CN104004942B - TiC particle-reinforced nickel-based composite material and preparation method thereof - Google Patents
TiC particle-reinforced nickel-based composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a TiC particle-reinforced nickel-based composite material. The TiC particle-reinforced nickel-based composite material comprises, by volume, 3-30% of TiC particles and the balance a mother alloy. The mother alloy is one of all nickel alloys. The preparation method comprises that a precast block green-blank Ni-Ti-C as a particle synthesis reactant, which comprises Ni powder, Ti powder and C powder and has Ni powder content of 5-50% by mass and a mole ratio of the Ti powder to the C powder of 1: 1, and the mother alloy are added into a vacuum induction furnace together and then are melted to form the TiC particle-reinforced nickel-based composite material. The preparation method effectively solves the problem that the traditional preparation method has a high cost, complex processes, various particle morphology, nonuniform distribution and poor density, has the characteristics of low cost and simple processes and can be used for manufacturing a nickel-based high-temperature alloy large-scale complex casting.
Description
Technical field
The present invention relates to field of compound material, in particular it relates to a kind of TiC particle enhanced nickel base composite material and
Preparation method.
Background technology
Nickel base superalloy is due to its excellent high performance, it has also become currently manufactured advanced aero engine and gas turbine heat
The main material of end pieces, mainly includes casing class bearing member, turbo blade, combustor, the turbine disk and part compressor
Blade etc..Aeronautical and space technology develops rapidly and requires that the complex parts of aircraft can bear more operation at high temperature, exploitation tool
The nickel-base high-temperature composite technology of preparing having higher heat resisting temperature is most important to improving engine thermal efficiency, it is possible to decrease combustion
Material consumption rate, promotes engine performance, improves aircraft range, has energy-saving and emission-reduction effect.Therefore to more operation at high temperature
Cast nickel-base alloy materials demand urgent.
The heat resisting temperature of the most common K4169 cast Ni-base alloy is 650 DEG C, and during more than 650 DEG C, its main high temperature is strong
Change phase γ ' ' will dissolve or be changed into δ phase, lose High-Temperature Strengthening effect.At present both at home and abroad mainly by add a large amount of Co,
The rare noble metal such as W, Re improves nickel-base alloy high-temperature behavior, and the present invention is by adding the increasing of low cost the second phase
Strong granule prepares nickel-base composite material to promote material at high temperature performance.
Particulate reinforced composite can be effectively improved the wearability of base alloy material, high-temperature behavior, and particle-reinforced method is by extensively
General for preparing metal-base composites.Shanghai Communications University Lv Wei is clean et al. utilizes TiC, TiB and rare earth oxide
As hardening constituent be prepared for titanium matrix composite (patent publication No. ZL02111575.3, ZL02112260.1 and
ZL200510029075.3 etc.).The report that aluminum matrix composite is prepared in employing granule enhancing is more, and meter Guo Fa et al. invents
A kind of method (ZL201210413996.x) preparing particle enhanced aluminum-based composite material, Wang Hongming et al. invention one
Plant the method (ZL201110037708.0) etc. of electric current and magnetic field synthesizing particle reinforced composite material under composite action.Jilin
University Wang Hui is remote et al. is added TiC granule to magnesium alloy and steel to put forward heavy alloyed wearability by in-situ authigenic method
Energy.Owing to being limited by matrix material performance, the high-temperature behavior of magnesio, aluminum base, titanio and iron base composite material all the time without
Method surmounts nickel-base high-temperature alloy material.
