%, and Sr is 1%～5%, and Sn is 0.05%～0.09%, and Sm is 0.003-0.09%, and Y is 0.5%～1.0%, and La is 0.5%～2%, and all the other are Ti.
The preparation method of amorphous/nanocrystalline titanium matrix composite fiber alloy of the present invention, the preparation process is following: will account for the raw material gross weight respectively and be 25%～30% Al, 5%～10% Cu; 1%～5% Sr; 0.05%～0.09% Sn, the Sm of 0.003%-0.09%, 0.5%～1.0% Y; 0.5%～2% La, all the other raw materials for Ti place to melt in the riser pipe that has heating unit and form titanium alloy liquid; Temperature of fusion 1780-1800 ℃, the riser pipe bottom is set with plunger, and plunger can move along riser pipe is upper and lower under PWR PLT drive; Can liquid level in the riser pipe be raised when moving on the plunger; Thereby be convenient to the runner flange alloy liquid is extracted, formed fiber, runner adopts wheel rim that the water-cooled copper alloy runner (putting specification sheets) of flange is arranged; Alloy liquid contacts with the water-cooled copper alloy runner flange of rotation through riser pipe; Water-cooled copper alloy runner runner flange is extracted alloy liquid, forms the titanium-based alloy material fiber, and the LV of runner flange is 18-21m/s; Runner is opened the runner water-cooling system before opening and changeing, and the water-cooling system inflow temperature is less than 30 ℃; The diameter of this titanium-based alloy material fiber is 10-45 μ m; With the alloy fiber that obtains place again 380-420 ℃ the insulation 15-30min after, naturally cooling just obtains amorphous/nanocrystalline titanium matrix composite fiber alloy.
The present invention compares prior art and has following effect:
In the amorphous/nanocrystalline titanium base fiber alloy of the present invention, Al, Cu, Sr, Sm, Y element combined action increase the ability that titanium alloy forms amorphous; Wherein: it is carefully brilliant that Al and the acting in conjunction of Sm element help after thermal treatment temp raises, to form nanometer.Cu, Sn and three element actings in conjunction of La help after thermal treatment temp raises, to suppress the excessive formation of crystal grain and growing up of crystal grain.
The nanocrystalline 20-50% (, the nanocrystal of disperse in noncrystal substrate, occurring) that accounts for alloy substrate in the amorphous/nanocrystalline titanium matrix composite fiber alloy of the present invention through being heated to 380-450 ℃ of insulation 15-30min.Its intensity of amorphous that forms matrix is high, the nanocrystalline good toughness in the matrix.Therefore, amorphous/nanocrystalline titanium base fiber alloy has superior intensity and toughness.
This alloy preparation technology is easy, the alloy material stable performance of production, and also production cost is low, is convenient to very much suitability for industrialized production.
Four, description of drawings
The metallographic structure of the amorphous/nanocrystalline titanium matrix composite fiber alloy that Fig. 1 obtains for the embodiment of the invention one.
Can see the tiny nano-crystalline granule on the noncrystal substrate by Fig. 1.
Five, embodiment
Below each embodiment only with of the present invention the explaining of opposing, weight percent wherein all can change weight g, kg or other weight unit into.
Embodiment one:
The preparation process of amorphous/nanocrystalline titanium base fiber alloy of the present invention: will account for raw material gross weight Al respectively is 25%; Cu is 5%, and Sr is 1%, and Sn is 0.05%; Sm is 0.003%; Y is 0.5%, and La is 0.5%, and surplus is that the raw material of Ti places the interior fusing of the riser pipe that has heating unit to form titanium alloy liquid; Temperature of fusion 1780-1800 ℃, the riser pipe bottom is set with plunger, and plunger can move along riser pipe is upper and lower under PWR PLT drive; Can liquid level in the riser pipe be raised when moving on the plunger; Thereby be convenient to the runner flange alloy liquid is extracted, formed fiber, runner adopts wheel rim that the water-cooled copper alloy runner of flange is arranged; Alloy liquid contacts with the water-cooled copper alloy runner flange of rotation through riser pipe; Water-cooled copper alloy runner runner flange is extracted alloy liquid, forms the titanium-based alloy material fiber, and the LV of runner flange is 18-21m/s; Runner is opened the runner water-cooling system before opening and changeing, and the water-cooling system inflow temperature is less than 30 ℃; The diameter of this titanium-based alloy material fiber is 10-45 μ m; With the alloy fiber that obtains place again 380-420 ℃ the insulation 15-30min after, naturally cooling just obtains amorphous/nanocrystalline titanium matrix composite fiber alloy.The metallographic structure of the amorphous/nanocrystalline titanium matrix composite fiber alloy that obtains is as shown in Figure 1, the tiny nano-crystalline granule on its noncrystal substrate.
Embodiment two:
To account for raw material gross weight: Al respectively is 30%, and Cu is 10%, and Sr is 5%, and Sn is 0.09%, and Sm is 0.09%, and Y is 1.0%, and La is 2%, and surplus is Ti.Press the preparation of embodiment one method, get product.
Embodiment three:
To account for raw material gross weight: Al respectively is 28%, and Cu is 7%, and Sr is 3%, and Sn is 0.07%, and Sm is 0.009%, and Y is 0.8%, and La is 0.8%, and surplus is Ti.Press the preparation of embodiment one method, get product.
