CN102493853A - Titanium aluminum based powder metallurgy material for automobile engine exhaust doors and manufacturing method of titanium aluminum based powder metallurgy material - Google Patents
Titanium aluminum based powder metallurgy material for automobile engine exhaust doors and manufacturing method of titanium aluminum based powder metallurgy material Download PDFInfo
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- CN102493853A CN102493853A CN2011104104171A CN201110410417A CN102493853A CN 102493853 A CN102493853 A CN 102493853A CN 2011104104171 A CN2011104104171 A CN 2011104104171A CN 201110410417 A CN201110410417 A CN 201110410417A CN 102493853 A CN102493853 A CN 102493853A
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Abstract
The invention discloses a titanium aluminum based powder metallurgy material for automobile engine exhaust doors and a manufacturing method of the titanium aluminum based powder metallurgy material. The ingredient and the content (in atomic percent) of the metallurgy powder material include that Ti takes 45.7% to 48.9%, Al takes 45.7% to 47.5%, and Nb takes 5.4% to 6.8%; purity of powder is 99.5%, , granularity of each of Ti and Al is smaller than 50 mu m, and granularity of Nb is smaller than 70 mu m; the powder which is prepared according to certain ingredients passes through a high-energy ball mill, rotation speed of the ball mill is 330 r/min, ball-to-powder weight ratio is 12:1, ball milling time is 30 hours, both a powder weighing and preparing process and a ball milling process are realized under protection of argon, pre-ball-milling powdery particles are nanocrystalline, and parts of the powder are in combination reaction; powder after ball milling pre-synthesizing is placed in a mold to be in hot-pressing vacuum sintering; and a prepared TiAl based alloy exhaust door has ultra-fine grains/ nanocrystalline tissues, wherein the size of TiAl phase grains is smaller than 500nm, the size of Ti3Al phase grains is smaller than 100nm, ingredients are uniform, and performances are excellent.
Description
Technical field
The present invention relates to a kind of titanium aluminium base powder metallurgy automobile engine exhaust port material and production method thereof.
Background technique
At present, Along with people's is energy-conservation and pursuit efficiently to product, and often temperature is higher to use for advanced design concept, quality is lighter and motion speed is the basis sooner.Yet the performance of present employed common metal material system is near their limit, and further develop just needs the novel material of development.Generally believe now; The Intermatallic Ti-Al compound that is the basis with intermetallic compounds TiAl and Ti3Al most possibly satisfies above-mentioned designing requirement; Be considered to have most the lightening fire resistant structural material of new generation of application potential, be expected in component productions such as aviation, automotive industry, power station turbo machine and combustion turbine engine, be used widely.
Why the TiAl base intermetallic compound is placed high hopes; Be because this compound has the characteristic that metal and covalent bond coexist between atom long-range order structure arranged characteristic and atom; This specific character makes the hot strength of its plasticity that possibly take into account metal simultaneously and pottery; Compare with nickel base superalloy with conventional titanium alloy, TiAl base alloy has performance advantages such as low-gravity, high creep resistance.
But titanium aluminium base alloy exists the defective on some performances as a kind of intermetallic compounds, like room temperature fragility and relatively poor formability (comprising hot and cold processibility and castability).And at present the production method of titanium aluminium base alloy mainly adopts is exactly precision casting and hot forging method, thereby, received very big restriction with the product performance and the kind of titanium-aluminium alloy manufacturing.Adopt powder metallurgy process then can solve casting and the existing problem of forged titanium aluminum alloy.Powder metallurgy process can once be made clean formed product, has solved the processing difficulties problem and has improved utilization ratio of raw materials.Secondly, in powder diffraction method, can make the uniformity of composition, granularity and crystal refinement reach high level through the processing to powder, this has just solved the problem that the as cast condition method is faced.Through powder metallurgy process, can be raw material with simple substance or alloy powder, adjust the ratio of alloying element arbitrarily, and guarantee that composition is even.Adopt powder metallurgy process to prepare titanium-aluminium alloy at present some research reports are arranged; But adopt technological method manufacturings such as regular particle size mixed-powder hot isostatic pressing or vacuum sintering usually; This method is organized thick, does not solve the problem that TiAl alloy fragility is big, be difficult for processing.Adopting preparatory synthesis of nano particle powder of mechanical alloying and vacuum heating-press sintering technology to make the automobile engine to exhaust door also is not reported.