Prepare the patent of metal-base composites about granule enhancing and document is more, but TiC granule strengthens and prepares Ni-based conjunction
Document prepared by metal/composite material is little.The representative Harbin Institute of Technology Zhang Xinghong et al. that has utilizes self-propagating high
Temperature conbustion synthesis (SHS) combines high temperature insostatic pressing (HIP) and prepares TiC-Ni base metal-ceramic material, and the method is limited by technical equipment,
The composite that Ni content is relatively low can only be prepared, if Ni content will be unable to more than 70% SHS synthetic reaction.By
Raw material in this technology of preparing is all powder, needs compressing, prepares complex-shaped workpiece difficulty, the consistency of finished product
Can not show a candle to workpiece prepared by casting technique, and this technology production cost is high.Bao Yanrong of North China Electric Power University et al. is at gold
The article " microstructure and property of hot pressing in-situ synthesizing TiC-xNi composite " delivered on genus heat treatment describes one and adopts
The method preparing nickel-base composite material material by powder metallurgic method, but the workpiece prepared by powder metallurgic method is to finished product pattern
Have some limitations with the consistency of material.Additionally, Liu Zongde of North China Electric Power University et al. is at " Materials
Science and Engineering A " on deliver one prepare nickel-base composite material about in-situ authigenic method, the method
Technological process is: first Ti Yu C mixed-powder is pressed into prefabricated section, then passes through Ti-C prefabricated section with electrolytic nickel very
Adding hot smelting in empty induction furnace and prepare TiC particle enhanced nickel base composite material, result shows TiC and is distributed not in ingot casting
Uniformly, and granule-morphology has square and needle-like two kinds, and TiC particle enhanced nickel base composite material performance prepared by this technique is not
Stable.Additionally, the granule of this TiC particle enhanced nickel base composite material prepares the binary that raw material is Ti powder and C powder composition
System, the temperature spot of Ti-C binary system generation synthetic reaction is high, the fusing point of high-temperature metal Ni, close to the fusing point of Ti,
It is unfavorable for that particle size controls and is uniformly distributed.Liu Zongde et al. also invented a kind of in-situ reactive synthesis TiCxGranule strengthens
The preparation method (ZL200910091602.1) of nickel-base composite material, Ti, C, Al, Fe and Mo are mixed by the method
Powder nickel foil packages, and adds in vacuum medium frequency induction furnace after briquet, melting casting together with electrolytic nickel, preparation
Go out consistency close to 100%, the TiC that elevated temperature strength and hardness significantly improvexParticle enhanced nickel base composite material.This technique
Ni substrate used is based on metallic nickel powder, expensive, and needs to wrap up mixed-powder briquet, work with nickel foil
Skill is complicated, is not suitable for the big production of industrialization.
Summary of the invention
For defect of the prior art, it is an object of the invention to provide a kind of TiC particle enhanced nickel base composite material
And preparation method thereof, technique is simple, the size of TiC granule and quantity in low cost, and controllable composite.
According to an aspect of the present invention, it is provided that a kind of TiC particle enhanced nickel base composite material, described material comprises
Component and content be: TiC particle volume percentage composition is 3%-30%, and remaining is foundry alloy；Described foundry alloy is institute
There is the one in nickel alloy.
Preferably, described TiC granule is to be generated by the reaction of Ni-Ti-C prefabricated section green compact, Ni-Ti-C prefabricated section green compact
Consist of Ni powder, Ti powder and C powder, Ni powder weight/mass percentage composition is 5-50%, Ti powder and the mol ratio of C powder is
1:1.It is highly preferred that Ni powder weight/mass percentage composition is 20-30%.
Preferably, described Ni powder footpath is 200-800 mesh, purity >=99.5%.
Preferably, described Ti powder footpath is 200-800 mesh, purity >=99.5%.
Preferably, described C powder footpath is≤2000 mesh, purity >=99.5%.
Preferably, described TiC particle volume percentage composition is 3-10%, further, for 4-7%, in this scope
In can obtain performance more preferable TiC particle enhanced nickel base composite material.
Preferably, described TiC granule be smaller in size than 10 microns, it is highly preferred that TiC granule to be smaller in size than 5 micro-
Rice.
Preferably, the pattern of described TiC granule such as is at the shaft-like, spherical or cubic, it is highly preferred that be spherical.
