CN106319288A - Directly-introduced and in-situ generated TiC particle commonly-enhanced nickel-base composite and preparing method and application thereof - Google Patents
Directly-introduced and in-situ generated TiC particle commonly-enhanced nickel-base composite and preparing method and application thereof Download PDFInfo
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- CN106319288A CN106319288A CN201510390397.4A CN201510390397A CN106319288A CN 106319288 A CN106319288 A CN 106319288A CN 201510390397 A CN201510390397 A CN 201510390397A CN 106319288 A CN106319288 A CN 106319288A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention relates to a directly-introduced and in-situ generated TiC particle commonly-enhanced nickel-base composite and a preparing method and application thereof. The composite comprises a nickel-base alloy base body, directly-introduced TiC particles and in-situ generated TiC particles, wherein the directly-introduced TiC particles and the in-situ generated TiC particles are evenly distributed in the nickel-base alloy base body. The in-situ generated TiC particles account for 10 wt.%-40 wt.% of the total mass of TiC. According to the directly-introduced and in-situ generated TiC particle commonly-enhanced nickel-base composite, the heat expansion coefficient of the nickel-base alloy is effectively reduced, and meanwhile good linear expansion behaviors and high electric conductivity are kept.
Description
Technical field
The present invention relates to field of metal matrix composite, be particularly used for intermediate temperature solid oxide fuel cell (SOFC)
A kind of Novel connecting body material is introduced directly into and jointly strengthens nickel-base composite material and preparation side thereof with In-situ Synthesis TiC Particle
Method.
Background technology
SOFC (SOFC) is efficient, clean, all solid state electrochemical appliance, can pass through electrochemistry
Chemical energy in Fossil fuel is directly converted into the continuous generating device of electric energy by reaction.Its core is cathode-electrolyte-anode group
The PEN structure become.Monomer SOFC power limited, it is therefore desirable to several monocells with series, parallel or are mixed by connector
The mode of connection is assembled into set of cells power required for obtaining.The Main Function of connector is that each monocell is coupled together,
Improve output voltage and electric current, separate fuel gas and the oxidizing gas of cathode side of anode-side and support the effect protected.Therefore
Performance requirement to metallic interconnection materials is to have good conduction, heat conductivility and chemical stability；The heat good with other assemblies
Coefficient of expansion matching；Excellent antioxidation, curability；Good mechanical property and processing characteristics.
Along with having the appearance of higher oxygen ionic conductivity electrolyte under middle temperature, the use temperature of fuel cell from
Being down to less than 800 DEG C for 1000 DEG C, metallic interconnection materials can be by conduction, heat conduction and excellent in mechanical performance, it is easy to the metal material of processing
Replace high cost, the chromic lanthanum ceramics of preparation difficulty.Conventional connector metal material includes Ni-based, chromio, ferrous alloy.
Chromium-base alloy has good corrosion-resistant, and antioxygenic property and its coefficient of expansion are preferable with electrolyte matching, but the preparation of complexity
Technique and higher cost limit the extensive application of chromium-base alloy.Ferrous alloy is cheap, the coefficient of expansion and electrolyte
Joining property is good, but its high-temperature oxidation resistance is poor, needs to prepare face coat to improve its high-temperature oxidation resistance, adds work
The complexity of skill.Nickel-base alloy has good mechanical behavior under high temperature and antioxygenic property, but its higher coefficient of expansion becomes
Limit the nickel-base alloy principal element as intermediate temperature solid oxide fuel cell metallic interconnection materials.Existing regulation nickel-base alloy expands
The method of coefficient as reduced the content of chromium by regulating the content of alloying element, can increase the content etc. of molybdenum, but the method can be led
Cause the reduction of nickel-base alloy high-temperature oxidation resistance and the nonlinear change of expansion behavior.
Summary of the invention
The problem existed for prior art, it is an object of the invention to provide one and intermediate temperature solid oxide fuel cell
Matched expansion coefficient, compact structure, there is the metallic interconnection materials of excellent conductive performance, be i.e. introduced directly into and in-situ preparation
TiC granule strengthens nickel-base composite material jointly, can solve nickel-base alloy as the higher problem of the metallic interconnection materials coefficient of expansion,
Keep its preferable electric conductivity and linear expansion behavior simultaneously, SOFC has stronger practicality prospect.