Summary of the invention
The objective of the invention is to overcome conventional casting, forging, sintering TiAl base alloy structure thick, be difficult to cutting, can't prepare shortcoming such as fine grain titanium aluminium base alloy, a kind of automobile engine to exhaust door powdered metallurgical material is provided.
Another object of the present invention provides the production method of this automobile engine to exhaust door metallurgical material.
The present invention is in order to obtain to have the TiAl base alloy exhaust valve of ultra-fine crystalline substance/nanometer crystal microstructure, the method that adopts mechanical ball milling to combine with vacuum sintering.Obtain required tissue through control composition, ball milling and sintering process.
Powdered metallurgical material composition of the present invention is Ti, Al, Nb.
The composition and the content of preparation metallurgical powder material are (atom percent): Ti45.7-48.9%, Al45.7-47.5%, Nb 5.4-6.8%.Powder purity is 99.5%, and granularity is Ti, Al＜50 μ m, and Nb＜70 μ m,
The production method of the aluminium base powder metallurgy automobile engine exhaust port of titanium pre-alloyed powder is: at first in ball grinding drum, carry out high-energy ball milling by the composition proportion powder formulated; Drum's speed of rotation is 330r/min; Ratio of grinding media to material is that 12: 1 ball milling time was 30 hours; The weighing preparation and the mechanical milling process of powder all carry out under argon shield, in advance the ball-milled powder particle be nanocrystalline (＜100nm), part powder generation combination reaction.Powder with ball milling after in advance synthetic places mould, carries out hot pressing vacuum sintering.The TiAl base alloy exhaust valve of preparation has ultra-fine crystalline substance/nanometer crystal microstructure, TiAl phase crystallite dimension＜500nm wherein, Ti
3Al phase crystallite dimension＜100nm, composition is even, excellent performance.Sintering furnace degree of vacuum is 10 * 10
-3Pa, 930～1000 ℃ of sintering temperatures, warming velocity is 30～35 ℃/min, sintering time 30～40 minutes, hot isostatic pressing power 60～80MPa.
Beneficial effect of the present invention: at first obtain nanometer-size die through high-energy ball milling, carry out hot isobaric vacuum sintering to reach nano level powder through ball milling then, obtain to have the TiAl base alloy exhaust valve of ultra-fine crystalline substance/nanocrystalline sintering structure structure.Compare with the exhaust valve tissue that casting, the forging process manufacturing of routine are same, that the exhaust valve of preparation is organized is tiny, composition is even, and density is high, and proportion is little, and has good high-temperature intensity, room temperature toughness etc.
Description of drawings
Fig. 1 is the ESEM pattern of Ti-45.7Al-5.4Nb ball milling 8h powder.
Fig. 2 is the ESEM pattern of Ti-45.7Al-5.4Nb ball milling 16h powder.
Fig. 3 is the ESEM pattern of Ti-45.7Al-5.4Nb ball milling 24h powder.
Fig. 4 is the ESEM pattern of Ti-45.7Al-5.4Nb ball milling 30h powder.
Fig. 5 is the TEM pattern and the electron diffraction pattern of Ti-45.7Al-5.4Nb ball milling 30h powder.
Fig. 6 is the ESEM pattern of Ti-47.5Al-6.8Nb ball milling 8h powder.
Fig. 7 is the ESEM pattern of Ti-47.5Al-6.8Nb ball milling 16h powder.
Fig. 8 is the ESEM pattern of Ti-47.5Al-6.8Nb ball milling 24h powder.
Fig. 9 is the ESEM pattern of Ti-47.5Al-6.8Nb ball milling 30h powder.
Figure 10 is the TEM pattern and the electron diffraction pattern of Ti-47.5Al-6.8Nb ball milling 30h powder.
Figure 11 is the ESEM pattern of Ti-45.7Al-6.2Nb ball milling 30h powder.