According to another aspect of the present invention, it is provided that the preparation side of a kind of above-mentioned TiC particle enhanced nickel base composite material
Method, described method using prefabricated section green compact (Ni-Ti-C) as granule synthetic reaction thing, together add with foundry alloy to
In vaccum sensitive stove, TiC particulate reinforced composite is prepared in melting, specifically includes following steps:
(1) weigh Ni powder, Ti powder, C powder and foundry alloy according to the mass percent of each component；
(2) use mixing plant by powder mix homogeneously good for step (1) proportioning；
(3) the powder of step (2) mix homogeneously is pressed into Ni-Ti-C prefabricated section green compact；
(4) in green compact prefabricated section and foundry alloy together being inserted vaccum sensitive stove, melting is cast into ingot.
Preferably, described step (2) in: use the mixed method such as blender, batch mixer or ball mill by Ni powder, Ti
Powder and C powder mix homogeneously.
Preferably, described step (3) in: use cold isostatic pressing method mixed-powder is prepared as Ni-Ti-C prefabricated section
Green compact, green compact compacting consistency is 50-90%.
It is highly preferred that described step (3) in: by step (2) in the powder of mix homogeneously load in mould, apply 50-100MPa
Pressure, pressing time is the 10-20 second, is prepared as Ni-Ti-C prefabricated section green compact, and its consistency is 50-90%.
Preferably, described step is (4), specific as follows:
1. sample is filled: the prefabricated section green compact of preparation and foundry alloy are together inserted melting in vaccum sensitive stove；
2. melting atmosphere: vacuum in stove is evacuated to 1 × 10-2-1×10-4Pa, is passed through argon so that it is pressure is
0.01-0.08MPa,
3. melting casting: in-furnace temperature rises to 1450-1800 DEG C, and refine was cast into ingot after 3-8 minute, obtains described
TiC particle enhanced nickel base composite material.
The inventive method utilize prefabricated section green compact (Ni-Ti-C system) as reactant, by it together with Ni-based foundry alloy
Melting, successfully prepares TiC particle enhanced nickel base composite material.Green compact prefabricated section vacuum induction is heated to reaction temperature, closes
Become pattern rule (spherical), Sizes (＜ 10 μm) and the TiC granule clean with basal body interface, and by sense
Should stir, make TiC granule be uniformly distributed in base alloy.This technology efficiently solves conventional Ti C granule and strengthens nickel
Based composites preparation cost is high, complex process and granule-morphology is various poor with skewness and consistency etc. asks
Topic.The present invention uses the technique that in-situ synthesis combines with traditional melting casting, is a kind of with low cost and technique letter
Single TiC particle enhanced nickel base composite material preparation method, and the method to can be used for manufacturing nickel base superalloy large-scale multiple
Miscellaneous foundry goods.The present invention, by adjusting the composition of in-situ synthesized reaction thing (Ni-Ti-C prefabricated section green compact), can control multiple
Particle size, pattern and quantity in condensation material.
Compared with prior art, the present invention has a following beneficial effect:
1. the present invention wraps up mixed-powder without nickel foil, can be high by the method preparation that technique is simple and with low cost
The nickel-base composite material of performance；
2. spherical TiC granule-morphology rule, the Sizes that prepared by the present invention, it is evenly distributed；
3. the present invention can adjust the addition of prefabricated section green compact and controls the content of reinforcement in composite
(3%-30%), prepare the nickel-base composite material of different performance with this, meet different demand with this；
4. due to the fact that it is melting cast molding, therefore can produce and prepare outside high-compactness, large scale, complexity
The product of shape.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following example will assist in those skilled in the art
Member is further appreciated by the present invention, but limits the present invention the most in any form.It should be pointed out that, the common skill to this area
For art personnel, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement.These broadly fall into
Protection scope of the present invention.Following example do not have the part described in detail prior art all can be used to realize.