On the one hand here, the present invention provides one to be introduced directly into In-situ Synthesis TiC Particle jointly to strengthen Ni-based composite wood
Material, it includes Superalloy Substrate and the TiC granule being introduced directly into being evenly distributed in described Superalloy Substrate and former
The TiC granule that position generates, wherein, it is 10～40wt.% that generated in-situ TiC granule accounts for the mass fraction of total TiC.
It is preferred that described composite is to be obtained by TiC-Ti-C precast body and the reactive infiltration of Ni-based foundry alloy, described
The TiC granule being introduced directly into is from the TiC in TiC-Ti-C precast body, and described generated in-situ TiC granule is Ni-based foundry alloy
After fusing, spontaneous infiltration is in TiC-Ti-C precast body, and by Ti powder, C powder and foundry alloy react the TiC generated.
It is preferred that part TiC granule is nucleocapsid structure, generated in-situ TiC particle size≤2 μm, it is introduced directly into
TiC particle size is 5～10 μm.
It is preferred that it is 50～60vol.% that TiC granule accounts for the volume fraction of described composite.
It is preferred that described nickel-base alloy is Ni-Fe, Ni-Mo, Ni-Mo-Cr, Ni-Fe-Co, Ni-Cr-Fe, Ni-Mo-
Any one in Ti and Ni-Mo-Nb.
Described composite in the mean thermal expansion coefficients scope of 25～450 DEG C of temperature ranges 9～11 × 10-6K-1Between,
And vary with temperature holding linear expansion behavior.The electrical resistivity range of described composite is between 4～7m Ω cm.
Therefore, being introduced directly into of the present invention jointly strengthens nickel-base composite material and significantly reduces nickel with In-situ Synthesis TiC Particle
The thermal coefficient of expansion of base alloy, keeps good linear expansion behavior and high electrical conductivity simultaneously.
On the other hand, the present invention provides above-mentioned being introduced directly into jointly to strengthen nickel-base composite material with In-situ Synthesis TiC Particle
Preparation method, comprises the following steps:
(1) TiC powder, Ti powder, C powder and foundry alloy are weighed according to the mass percent of each design of components；
(2) after TiC powder, Ti powder and C powder mix homogeneously, it is pressed into TiC-Ti-C precast body；
(3) foundry alloy is placed in above TiC-Ti-C precast body, carries out adding heat fusing pressureless penetration.
The present invention prepares employing technique simple pressureless penetration method and the TiC powder of low cost, Ti powder and C powder, preparation cost
Relatively low, there is the biggest practical application foreground.
It is preferred that in TiC-Ti-C precast body, TiC particle diameter is 5～10 μm, purity >=99.5%；Ti powder footpath is
1～5 μm, purity >=99.9%；C powder footpath is 1～5 μm, purity >=99.9%, and Ti powder and the mol ratio of C powder
For 1:1；The porosity of described TiC-Ti-C precast body is 40～50%.
It is preferred that the environment of pressureless penetration is inert atmosphere (argon) or vacuum, the temperature of pressureless penetration is
1400 DEG C～1600 DEG C, temperature retention time is 10～60 minutes.
Another aspect, the present invention provides above-mentioned being introduced directly into jointly to strengthen nickel-base composite material with In-situ Synthesis TiC Particle
Application, i.e. it can be used as the metallic interconnection materials of intermediate temperature solid oxide fuel cell.
