CN101812604A - Method for improving long-term oxidation resistance of high-niobium titanium-aluminum alloy through adding yttrium at high temperature - Google Patents
Method for improving long-term oxidation resistance of high-niobium titanium-aluminum alloy through adding yttrium at high temperature Download PDFInfo
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- CN101812604A CN101812604A CN 201010148618 CN201010148618A CN101812604A CN 101812604 A CN101812604 A CN 101812604A CN 201010148618 CN201010148618 CN 201010148618 CN 201010148618 A CN201010148618 A CN 201010148618A CN 101812604 A CN101812604 A CN 101812604A
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 76
- 230000003647 oxidation Effects 0.000 title claims abstract description 75
- 239000010955 niobium Substances 0.000 title claims abstract description 18
- 229910052727 yttrium Inorganic materials 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000007774 longterm Effects 0.000 title claims abstract description 13
- 229910052758 niobium Inorganic materials 0.000 title claims abstract description 12
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 10
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 title claims abstract description 8
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 title claims abstract 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 63
- 239000000956 alloy Substances 0.000 claims abstract description 63
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 238000011282 treatment Methods 0.000 claims abstract description 5
- 238000000265 homogenisation Methods 0.000 claims abstract 4
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 2
- 238000002474 experimental method Methods 0.000 abstract description 8
- 238000001816 cooling Methods 0.000 abstract description 7
- 238000005336 cracking Methods 0.000 abstract description 5
- 238000006735 epoxidation reaction Methods 0.000 abstract description 5
- 238000009413 insulation Methods 0.000 abstract description 5
- 229910052593 corundum Inorganic materials 0.000 abstract description 4
- 229910002064 alloy oxide Inorganic materials 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000007769 metal material Substances 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 229910010038 TiAl Inorganic materials 0.000 description 10
- 239000010936 titanium Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 230000004584 weight gain Effects 0.000 description 7
- 235000019786 weight gain Nutrition 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 244000137852 Petrea volubilis Species 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001073 sample cooling Methods 0.000 description 3
- 229910000952 Be alloy Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 238000007792 addition Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009760 electrical discharge machining Methods 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021324 titanium aluminide Inorganic materials 0.000 description 1
- 229910006281 γ-TiAl Inorganic materials 0.000 description 1
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Abstract
The invention discloses a method for improving long-term oxidation resistance of a high-niobium titanium-aluminum alloy through adding yttrium at high temperature, belonging to the high temperature oxidization field of the metal material. The invention is characterized in that Y is added in a Ti 45Aa17Nb alloy or a Ti 45Al 8Nb alloy, a tiny yttrium doping high-niobium titanium-aluminum alloy complete lamellar structure is obtained after using vacuum melting and homogenization treatments; the alloy comprises the following components by atomic percent: 46.4-47.9% of Ti, 45% of Al, 7-8% of Nb and 0.1-0.8% of Y; and the homogenization treatment process comprises the following steps: heat insulation is carried out at a temperature of 1320 DEG C for 12h, a converter is insulated for 30 minutes at a temperature of 900 DEG C and then taken out for air cooling. The invention has the advantages that adding proper amount of Y increases the proportion of Al2O3 in an oxide film, reduces the thickness of the oxide film, refines particles producing the oxide, facilitates plastic deformation of the oxide film and reduces cracking of the film; and by epoxidation experiments, after all alloys containing Y go through 1000 cycle periods, no obvious shedding phenomenon occurs in the oxide film, and addition of Y improves the adhesion of the alloy oxide film and raises the use temperature of the high-niobium titanium-aluminum alloy to the temperature of more than 900 DEG C.
Description
Technical field
The invention belongs to metallic substance high temperature oxidation field, a kind of method that improves the high temperature long-term oxidation resistance of high niobium containing titanium aluminium alloy by the interpolation yttrium is provided.
Technical background
The TiAl base intermetallic compound has low density, high-melting-point and higher high temperature specific tenacity, be considered to be in the high-temperature structural material of new generation that has wide application prospect most in aerospace, automobile, chemical industry and other industrial circle, but the relatively poor major obstacle that limits its practical application that becomes of its oxidation-resistance more than 800 ℃.High Nb-TiAl alloy is better than general T iAl alloy greatly in oxidation-resistance more than 800 ℃, and we are as far back as Corrosion1992; Pointed out first among the 48:939 that the Nb element can significantly improve the high-temperature oxidation resistance of alloy, after this also there are many scholars to experimental results show that the interpolation of Nb element can improve the high-temperature oxidation resistance of TiAl alloy greatly, therefore high Nb-TiAl alloy might have been expanded the range of application of conventional TiAl alloy 800-900 ℃ of use.