Figure 12 is the ESEM pattern of Ti-45.7Al-6.8Nb ball milling 30h powder.
Figure 13 is the ESEM pattern of Ti-47.5Al-5.4Nb ball milling 30h powder.
Figure 14 is the ESEM pattern of Ti-47.5Al-6.2Nb ball milling 30h powder.
Figure 15 is the x-ray diffraction pattern of Ti-45.7Al-5.4Nb ball milling 30h powder.
Figure 16 is the x-ray diffraction pattern of Ti-45.7Al-6.8Nb ball milling 30h powder.
Figure 17 is the x-ray diffraction pattern of Ti-47.5Al-5.4Nb ball milling 30h powder.
Figure 18 is the x-ray diffraction pattern of Ti-47.5Al-6.8Nb ball milling 30h powder.
Figure 19 is the transmission electron microscope pattern and the electron diffraction pattern of Ti-45.7Al-5.4Nb ball milling 30h powder vacuum sintering tissue.
Figure 20 is the x-ray diffraction pattern of Ti-45.7Al-5.4Nb ball milling 30h powder vacuum sintering tissue.
Figure 21 is the x-ray diffraction pattern of Ti-47.5Al-6.8Nb ball milling 30h powder vacuum sintering tissue.
Figure 22 is a Ti-47.5Al-6.8Nb sintering structure backscattered electron analysis result.
Embodiment
Embodiment 1: adopt the mechanical alloying method, promptly make mixed-powder generation refinement and pre-alloyed through high-energy ball milling.Acquisition comprises Ti, Al, Nb simple substance and Ti
3Al, TiAl, Ti
2Intermetallic compoundss such as Al are at interior nanometer-size die.Through the control ball-milling technology, form the Intermatallic Ti-Al compound metastable phase in the control mixed-powder and the content of the Al powder etc. of chemical combination does not take place.Cold welding and fragmentation constantly take place in powder under great plastic deformation condition, with the prolongation of ball milling time, powder particle size diminishes gradually, and size of grain is also more even.Visible from the ball milling scanned photograph of Fig. 1 (Ti-45.7Al-5.4Nb composition mixed-powder), behind the 8h, the part powder particle also keeps original powder morphology; Particle mean size is at 40～50 μ m, and with the increase gradually of ball milling time, refinement constantly takes place powder particle; As shown in Figures 2 and 3; In the time of 30 hours, as shown in Figure 4, obviously the attenuate effect of powder ball milling refinement of powder particle is very obvious; Viewed powder particle is rolled into a ball average-size at 0.8 μ m, and cluster of grains is the result that nanocrystalline generation is reunited.
As shown in Figure 5, behind high-energy ball milling 30h, the small grains of many sizes about several nm arranged on the reunion powder film, analyzing its diffraction disk is TiAl and Ti
3The interrupted polycrystal film ring of Al, TiAl and Ti
3The appearance of the interrupted polycrystalline ring of Al explains that powder particle is very tiny at this moment, has formed nanocrystalline.And can confirm that ball milling causes between Ti, Al powder alloyage having taken place, formed nano level TiAl intermetallic compounds.
The interface reaction and the diffusion reaction that take place in the alloyage of ball-milled powder and the mechanical milling process are relevant.When powder becomes very tiny through high-energy ball milling powder particle after to a certain degree,, strengthened the probability that directly reacts at the interface between the particle along with the increase of granule surface area.Powder produces a large amount of unsalted surfaces through constantly colliding simultaneously; Seam and take place to combine between atom each other when reaching certain interatomic distance between the particle; Reaction constantly produces, and is because mutual collision is being carried out continuing, and has generated compound at last.