The invention have the characteristics that
1. being introduced directly into of the present invention jointly strengthens the thermal coefficient of expansion of nickel-base composite material and the phase of YSZ with In-situ Synthesis TiC Particle
Closely, for 9-11 × 10-6K-1, and in the range of 25-450 DEG C, keep good linear expansion behavior, such that it is able to reduce connector
The thermal stress produced during materials'use；
2. the present invention is introduced directly into and jointly strengthens nickel-base composite material with In-situ Synthesis TiC Particle and have good electric conductivity, wherein resistance
Rate is 4-7m Ω cm；
3. the present invention is introduced directly into jointly strengthen with In-situ Synthesis TiC Particle nickel-base composite material use pressureless penetration method prepare；
Situ the most of the present invention generate TiC granule be melted by Ni-based foundry alloy after spontaneous infiltration in TiC-Ti-C precast body, wherein
Ti powder and C powder and foundry alloy react and generate TiC, therefore, strengthen granule and are made up of two parts, directly draw in composite
Enter and generated in-situ TiC granule, and In-situ Synthesis TiC Particle particle diameter is less than the TiC granule being introduced directly into；
5. the present invention uses technique simple pressureless penetration method, is a kind of simple, it is easy to business-like intermediate temperature solid oxide fuel cell
Metallic interconnection materials.
Accompanying drawing explanation
Fig. 1 jointly strengthens nickel-base composite material appearance picture for being introduced directly into In-situ Synthesis TiC Particle；
Fig. 2 for be introduced directly into jointly strengthen with In-situ Synthesis TiC Particle nickel-base composite material situ generate TiC account for total TiC mass
The XRD result of 10-40%: TiC-TG1:10%in-situ TiC；TiC-TG2:20%in-situ TiC；TiC-TG3:
30%in-situ TiC；TiC-TG4:40%in-situ TiC；
Fig. 3 for be introduced directly into jointly strengthen with In-situ Synthesis TiC Particle nickel-base composite material situ generate TiC account for total TiC mass
10-40% SEM result: (a) 10%in-situ TiC；(b) 20%in-situ TiC；(c) 30%in-situ TiC；(d)
40%in-situ TiC；
Fig. 4 for be introduced directly into jointly strengthen with In-situ Synthesis TiC Particle nickel-base composite material situ generate TiC account for total TiC mass
The expansion behavior of 10-40% varies with temperature curve: [1] 10%in-situ TiC；[2] 20%in-situ TiC；[3] 30%in-situ
TiC；[4] 40%in-situ TiC.
Detailed description of the invention
The present invention is further illustrated, it should be appreciated that accompanying drawing and following embodiment are only below in conjunction with accompanying drawing and following embodiment
For the present invention is described, and the unrestricted present invention.
One aspect of the present invention offer one is introduced directly into and jointly strengthens nickel-base composite material with In-situ Synthesis TiC Particle, and this is multiple
Condensation material includes Superalloy Substrate and the TiC granule being introduced directly into being evenly distributed in described Superalloy Substrate and former
The TiC granule that position generates.Wherein, all TiC granules account for the volume fraction of described composite can be 50～60vol.%.
The composite of the present invention can be by the component structure design of TiC-Ti-C precast body and the reactive infiltration of nickel-base alloy
Prepare.Wherein, the TiC granule being introduced directly into is from the TiC in TiC-Ti-C precast body, and generated in-situ TiC granule is nickel
After the fusing of base foundry alloy, spontaneous infiltration is in TiC-Ti-C precast body, and by Ti powder, C powder and foundry alloy react and generate
TiC.The composite of the present invention contains the TiC granule being introduced directly into and generated in-situ TiC granule simultaneously, can reduce
The thermal coefficient of expansion of former nickel-base alloy, and keep its preferable electric conductivity and linear expansion behavior.It is introduced directly into if comprised only
TiC granule, then grain composition degree is less than part in-situ preparation, and the mechanical strength of composite can reduce；And if comprising only former
The TiC granule that position generates, then deformation aggravation in composite preparation process, because reaction in-situ has certain volume contraction,
And cost is introduced directly into TiC granule, because the price of Ti powder (1200 yuan/kg) is significantly larger than TiC powder higher than containing part
(150 yuan/kg).Preferably, generated in-situ TiC granule accounts for total TiC mass fraction and can adjust between 10-40wt.%
Joint.If generated in-situ TiC granule accounts for total TiC mass fraction outside this range, then cost improves, and in-situ preparation
The increase of TiC amounts of particles can cause little amounts of particles to increase, then the restriction ability of the thermal expansion behavior of matrix is dropped by TiC granule
Low, cause the coefficient of expansion of composite higher than electrolyte (YSZ), meanwhile, the increase that TiC specific grain surface amasss can be strengthened
Scattering to electronics makes the increase of resistivity, causes the reduction of composite overall performance.