But, document M.Yoshihara, Y.W.Kim.A comparative study of oxidation resistanceof engineering gamma TiAl alloys, in Proc.of Gamma Titanium Aluminides, TMS, point out high Nb-TiAl alloy among the 1999:753 when 870 ℃ of long-term cyclic oxidations, oxidation occurred between 250 to 300 times (about 500 hours to 600 hours) circulation and sharply increased weight the stage that major cause is that oxide film came off in this stage.
Be to improve the long-term resistance of oxidation of alloy high-temp, can improve alloy oxide film antistripping ability by the adding quaternary of trace on the basis that does not influence the alloy comprehensive mechanical property or multicomponent alloy element more.M.Yoshihara points out the Si of trace, B, and the adding of C and Ha does not all have beneficial effect to the alloy high-temp long-term oxidation resistance.In addition, can also come to provide protection by the method that the surface applies suitable oxidation resistant coating to the TiAlNb alloy.Document bear jade is bright; Zhu Shenglong; Wang Fuhui. the TiAlNb alloy high-temp oxidation behavior of band coating. Rare Metals Materials and engineering .2006; 35:213 has studied and has had NiCrAlY; the oxidation behavior of 800 ℃ of the TiAlNb alloys of TiAlCr and enamel coating and 900 ℃; this method can only play protective effect to alloy to a certain extent; long oxidation all exists disbonding and wild effect; this external coating (EC)/alloy interface mutual diffusion influences the mechanical property of coating and alloy; improve in the method for alloy oxidation-resistance this shortcoming ubiquity by surface modification and surface-coated at other.Therefore, improving the long-term resistance of oxidation of alloy high-temp by the microalloy alloying is valid approach the most at present.People such as Wu are at document Wu Y, Umakoshi Y, Li X, 900 ℃ of .Oxidation of of et al.Isothermal Oxidation Behavior of Ti-50Al Alloy with Y Additions at 800 and Metals.2006,66 (5): 321 and Wu Y, Hagihara K, Umakoshi Y.Improvement of cyclic oxidation resistance of Y-containing TiAl-based alloys withequiaxial gamma microstructures.Intermetallics.2005,13 (8): the adding of pointing out an amount of Y element in 879 can improve TiAl alloy high-temp oxidation-resistance and oxide film antistripping ability, but its long-term oxidation resistance and oxide film adhesion are not had report.
Summary of the invention
The object of the present invention is to provide a kind of raising high Nb-TiAl alloy high-temp long-term oxidation resistance and oxidation-resistant film method for exfoliating, further improve the use temperature of alloy.
A kind of by adding the method for yttrium raising high niobium containing titanium aluminium alloy high temperature long-term oxidation resistance, it is characterized in that adding atomic percent in Ti45Al7Nb alloy or Ti45Al8Nb alloy is the Y of 0.1-0.8, adopt vacuum melting, homogenizing to obtain tiny yttrium doping high niobium containing titanium aluminium alloy complete lamellar structure after handling.The alloying constituent atomic percent is: Ti:46.4-47.9%, Al:45%, Nb:7-8%, Y:0.1-0.8%.The homogenizing treatment process is: 1320 ℃ (α single phase region) insulation 12 hours, converter is taken out air cooling 900 ℃ of insulations 30 minutes.
Carry out isothermal oxidation and epoxidation experiments through 900 ℃ and find that the adding of an amount of Y has reduced the oxidation weight gain of alloy, rate of oxidation reduces, and oxide film antistripping ability improves, and does not still come off at 1000 circulation rear oxidation films.
The experimental program that the present invention adopts:
(1) melting: adopt vacuum melting, the raw material of melting is sponge Ti (99.9%), pure Al (99.99%), pure Y, NbAl master alloy.
(2) homogenizing is handled: 1320 ℃ (α single phase region) insulation 12 hours, converter is taken out air cooling 900 ℃ of insulations 30 minutes, obtains tiny complete lamellar structure.
(3) oxidised samples preparation: line cuts into and is of a size of 10 * 10 * 1mm
3Thin slice, 6 surfaces of sample all are ground to No. 1200 through SiC sand paper is from coarse to fine, ultrasonic cleaning 15min in acetone then, and the sample after the cleaning is put into the moisture eliminator drying for standby.
(4) isothermal oxidation experiment: carry out in chamber type electric resistance furnace, test medium is a still air, and experimental temperature is 900 ℃.For guaranteeing that 6 surfaces of sample all contact with air, the sample of measuring size is inclined in the corundum crucible, behind the oxidation certain hour crucible is taken out, to treat to weigh after the sample cooling, the sample that has claimed continues to put into the stove oxidation, sample accumulation oxidation 1000h.