Embodiment 1: prepare the nickel-base composite material that TiC volumn concentration is 3%
1. the preparation of mixed-powder: weigh nickel by powder (purity: 99.5%, granularity :-200 mesh), titanium powder by proportioning (pure
Degree: 99.5%, granularity :-200 mesh) and C powder (purity: 99.5%, granularity :-12500 mesh), Ni powder 50wt.%,
Ti powder is 1:1 with the mol ratio of C powder, by three kinds of powder self-control blender mix homogeneously；
2. prepared by green compact: mixed-powder loads in the mould that internal diameter is Ф 50mm, applies the pressure of 100MPa, pressurization
Time is 20 seconds, is prepared as the green compact prefabricated section of Ф 50mm × 10mm, and its consistency is 90%；
3. melting casting: green compact prefabricated section is inserted in vacuum induction melting furnace together with K4169 foundry alloy, green compact with
The mass percent of K4169 foundry alloy is about 1:55.In stove, vacuum is evacuated to 1 × 10-4Pa, is passed through argon so that it is pressure
For 0.01MPa.Starting melting, in-furnace temperature rises to 1450 DEG C, and refine was cast into ingot after 3 minutes；
In this embodiment, 50%Ni-Ti-C system is synthesized the size spherical TiC granule about 3 μm, and granule is equal
Even being distributed in base alloy, its volumn concentration accounts for about 3%.
Embodiment 2: prepare the nickel-base composite material that TiC volumn concentration is 5%
1. the preparation of mixed-powder: weigh nickel by powder (purity: 99.5%, granularity :-400 mesh), titanium powder by proportioning (pure
Degree: 99.5%, granularity :-400 mesh) and C powder (purity: 99.5%, granularity :-8000 mesh), Ni powder 10wt.%,
Ti powder is 1:1 with the mol ratio of C powder, by three kinds of powder batch mixer mix homogeneously；
2. prepared by green compact: mixed-powder loads in the mould that internal diameter is Ф 50mm, applies the pressure of 80MPa, during pressurization
Between be 15 seconds, be prepared as the green compact prefabricated section of Ф 50mm × 12mm, its consistency is 70%；
3. melting casting: green compact prefabricated section is inserted in vacuum induction melting furnace together with K4169 foundry alloy, green compact with
The mass percent of K4169 foundry alloy is about 1:26.In stove, vacuum is evacuated to 0.6 × 10-3Pa, is passed through argon so that it is pressure
Strong is 0.04MPa.Starting melting, in-furnace temperature rises to 1650 DEG C, and refine was cast into ingot after 5 minutes；
In this embodiment, 10%Ni-Ti-C system is synthesized size at the spherical TiC granule less than 8 μm, and granule is uniform
Being distributed in base alloy, its volumn concentration accounts for about 5%.
Embodiment 3: preparing TiC particle volume percentage composition is the nickel-base composite material of 15%
1. the preparation of mixed-powder: weigh nickel by powder (purity: 99.5%, granularity :-400 mesh), titanium powder by proportioning (pure
Degree: 99.5%, granularity :-400 mesh) and C powder (purity: 99.5%, granularity :-8000 mesh), Ni powder 20wt.%,
Ti powder is 1:1 with the mol ratio of C powder, by three kinds of powder batch mixer mix homogeneously；
2. prepared by green compact: mixed-powder loads in the mould that internal diameter is Ф 50mm, applies the pressure of 75MPa, during pressurization
Between be 15 seconds, be prepared as the green compact prefabricated section of Ф 50mm × 13mm, its consistency is 65%；
3. melting casting: green compact prefabricated section is inserted in vacuum induction melting furnace together with K4202 foundry alloy, green compact with
The mass percent of K4202 foundry alloy is about 1:7.5.In stove, vacuum is evacuated to 0.6 × 10-3Pa, is passed through argon so that it is pressure
Strong is 0.04MPa.Starting melting, in-furnace temperature rises to 1650 DEG C, and refine was cast into ingot after 5 minutes；
In this embodiment, 20%Ni-Ti-C system is synthesized size at the spherical TiC granule less than 8 μm, and granule is uniform
Being distributed in K4202 base alloy, its volumn concentration accounts for about 15%.