It addition, the particle diameter of generated in-situ TiC granule is less than the TiC granule being introduced directly into.Such as, generated in-situ TiC
Particle size≤2 μm, the TiC particle size being introduced directly into is that 5～10 μm, grain refine and grating are conducive to raising compound
The intensity of material.Both particle dispersions are distributed in the matrix of nickel-base alloy.It addition, part TiC granule is nucleocapsid structure.
The composite of the present invention has the thermal coefficient of expansion good with SOFC matching, and its thermal coefficient of expansion can be at 9-
11×10-6K-1In the range of (25-450 DEG C) adjustable, with the thermal coefficient of expansion 10.5 × 10 of electrolyte yttrium stable zirconium oxide (YSZ)- 6K-1Close, and vary with temperature the linear expansion behavior keeping good.Additionally, this material has good electric conductivity, resistance
Rate is 4-7m Ω cm.Therefore, the present invention be introduced directly into that jointly strengthen nickel-base composite material with In-situ Synthesis TiC Particle effective
Reduce the thermal coefficient of expansion of nickel-base alloy, keep good linear expansion behavior and high electrical conductivity simultaneously, can be used for replacing
Tradition nickel-base alloy is as the metallic interconnection materials of intermediate temperature solid oxide fuel cell.
It addition, the Superalloy Substrate in the present invention includes all nickel alloys, it is preferably suitable for as middle temperature solid-oxide
The nickel alloy of fuel cell connector material, includes but not limited to Ni-Fe, Ni-Mo, Ni-Mo-Cr, Ni-Fe-Co, Ni-Cr-
Any one in Fe, Ni-Mo-Ti, Ni-Mo-Nb.
Being introduced directly into of the present invention jointly strengthens nickel-base composite material with In-situ Synthesis TiC Particle can be prefabricated by TiC-Ti-C
Prepared by the pressureless penetration method of body.By TiC-Ti-C precast body composition is designed, introduces titanium valve and carbon dust, preparing
The reaction of journey situ generates TiC granule.It is introduced directly into by control and reduces the heat of former nickel-base alloy with In-situ Synthesis TiC Particle
The coefficient of expansion.
Described TiC-Ti-C precast body be mixed by TiC powder, Ti powder and C powder after suppress and form.In one example,
TiC powder footpath is 5-10 μm, purity >=99.5%；Ti powder footpath is 1-5 μm, purity >=99.9%；C powder footpath is 1-
5 μm, purity >=99.9%, and the mol ratio of Ti powder and C powder are that 1:1, the TiC powder mol ratio with Ti powder is according to component structure
Design.The pressure of 20-30MPa can be applied, so that the porosity of precast body is 50～60% during compacting.
Being placed on precast body by foundry alloy and heat together, after foundry alloy fusing, spontaneous infiltration is to TiC-Ti-C precast body
In, wherein Ti powder reacts with C powder and foundry alloy and generates TiC.The temperature of heating can be 1400 DEG C～1600 DEG C, insulation
Time can be 10～60 minutes.The environment of pressureless penetration can be inert atmosphere (such as argon) or vacuum.
In one example, being placed in alumina crucible by precast body, foundry alloy is placed in above precast body；By aluminium oxide earthenware
Crucible is placed in normal pressure graphite atmosphere furnace, heating melt infiltration preparation be introduced directly into jointly strengthen with In-situ Synthesis TiC Particle Ni-based multiple
Condensation material.Specifically, may comprise steps of:
(1) TiC powder, Ti powder, C powder and foundry alloy are weighed according to the mass percent of each design of components；
(2) use planetary ball mill by powder mix homogeneously good for proportioning；
(3) powder of step (2) mix homogeneously is pressed into precast body；
(4) precast body is placed in alumina crucible, foundry alloy block is placed in above precast body；
(5) alumina crucible is placed in graphite furnace heating melt infiltration.