(5) epoxidation experiments: carry out in the cyclic oxidation stove, test medium is a still air, and experimental temperature is 900 ℃.Furnace high-temperature oxidation 1 hour, the outer room temperature cooling of stove was a loop cycle in 12 minutes, was oxidizing to the sample oxide film record loop cycle that comes off.
Effect of the present invention:
(1) be alloy for Ti-45Al-7Nb, the raising that the interpolation of 0.4%Y is best alloy 900 ℃ oxidation-resistance, its interpolation makes isothermal oxidation rear oxidation weightening finish in 1000 hours reduce 30% than no y alloy, the adding of 0.4%Y element has promoted Al
2O
3Formation, reduced the thickness of oxide film, refinement generate the particle of oxide compound, help the viscous deformation of oxide film, reduced the cracking of film.
(2) be alloy for Ti-45Al-8Nb, the raising that the interpolation of 0.1%Y is best alloy 900 ℃ oxidation-resistance, its interpolation makes isothermal oxidation rear oxidation weightening finish in 1000 hours reduce 20% than no y alloy, the adding of 0.1%Y has increased Al in the oxide film
2O
3Ratio, reduced the thickness of oxide film, help the viscous deformation of oxide film, reduced the cracking of film.
(3) all contain 1000 loop cycle rear oxidations of y alloy film and all take place significantly to come off in the epoxidation experiments, and have 300 loop cycle rear oxidations of y alloy film in process of cooling because thermal stresses does not come off, increase the rate of oxidation rising with Y content.
(4) adding of Y makes alloy that interior oxidation at high temperature take place, dendritic Al
2O
3Extend to matrix perpendicular to the interface, oxide film is played pinning effect, the inhibited oxidation film comes off under internal stress, but excessive interior oxidation again for oxygen provide passage to internal diffusion, accelerate alloy oxidation speed.
An amount of Y's is added in when improving alloy oxide film antistripping ability greatly among the present invention, also reduced the rate of oxidation of alloy, and the adding of micro-Y has no adverse effect to the alloy comprehensive mechanical property, therefore the present invention can improve high Nb-TiAl alloy high-temp long-term oxidation resistance greatly, and its use temperature is brought up to 900 ℃.
Description of drawings
Fig. 1 is 1000 hours a oxidation weight gain curve of 900 ℃ of oxidations of Ti-45Al-7Nb series alloy.
Fig. 2 is 1000 hours a oxidation weight gain curve of 900 ℃ of oxidations of Ti-45Al-8Nb series alloy.
Fig. 3 is 900 ℃ of following cyclic oxidation weightening finish curves of Ti-45Al-8Nb series alloy.
Fig. 4 is the SEM figure in 1000 hours rear oxidation films of 900 ℃ of oxidations of Ti-45Al-7Nb series alloy cross section.
Fig. 5 is the SEM figure in 1000 hours rear oxidation films of 900 ℃ of oxidations of Ti-45Al-8Nb series alloy cross section.
Embodiment
Table 1 Ti-45Al-7Nb be the alloy designs composition (atomic fraction, %)
| Ti-45Al-7Nb system | ??Al | ??Ti | ??Nb | ??Y |
| ??1 | ??45 | ??48.0 | ??7 | ??0 |
| ??2 | ??45 | ??47.9 | ??7 | ??0.1 |
| ??3 | ??45 | ??47.7 | ??7 | ??0.3 |
| ??4 | ??45 | ??47.6 | ??7 | ??0.4 |
| ??5 | ??45 | ??47.4 | ??7 | ??0.6 |
| ??6 | ??45 | ??47.2 | ??7 | ??0.8 |
Table 2 Ti-45Al-8Nb be the alloy designs composition (atomic fraction, %)
| Ti-45Al-8Nb system | ??Al | ??Ti | ??Nb | ??Y |
| ??1 | ??45 | ??47.0 | ??8 | ??0 |
| ??2 | ??45 | ??46.9 | ??8 | ??0.1 |
| ??3 | ??45 | ??46.7 | ??8 | ??0.3 |
| ??4 | ??45 | ??46.6 | ??8 | ??0.4 |
| ??5 | ??45 | ??46.4 | ??8 | ??0.6 |
| Ti-45Al-8Nb system | ??Al | ??Ti | ??Nb | ??Y |
| ??6 | ??45 | ??46.2 | ??8 | ??0.8 |
The vacuum melting nominal composition is the alloy of Ti-45Al-7Nb-(0,0.1,0.3,0.4,0.6,0.8) Y, and after homogenizing was handled, line cut into and is of a size of 10 * 10 * 1mm
3Thin slice, 6 surfaces of sample all are ground to No. 1200 through SiC sand paper is from coarse to fine, then ultrasonic cleaning 15min in acetone.Carry out the isothermal oxidation experiment in chamber type electric resistance furnace, test medium is a still air, and experimental temperature is 900 ℃.For guaranteeing that 6 surfaces of sample all contact with air, the sample of measuring size is inclined in the corundum crucible, behind the oxidation certain hour crucible is taken out, to treat to weigh after the sample cooling, the sample that has claimed continues to put into the stove oxidation, sample accumulation oxidation 1000h.Fig. 1 is an oxidation weight gain curve, and the Ti-45Al-7Nb-0.4Y alloy shows best oxidation-resistance, and its oxidation weight gain has reduced 30% than no y alloy, and Fig. 4 is the SEM figure in oxide film cross section, and the adding of 0.4%Y element has promoted Al
2O
3Formation, reduced the thickness of oxide film, refinement generate the particle of oxide compound, help the viscous deformation of oxide film, reduced the cracking of film.