Embodiment 4: preparing TiC particle volume percentage composition is the nickel-base composite material of 30%
1. the preparation of mixed-powder: weigh nickel by powder (purity: 99.5%, granularity :-800 mesh), titanium powder by proportioning (pure
Degree: 99.5%, granularity :-800 mesh) and C powder (purity: 99.5%, granularity :-2000 mesh), Ni powder 5wt.%,
Ti powder is 1:1 with the mol ratio of C powder, by three kinds of powder ball mill mix homogeneously；
2. prepared by green compact: mixed-powder loads in the mould that internal diameter is Ф 50mm, applies the pressure of 50MPa, during pressurization
Between be 10 seconds, be prepared as Ф 50mm × 15mm, consistency is the green compact prefabricated section of 50%；
3. melting casting: green compact prefabricated section is inserted in vacuum induction melting furnace together with K4169 foundry alloy, green compact with
The mass percent of K4169 foundry alloy is about 1:36.In stove, vacuum is evacuated to 1 × 10-2Pa, is passed through argon so that it is pressure
For 0.08MPa.Starting melting, in-furnace temperature rises to 1800 DEG C, and refine was cast into ingot after 8 minutes；
In this embodiment, 5%Ni-Ti-C system is synthesized size at the spherical TiC granule less than 10 μm, and granule is uniform
Being distributed in base alloy, its volumn concentration accounts for about 30%.
Above the specific embodiment of the present invention is described.It is to be appreciated that the invention is not limited in
Stating particular implementation, those skilled in the art can make various deformation or amendment within the scope of the claims,
This has no effect on the flesh and blood of the present invention.
Claims (13)
1. a TiC particle enhanced nickel base composite material, it is characterised in that component that described material comprises and percentage
Content is: TiC particle volume percentage composition is 3%-30%, and remaining is foundry alloy；Described foundry alloy is all nickel alloys
In one；
Described TiC granule is to be generated by the reaction of Ni-Ti-C prefabricated section green compact, consisting of of Ni-Ti-C prefabricated section green compact
Ni powder, Ti powder and C powder, Ni powder weight/mass percentage composition is 5-50%, Ti powder and the mol ratio of C powder is 1:1.
TiC particle enhanced nickel base composite material the most according to claim 1, it is characterised in that described Ni powder
Weight/mass percentage composition is 20-30%.
TiC particle enhanced nickel base composite material the most according to claim 1, it is characterised in that described Ni powder
Particle diameter is 200-800 mesh, purity >=99.5%；Described Ti powder footpath is 200-800 mesh, purity >=99.5%；Described C
Powder footpath is≤2000 mesh, purity >=99.5%.
4. according to the TiC particle enhanced nickel base composite material described in any one of claim 1-3, it is characterised in that institute
Stating TiC particle volume percentage composition is 3-10%.
TiC particle enhanced nickel base composite material the most according to claim 4, it is characterised in that described TiC
Granule be smaller in size than 10 microns.
TiC particle enhanced nickel base composite material the most according to claim 5, it is characterised in that described TiC
Granule be smaller in size than 5 microns.
7. according to the TiC particle enhanced nickel base composite material described in any one of claim 1-3, it is characterised in that institute
Stating the pattern of TiC granule the shaft-like, spherical or cubic such as is.
TiC particle enhanced nickel base composite material the most according to claim 7, it is characterised in that described TiC
The pattern of granule is spherical.
9. according to a preparation method for the TiC particle enhanced nickel base composite material described in any one of claim 1-8,
It is characterized in that, described method, using prefabricated section green compact Ni-Ti-C as granule synthetic reaction thing, together adds with foundry alloy
Add to melting in vaccum sensitive stove and prepare TiC particulate reinforced composite；Specifically include following steps:
(1) weigh Ni powder, Ti powder, C powder and foundry alloy according to the mass percent of each component；
(2) use mixing plant by powder mix homogeneously good for step (1) proportioning；
(3) the powder of step (2) mix homogeneously is pressed into Ni-Ti-C prefabricated section green compact；
(4) Ni-Ti-C prefabricated section green compact and foundry alloy are together inserted melting in vaccum sensitive stove be cast into ingot and obtain institute
State composite.