Preferably, in described step (3), within the powder body of mix homogeneously loads mould in step (2), apply 20-
The pressure of 30MPa, the TiC-Ti-C precast body being prepared as.
Preferably, described step (4), specific as follows:
1. sample is filled: be placed in by the precast body of preparation in the suitable alumina crucible of size, then be placed in above precast body by foundry alloy block；
2. infiltration: alumina crucible is placed in graphite furnace heating, is penetrated in precast body by capillary force action after foundry alloy fusing
Portion；
3. osmotic atmosphere: vacuum in stove is extracted into 10-1Pa (is passed through argon)；
4. melt infiltration: in-furnace temperature rises to 1400-1600 DEG C, is incubated 10-60min, obtains described being introduced directly into the most raw
TiC granule is become jointly to strengthen nickel-base composite material.
The composite preparation of the present invention uses technique simple pressureless penetration method and conventional firing equipment (such as normal pressure stone
Ink atmosphere furnace), preparation cost is relatively low, is a kind of intermediate temperature solid oxide fuel cell connector with the biggest practical application foreground
Material.
Enumerate embodiment further below to describe the present invention in detail.It will similarly be understood that following example are served only for this
Bright it is further described, it is impossible to being interpreted as limiting the scope of the invention, those skilled in the art is according to the present invention's
Some nonessential improvement and adjustment that foregoing is made belong to protection scope of the present invention.The technique ginseng that following example is concrete
Number etc. is the most only an example in OK range, in the range of i.e. those skilled in the art can be done suitably by explanation herein
Select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1: prepare In-situ Synthesis TiC Particle and account for the nickel-base composite material of TiC gross mass 10wt.%
1. the preparation of mixed-powder: weigh carbonized titanium powder (purity >=99.5%, granularity 5-10 μm): 90wt.%, titanium valve (purity
>=99.9%, granularity 1-5 μm): three kinds of powder body are used by 8wt.%, C powder (purity >=99.9%, granularity 1-5 μm): 2wt.%
Planetary ball mill mix homogeneously；
2. prepared by precast body: is loaded by the mixed-powder 1. obtained in the mould of a diameter of 45mm, applies the pressure of 20-30MPa,
Being prepared as the precast body of Φ 45 × 8mm, its porosity is 40%；
3. melted infiltration: being placed in together with foundry alloy in graphite atmosphere furnace by the precast body 2. obtained, the quality of foundry alloy is required theory
Quality (the porosity × ρFoundry alloy) twice；In stove, vacuum is evacuated to 10-1Pa (is passed through argon)；In-furnace temperature rises to 1400-
1450 DEG C, it is incubated 10-20min；
This embodiment situ synthesis TiC account for total TiC mass fraction 10wt.%, obtained composite appearance as it is shown in figure 1,
XRD result is as shown in the TiC-TG1 in Fig. 2, and SEM result is as shown in (a) in Fig. 3, and expansion behavior becomes with temperature
Change curve as shown in [1] in Fig. 4, it can be seen that granule is evenly distributed in metallic matrix, part TiC granule occur core-
Shell structure, and In-situ Synthesis TiC Particle particle diameter (≤2 μm) is less than being introduced directly into TiC granule (5-10 μm), at 25-
Good linear expansion behavior is kept in the range of 450 DEG C.