Embodiment four: (each proportioning components of raw material is the instance in ratio range of the present invention not)
To account for raw material gross weight: Al respectively is 24%, and Cu is 4%, and Sr is 0.3%, and Sn is 0.05%, and Sm is 0.002%, and Y is 0.4%, and La is 0.4%, and Ti is 70.848%.Press the preparation of embodiment one method, get product.
Embodiment five: (each proportioning components of raw material is the instance in ratio range of the present invention not)
To account for raw material gross weight: Al respectively is 31%, and Cu is 11%, and Sr is 6%, and Sn is 0.1%, and Sm is 0.1%, and Y is 1.1%, and La is 3%, and Ti is 47.7%.Press the preparation of embodiment one method, get product.
Following table is the alloy property synopsis of different components and proportioning:
Table 1:
Visible by last table, Al, Cu, Sr, Sn, Sm, Y, La content increase in this case scope in the alloy, and like product one, product two and product three, tensile strength and elongation improve; If Al, Cu, Sr, Sn, Sm, Y, La content exceed this case scope, perhaps the quantity because of element is not enough, and element interaction is difficult to performance; Cause mechanical property not improve; Perhaps frangible compounds quantity increases, and forms nettedly, can obviously reduce the mechanical property of material.Like product four, product five.
Claims (2)
1. amorphous/nanocrystalline titanium matrix composite fiber alloy; This alloy material is a matrix with the titanium base alloy fiber; This matrix is a noncrystal substrate; Be uniform-distribution with nanometer-size die on this noncrystal substrate, it is 20-50% that this nanometer-size die accounts for matrix material volume per-cent, and nanometer-size die is of a size of 50nm-100nm; Wherein the titanium alloy material following chemical components in percentage by weight is: Al is 25%～30%, and Cu is 5%～10%, and Sr is 1%～5%; Sn is 0.05%～0.09%; Sm is 0.003-0.09%, and Y is 0.5%～1.0%, and La is 0.5%～2%; All the other are Ti, and the diameter of said titanium base alloy fiber is 10-45 μ m.
2. the preparation method of an amorphous/nanocrystalline titanium matrix composite fiber alloy is characterized in that the preparation process is following: will account for the raw material gross weight respectively and be 25%～30% Al, 5%～10% Cu; 1%～5% Sr; 0.05%～0.09% Sn, the Sm of 0.003%-0.09%, 0.5%～1.0% Y; 0.5%～2% La, all the other raw materials for Ti place to melt in the riser pipe that has heating unit and form titanium alloy liquid; Temperature of fusion 1780-1800 ℃, alloy liquid contacts with the water-cooled copper alloy runner flange of rotation through riser pipe, and water-cooled copper alloy runner flange is extracted alloy liquid, forms the titanium-based alloy material fiber, and the LV of runner flange is 18-21m/s; Runner is opened the runner water-cooling system before opening and changeing, and the water-cooling system inflow temperature is less than 30 ℃; The diameter of this titanium-based alloy material fiber is 10-45 μ m; With the alloy fiber that obtains place again 380-420 ℃ the insulation 15-30min after, naturally cooling just obtains amorphous/nanocrystalline titanium matrix composite fiber alloy.
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| CN101880841B true CN101880841B (en) | 2012-08-22 |
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| CN106756232A (en) * | 2016-12-12 | 2017-05-31 | 苏州陈恒织造有限公司 | A kind of low temperature resistant oil-immersed type transformer housing of cracking resistance |
| CN106590075A (en) * | 2016-12-15 | 2017-04-26 | 苏州富艾姆工业设备有限公司 | Treatment technology of piston body for high-strength wear-resisting water pump |
| CN112063890B (en) * | 2020-09-29 | 2021-12-10 | 中国科学院金属研究所 | High-thermal-stability equiaxial nanocrystalline Ti-Ag alloy and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1070558A2 (en) * | 1999-07-13 | 2001-01-24 | Bridgestone Corporation | Method of manufacturing titanium fiber or titanium alloy fiber |
| CN1923394A (en) * | 2005-09-02 | 2007-03-07 | 西安赛特金属材料开发有限公司 | Processing method for high surface quality filament stock of titanium and titanium alloy |
| CN101492781A (en) * | 2008-11-18 | 2009-07-29 | 华南理工大学 | High-ductility titanium based ultra-fine crystal composite material and method for producing the same |
| CN101550522A (en) * | 2009-05-27 | 2009-10-07 | 清华大学 | Ti-based bulk amorphous alloy capable of improving strength and plasticity simultaneity |
-
2010
- 2010-07-06 CN CN2010102202480A patent/CN101880841B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1070558A2 (en) * | 1999-07-13 | 2001-01-24 | Bridgestone Corporation | Method of manufacturing titanium fiber or titanium alloy fiber |
| CN1923394A (en) * | 2005-09-02 | 2007-03-07 | 西安赛特金属材料开发有限公司 | Processing method for high surface quality filament stock of titanium and titanium alloy |
| CN101492781A (en) * | 2008-11-18 | 2009-07-29 | 华南理工大学 | High-ductility titanium based ultra-fine crystal composite material and method for producing the same |
| CN101550522A (en) * | 2009-05-27 | 2009-10-07 | 清华大学 | Ti-based bulk amorphous alloy capable of improving strength and plasticity simultaneity |
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