The preparation method of TiC particle enhanced nickel base composite material the most according to claim 9, it is characterised in that
Described step (2) in: use blender, batch mixer or ball mill by Ni powder, Ti powder and C powder mix homogeneously.
The preparation method of 11. TiC particle enhanced nickel base composite materials according to claim 9, it is characterised in that
Described step (3) in: use cold isostatic pressing method mixed-powder is prepared as Ni-Ti-C prefabricated section green compact, Ni-Ti-C
Prefabricated section green compact compacting consistency is 50-90%.
The preparation method of 12. TiC particle enhanced nickel base composite materials according to claim 9, it is characterised in that
Described step (3) in: by step (2) in the powder of mix homogeneously load in mould, apply the pressure of 50-100MPa, add
The pressure time is the 10-20 second, is prepared as Ni-Ti-C prefabricated section green compact, and its consistency is 50-90%.
13. according to the preparation method of the TiC particle enhanced nickel base composite material described in any one of claim 9-12, its
Being characterised by, described step is (4), specific as follows:
1. sample is filled: the prefabricated section green compact of preparation and foundry alloy are together inserted melting in vaccum sensitive stove；
2. melting atmosphere: vacuum in stove is evacuated to 1 × 10-2-1×10-4Pa, is passed through argon so that it is pressure is
0.01-0.08MPa,
3. melting casting: in-furnace temperature rises to 1450-1800 DEG C, and refine was cast into ingot after 3-8 minute, obtains described
TiC particle enhanced nickel base composite material.
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| CN106319288B (en) * | 2015-07-03 | 2017-12-08 | 中国科学院上海硅酸盐研究所 | Be introduced directly into strengthens nickel-base composite material and its preparation method and application jointly with In-situ Synthesis TiC Particle |
| CN106058291B (en) * | 2016-07-01 | 2018-12-07 | 中国科学院上海硅酸盐研究所 | A kind of metallic interconnection materials and preparation method thereof for solid oxide fuel cell |
| CN108504886B (en) * | 2017-02-24 | 2020-01-17 | 中国科学院上海硅酸盐研究所 | Preparation method of TiC-C nickel-based alloy self-lubricating composite material |
| CN108486402B (en) * | 2018-03-07 | 2020-01-07 | 上海交通大学 | TiN particle reinforced nickel-based composite material and preparation method thereof |
| CN113718132B (en) * | 2021-08-31 | 2022-09-16 | 华中科技大学 | Ni alloy for refining grains by solute interaction and preparation method thereof |
| CN114525425B (en) * | 2022-02-21 | 2023-02-14 | 大连理工大学 | MC type carbide reinforced nickel-based superalloy composite material, preparation method and application thereof |
| CN115475947B (en) * | 2022-10-17 | 2024-01-12 | 吉林大学 | Preparation method and application of surface {100} crystal face cube transition metal carbide particles |
| CN116334422A (en) * | 2023-03-17 | 2023-06-27 | 西安航天发动机有限公司 | Forming method capable of realizing grain refinement of K4202 superalloy |
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| GB2076019A (en) * | 1980-05-16 | 1981-11-25 | Metallurg Ind Inc | Erosion-resistant Alloys |
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| CN1091473A (en) * | 1993-11-08 | 1994-08-31 | 武汉工业大学 | Autoreaction-fusion technology prepares metal-base composites |
| CN1137273C (en) * | 2000-07-27 | 2004-02-04 | 钢铁研究总院 | Process for preparing ceramic-phase diffusion enhanced alloy and particle enhanced metal-base composition |
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| GB2076019A (en) * | 1980-05-16 | 1981-11-25 | Metallurg Ind Inc | Erosion-resistant Alloys |
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| Title |
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