Embodiment 2: prepare In-situ Synthesis TiC Particle and account for the nickel-base composite material of TiC gross mass 20wt.%
1. the preparation of mixed-powder: weigh carbonized titanium powder (purity >=99.5%, granularity 5-10 μm): 80wt.%, titanium valve (purity
>=99.9%, granularity 1-5 μm): three kinds of powder body are used by 16wt.%, C powder (purity >=99.9%, granularity 1-5 μm): 4wt.%
Planetary ball mill mix homogeneously；
2. prepared by precast body: is loaded by the mixed-powder 1. obtained in the mould of a diameter of 45mm, applies the pressure of 20-30MPa,
Being prepared as the precast body of Φ 45 × 8mm, its porosity is 45%；
3. melted infiltration: being placed in together with foundry alloy in graphite atmosphere furnace by the precast body 2. obtained, the quality of foundry alloy is required theory
Quality (the porosity × ρFoundry alloy) twice；In stove, vacuum is evacuated to 10-1Pa (is passed through argon)；In-furnace temperature rises to 1450-
1500 DEG C, it is incubated 20-30min；
This embodiment situ synthesis TiC accounts for total TiC mass fraction 20wt.%, and obtained composite XRD result is as in Fig. 2
TiC-TG2 shown in, SEM result is as shown in (b) in Fig. 3, and expansion behavior varies with temperature curve such as [2] in Fig. 4
Shown in, it can be seen that granule is evenly distributed in metallic matrix, and nucleocapsid structure, little amounts of particles occurs in part TiC granule
More than embodiment 1, and In-situ Synthesis TiC Particle particle diameter (≤2 μm) is less than being introduced directly into TiC granule (5-10 μm).
Embodiment 3: prepare In-situ Synthesis TiC Particle and account for the nickel-base composite material of TiC gross mass 30wt.%
1. the preparation of mixed-powder: weigh carbonized titanium powder (purity >=99.5%, granularity 5-10 μm): 70wt.%, titanium valve (purity
>=99.9%, granularity 1-5 μm): three kinds of powder body are used by 24wt.%, C powder (purity >=99.9%, granularity 1-5 μm): 6wt.%
Planetary ball mill mix homogeneously；
2. prepared by precast body: is loaded by the mixed-powder 1. obtained in the mould of a diameter of 45mm, applies the pressure of 20-30MPa,
Being prepared as the precast body of Φ 45 × 8mm, its porosity is 46%；
3. melted infiltration: being placed in together with foundry alloy in graphite atmosphere furnace by the precast body 2. obtained, the quality of foundry alloy is required theory
Quality (the porosity × ρFoundry alloy) twice；In stove, vacuum is evacuated to 10-1Pa (is passed through argon)；In-furnace temperature rises to 1500-
1550 DEG C, it is incubated 30-40min；
This embodiment situ synthesis TiC accounts for total TiC mass fraction 30wt.%, and obtained composite XRD result is as in Fig. 2
TiC-TG3 shown in, SEM result is as shown in (c) in Fig. 3, and expansion behavior varies with temperature curve such as [3] in Fig. 4
Shown in, it can be seen that granule is evenly distributed in metallic matrix, and nucleocapsid structure, little amounts of particles occurs in part TiC granule
More than embodiment 2, and In-situ Synthesis TiC Particle particle diameter (≤2 μm) is less than being introduced directly into TiC granule (5-10 μm).
Embodiment 4: prepare In-situ Synthesis TiC Particle and account for the nickel-base composite material of TiC gross mass 40wt.%
1. the preparation of mixed-powder: weigh carbonized titanium powder (purity >=99.5%, granularity 5-10 μm): 60wt.%, titanium valve (purity
>=99.9%, granularity 1-5 μm): three kinds of powder body are used by 32wt.%, C powder (purity >=99.9%, granularity 1-5 μm): 8wt.%
Planetary ball mill mix homogeneously；
2. prepared by precast body: is loaded by the mixed-powder 1. obtained in the mould of a diameter of 45mm, applies the pressure of 20-30MPa,
Being prepared as the precast body of Φ 45 × 8mm, its porosity is 50%；
3. melted infiltration: being placed in together with foundry alloy in graphite atmosphere furnace by the precast body 2. obtained, the quality of foundry alloy is required theory
Quality (the porosity × ρFoundry alloy) twice；In stove, vacuum is evacuated to 10-1Pa (is passed through argon)；In-furnace temperature rises to 1550-
1600 DEG C, it is incubated 40-60min；
This embodiment situ synthesis TiC accounts for total TiC mass fraction 40wt.%, and obtained composite XRD result is as in Fig. 2
TiC-TG4 shown in, SEM result is as shown in (d) in Fig. 3, and expansion behavior varies with temperature curve such as [4] in Fig. 4
Shown in, it can be seen that granule is evenly distributed in metallic matrix, and nucleocapsid structure, little amounts of particles occurs in part TiC granule
Higher than embodiment 3, and In-situ Synthesis TiC Particle particle diameter (≤2 μm) is less than being introduced directly into TiC granule (5-10 μm).