Embodiment 2: Fig. 6 to Figure 10 is the form behind the Ti-47.5Al-6.8Nb ball milling, and the test result of powder fining rule and Ti-45.7Al-5.4Nb is similar.Like Fig. 6, Fig. 7, Fig. 8 and shown in Figure 9; With the growth of ball milling time, refinement takes place in powder gradually, because powder takes place to reunite and chemical combination in mechanical milling process; Thereby the particle size that arrives through scanning electron microscopic observation, especially the granularity of ball milling later stage powder mainly is the granularity of agglomerates.Figure 10 is shown as behind high-energy ball milling 30h; Powder particle TEM pattern and diffraction pattern; Can clearly observe very tiny powder particle from Figure 10; And because long ball milling, amorphous halo and interrupted polycrystalline ring have appearred in its diffraction pattern, and this explanation has noncrystal and nanocrystalline existence.
Embodiment 3: extremely shown in Figure 14 like Figure 11; Be respectively the form behind Ti-45.7Al-6.2Nb, Ti-45.7Al-6.8Nb, Ti-47.5Al-5.4Nb and the Ti-47.5Al-6.2Nb ball milling; It is thus clear that ball milling certain hour, powder particle evenly reach the Expected Results of refinement and alloyage.
Embodiment 4: to shown in Figure 180, be Ti-45.7Al-5.4Nb, Ti-45.7Al-6.2Nb, Ti-47.5Al-5.4Nb, the Ti-47.5Al-6.8Nb powder X-ray diffraction analysis result behind ball milling 30h like Figure 15.Visible from figure, the diffraction result of four kinds of powder is almost consistent, behind the 30h ball milling, has formed TiAl, Ti
3Al and Ti
2Al.From diffraction pattern, also can see, Ti and Al peak with the prolongation diffracted intensity of ball milling time weaken, wideization taken place in diffraction peak, this explanation powder particle size this moment is very little, and amorphous, nanocrystalline might occur.
Embodiment 5: shown in figure 19, be the transmission electron microscope pattern picture of powder sintered tissue behind the Ti-45.7Al-5.4Nb ball milling.It is thus clear that sintering structure is by the TiAl matrix and be distributed in the Ti on the matrix
3The Al phase composition, the most of crystal grain of TiAl matrix is below 500nm, and Ti
3Al has only 20～30 nanometers (shown in arrow among the figure) mutually, and its diffraction pattern is interrupted ring, explains that crystal grain is very thin.The mutual surface of contact of composite powder of the chimeric one-tenth multi-layer structure of nanometer ball-milled powder is very big, thereby element need not the very long distance of diffusion and just diffusion reaction can take place, and has formed ultra-fine brilliant TiAl phase and nanocrystalline Ti
3The Al phase constitution, obviously, Ti
3The diffusion of growing up of Al phase is more difficult.Through optimizing ball milling and sintering process, sintering structure and crystallite dimension have been controlled effectively.
Embodiment 6: like Figure 20 and shown in Figure 21, be the x-ray diffraction pattern of Ti-45.7Al-5.4Nb and Ti-47.5Al-6.8Nb ball milling 30h powder vacuum sintering tissue.It is thus clear that two kinds of powder sintered resulting tissues are TiAl and Ti
3The Al phase.Sintering structure mainly receive material composition, ball milling and sintering process influence, according to experiment at Ti 45.7-48.9% (at), Al 45.7-47.5% (at), sintering structure is TiAl and Ti in Nb 5.4-6.8% (at) composition range
3The Al phase.
Between the powder and powder behind the ball milling, bump between powder and the abrading-ball; Metal powder granulates bears extruding, fracture, welding and repeated extrusion-deformation, finally realizes the continuous refinement of powder, and tiny powder has higher activity; And powder is more tiny, and the activity of powder is also just high.Tiny powder has bigger surface area to make the diffusion admittance between the particle increase, and granule has reduced the diffusion distance of particle simultaneously, so sintering process is accomplished more easily.
Embodiment 7: Figure 22 is EBSD figure, visible Ti-47.5Al-6.8Nb sintering structure grain size distribution.Its abscissa is a crystallite dimension, and y coordinate is the shared quantity of various grain sizes.Can be known have to surpass 60% crystallite dimension all below 500nm by figure, most crystallite dimensions are all below 1 μ m.
Claims (3)
1. the aluminium base powder metallurgy automobile engine exhaust port of titanium material, the constituent and the atom percentage content of its dusty material are: Ti 45.7-48.9%, Al 45.7-47.5%, Nb 5.4-6.8%.