The vacuum melting nominal composition is the alloy of Ti-45Al-8Nb-(0,0.1,0.3,0.4,0.6,0.8) Y, and after homogenizing was handled, line cut into and is of a size of 10 * 10 * 1mm
3Thin slice, 6 surfaces of sample all are ground to No. 1200 through SiC sand paper is from coarse to fine, then ultrasonic cleaning 15min in acetone.Carry out the isothermal oxidation experiment in chamber type electric resistance furnace, test medium is a still air, and experimental temperature is 900 ℃.For guaranteeing that 6 surfaces of sample all contact with air, the sample of measuring size is inclined in the corundum crucible, behind the oxidation certain hour crucible is taken out, to treat to weigh after the sample cooling, the sample that has claimed continues to put into the stove oxidation, sample accumulation oxidation 1000h.Fig. 2 is an oxidation weight gain curve, and the Ti-45Al-8Nb-0.1Y alloy shows best oxidation-resistance, and its oxidation weight gain has reduced 20% than no y alloy, and Fig. 5 is the SEM figure in oxide film cross section, and the adding of 0.1%Y element has promoted Al
2O
3Formation, reduced the thickness of oxide film, help the viscous deformation of oxide film, reduced the cracking of film.
Embodiment 3
The vacuum melting nominal composition is the alloy of Ti-45Al-8Nb-(0,0.3,0.4,0.6,0.8) Y, and after homogenizing was handled, line cut into and is of a size of 10 * 10 * 1mm
3Thin slice, at sample one side electric spark-erosion perforation, 6 surfaces of sample all are ground to No. 1200 through SiC sand paper is from coarse to fine, then ultrasonic cleaning 15min in acetone.Sample hangs and carry out epoxidation experiments in the cyclic oxidation stove, test medium is a still air, experimental temperature is 900 ℃, furnace high-temperature oxidation 1 hour, the outer room temperature cooling of stove was a loop cycle in 12 minutes, all contain 1000 loop cycle rear oxidations of y alloy film tangible obscission all do not take place, and do not come off owing to thermal stresses in process of cooling and there is 300 loop cycle rear oxidations of y alloy film.Fig. 3 is cyclic oxidation weightening finish curve, increases rate of oxidation with Y content and raises.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074520A (en) * | 2013-01-14 | 2013-05-01 | 北京工业大学 | Er-containing high-niobium Ti-Al intermetallic compound material and preparation method thereof |
| CN103820672A (en) * | 2014-03-12 | 2014-05-28 | 北京工业大学 | Cr and Mn alloying beta phase solidifying high Nb-TiAl alloy and preparation method thereof |
| CN109112388A (en) * | 2018-10-30 | 2019-01-01 | 江苏亿超工程塑料有限公司 | A kind of composition metal tee pipe fitting and preparation method thereof |
| CN111961900A (en) * | 2020-09-07 | 2020-11-20 | 济南大学 | Novel titanium-aluminum-based composite material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074520A (en) * | 2013-01-14 | 2013-05-01 | 北京工业大学 | Er-containing high-niobium Ti-Al intermetallic compound material and preparation method thereof |
| CN103820672A (en) * | 2014-03-12 | 2014-05-28 | 北京工业大学 | Cr and Mn alloying beta phase solidifying high Nb-TiAl alloy and preparation method thereof |
| CN109112388A (en) * | 2018-10-30 | 2019-01-01 | 江苏亿超工程塑料有限公司 | A kind of composition metal tee pipe fitting and preparation method thereof |
| CN111961900A (en) * | 2020-09-07 | 2020-11-20 | 济南大学 | Novel titanium-aluminum-based composite material and preparation method thereof |
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