Comparative example 1: prepare In-situ Synthesis TiC Particle and account for the nickel-base composite material of TiC gross mass 0wt.%
1. the preparation of mixed-powder: weigh carbonized titanium powder (purity >=99.5%, granularity 5-10 μm): 100wt.%；
2. prepared by precast body: is loaded by the powder 1. obtained in the mould of a diameter of 45mm, applies the pressure of 20-30MPa, preparation
Becoming the precast body of Φ 45 × 8mm, its porosity is 38%；
3. melted infiltration: being placed in together with foundry alloy in graphite atmosphere furnace by the precast body 2. obtained, the quality of foundry alloy is required theory
Quality (the porosity × ρFoundry alloy) twice；In stove, vacuum is evacuated to 10-1Pa (is passed through argon)；In-furnace temperature rises to 1400-
1450 DEG C, it is incubated 10-20min；
Prepared material is carried out performance measurement, found that: in composite, the mean diameter of TiC granule is higher than being introduced directly into and portion
Divide the nickel-base composite material that in-situ preparation strengthens jointly, and then cause the reduction of its mechanical strength.
Comparative example 2: prepare In-situ Synthesis TiC Particle and account for the nickel-base composite material of TiC gross mass 100wt.%
1. the preparation of mixed-powder: weigh titanium valve (purity >=99.9%, granularity 1-5 μm): 80wt.%, C powder (purity >=99.9%,
Granularity 1-5 μm): 20wt.%, by two kinds of powder body planetary ball mill mix homogeneously；
2. prepared by precast body: is loaded by the mixed-powder 1. obtained in the mould of a diameter of 45mm, applies the pressure of 20-30MPa,
Being prepared as the precast body of Φ 45 × 8mm, its porosity is 55%；
3. melted infiltration: being placed in together with foundry alloy in graphite atmosphere furnace by the precast body 2. obtained, the quality of foundry alloy is required theory
Quality (the porosity × ρFoundry alloy) twice；In stove, vacuum is evacuated to 10-1Pa (is passed through argon)；In-furnace temperature rises to 1400-
1450 DEG C, it is incubated 10-20min；
Prepared material is carried out performance measurement, found that: in composite, the mean diameter of TiC is former with part less than being introduced directly into
Position generates the common nickel-base composite material strengthened, and its mechanical strength is also above the latter, but the short grained number of TiC in composite
Amount increases, and the restriction ability of matrix expansion behavior is reduced by ceramic phase, causes the composite coefficient of expansion far above electrolyte
(YSZ, 10.5 × 10-6K-1), meanwhile, the increase that TiC specific grain surface amasss can be strengthened causing electrical conductivity to drop the scattering of electronics
Low, unfavorable to the overall performance of composite.Further, (reaction in-situ has one with contraction in the deformation that final sample generation is certain
Determine volume contraction), change shape and size and the high expensive of initial prefabrication body.
Comparative example 3: prepare In-situ Synthesis TiC Particle and account for the nickel-base composite material of TiC gross mass 5wt.%
1. the preparation of mixed-powder: weigh carbonized titanium powder (purity >=99.5%, granularity 5-10 μm): 95wt.%, titanium valve (purity
>=99.9%, granularity 1-5 μm): three kinds of powder body are used by 4wt.%, C powder (purity >=99.9%, granularity 1-5 μm): 1wt.%
Planetary ball mill mix homogeneously；
2. prepared by precast body: is loaded by the mixed-powder 1. obtained in the mould of a diameter of 45mm, applies the pressure of 20-30MPa,
Being prepared as the precast body of Φ 45 × 8mm, its porosity is 39%；
3. melted infiltration: being placed in together with foundry alloy in graphite atmosphere furnace by the precast body 2. obtained, the quality of foundry alloy is required theory
Quality (the porosity × ρFoundry alloy) twice；In stove, vacuum is evacuated to 10-1Pa (is passed through argon)；In-furnace temperature rises to 1400-
1450 DEG C, it is incubated 10-20min；
Prepared material is carried out performance measurement, found that: on the low side owing to introducing TiC amount in situ, account for In-situ Synthesis TiC Particle
The composite of gross mass 0% is compared, and particle mean size and performance do not find substantially to optimize.