2. the aluminium base powder metallurgy automobile engine exhaust port of a kind of titanium according to claim 1 material, it is characterized in that: said powder purity is 99.5%; Said granularity is Ti and Al＜50 μ m, Nb＜70 μ m.
3. the production method of the aluminium base powder metallurgy automobile engine exhaust port of a titanium material, this method is:
To at first in ball grinding drum, carry out high-energy ball milling by the composition proportion powder formulated; Drum's speed of rotation is 330r/min; Ratio of grinding media to material is 12: 1, and the ball milling time is 30 hours, and the weighing preparation and the mechanical milling process of powder all carry out under argon shield; Preparatory ball-milled powder grain graininess＜100nm, part powder generation combination reaction;
Powder with ball milling after in advance synthetic places mould, carries out hot pressing vacuum sintering, and sintering furnace degree of vacuum is 10 * 10
-3Pa, 930～1000 ℃ of sintering temperatures, warming velocity is 30～35 ℃/min, sintering time 30～40 minutes, hot isostatic pressing power 60～80MPa.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106367624A (en) * | 2016-09-12 | 2017-02-01 | 江苏大学 | Y-microalloyed TiAl-based alloy being high in acid corrosion resistance |
| CN106367633A (en) * | 2016-09-12 | 2017-02-01 | 江苏大学 | La2O3-microalloyed TiAl-based alloy being high in acid corrosion resistance |
| CN107699738A (en) * | 2017-09-29 | 2018-02-16 | 成都露思特新材料科技有限公司 | A kind of fine-grained TiAl alloy and preparation method thereof, aero-engine, automobile |
| CN115261657A (en) * | 2022-08-03 | 2022-11-01 | 南京铖联激光科技有限公司 | Preparation method and preparation device of high-temperature alloy |
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|---|---|---|---|---|
| CN1490100A (en) * | 2002-10-17 | 2004-04-21 | 中国科学院金属研究所 | Manufacture of lightweight refractory titanium-aluminum based alloy exhaust gates |
| CN101245431A (en) * | 2008-03-25 | 2008-08-20 | 长春工业大学 | Gamma-group Ti-Al alloy material with high-temperature resistance oxidation and manufacture method thereof |
| CN101875106A (en) * | 2009-11-20 | 2010-11-03 | 北京科技大学 | Preparation method of directional solidification high-niobium TiAl-base alloy |
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- 2011-12-12 CN CN2011104104171A patent/CN102493853A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1490100A (en) * | 2002-10-17 | 2004-04-21 | 中国科学院金属研究所 | Manufacture of lightweight refractory titanium-aluminum based alloy exhaust gates |
| CN101245431A (en) * | 2008-03-25 | 2008-08-20 | 长春工业大学 | Gamma-group Ti-Al alloy material with high-temperature resistance oxidation and manufacture method thereof |
| CN101875106A (en) * | 2009-11-20 | 2010-11-03 | 北京科技大学 | Preparation method of directional solidification high-niobium TiAl-base alloy |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106367624A (en) * | 2016-09-12 | 2017-02-01 | 江苏大学 | Y-microalloyed TiAl-based alloy being high in acid corrosion resistance |
| CN106367633A (en) * | 2016-09-12 | 2017-02-01 | 江苏大学 | La2O3-microalloyed TiAl-based alloy being high in acid corrosion resistance |
| CN106367624B (en) * | 2016-09-12 | 2017-10-13 | 江苏大学 | High acid etching resistance Y microalloying TiAl-base alloys |
| CN107699738A (en) * | 2017-09-29 | 2018-02-16 | 成都露思特新材料科技有限公司 | A kind of fine-grained TiAl alloy and preparation method thereof, aero-engine, automobile |
| CN115261657A (en) * | 2022-08-03 | 2022-11-01 | 南京铖联激光科技有限公司 | Preparation method and preparation device of high-temperature alloy |
| CN115261657B (en) * | 2022-08-03 | 2023-02-28 | 南京铖联激光科技有限公司 | Preparation method and preparation device of high-temperature alloy |
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Application publication date: 20120613 |