Comparative example 4: prepare In-situ Synthesis TiC Particle and account for the nickel-base composite material of TiC gross mass 50wt.%
1. the preparation of mixed-powder: weigh carbonized titanium powder (purity >=99.5%, granularity 5-10 μm): 50wt.%, titanium valve (purity
>=99.9%, granularity 1-5 μm): 40wt.%, C powder (purity >=99.9%, granularity 1-5 μm): 10wt.%, by three kinds of powder body
Use planetary ball mill mix homogeneously；
2. prepared by precast body: is loaded by the mixed-powder 1. obtained in the mould of a diameter of 45mm, applies the pressure of 20-30MPa,
Being prepared as the precast body of Φ 45 × 8mm, its porosity is 53%；
3. melted infiltration: being placed in together with foundry alloy in graphite atmosphere furnace by the precast body 2. obtained, the quality of foundry alloy is required theory
Quality (the porosity × ρFoundry alloy) twice；In stove, vacuum is evacuated to 10-1Pa (is passed through argon)；In-furnace temperature rises to 1400-
1450 DEG C, it is incubated 10-20min；
Prepared material is carried out performance measurement, found that: in composite, the mean diameter of TiC is former with part less than being introduced directly into
Position generates the common nickel-base composite material strengthened, and its mechanical strength is also above the latter, but the short grained number of TiC in composite
Amount increases, and the restriction ability of matrix expansion behavior is reduced by ceramic phase, causes the composite coefficient of expansion to be slightly above electrolyte
(YSZ, 10.5 × 10-6K-1), meanwhile, the increase that TiC specific grain surface amasss can be strengthened causing electrical conductivity to drop the scattering of electronics
Low, unfavorable to the overall performance of composite.
Claims (10)
1. one kind is introduced directly into and jointly strengthens nickel-base composite material with In-situ Synthesis TiC Particle, it is characterized in that, the TiC granule being introduced directly into including Superalloy Substrate and being evenly distributed in described Superalloy Substrate and generated in-situ TiC granule, wherein, generated in-situ TiC granule accounts for the mass fraction of total TiC is 10～40wt.%.
The most according to claim 1 being introduced directly into jointly strengthens nickel-base composite material with In-situ Synthesis TiC Particle, it is characterized in that, described composite is to be obtained by TiC-Ti-C precast body and the reactive infiltration of Ni-based foundry alloy, the described TiC granule being introduced directly into is from the TiC in TiC-Ti-C precast body, described generated in-situ TiC granule be after the fusing of Ni-based foundry alloy spontaneous infiltration in TiC-Ti-C precast body, by Ti powder, C powder and foundry alloy react the TiC generated.
The most according to claim 1 and 2 being introduced directly into jointly strengthens nickel-base composite material with In-situ Synthesis TiC Particle, it is characterized in that, part TiC granule is nucleocapsid structure, generated in-situ TiC particle size≤2 μm, and the TiC particle size being introduced directly into is 5～10 μm.
The most according to any one of claim 1 to 3 being introduced directly into jointly strengthens nickel-base composite material with In-situ Synthesis TiC Particle, it is characterised in that it is 50-60vol.% that TiC granule accounts for the volume fraction of described composite.
The most according to any one of claim 1 to 4 being introduced directly into jointly strengthens nickel-base composite material with In-situ Synthesis TiC Particle, it is characterised in that described composite in the mean thermal expansion coefficients scope of 25～450 DEG C of temperature ranges 9～11 × 10-6K-1Between, and vary with temperature holding linear expansion behavior；The electrical resistivity range of described composite is between 4～7m Ω cm.
The most according to any one of claim 1 to 5 being introduced directly into jointly strengthens nickel-base composite material with In-situ Synthesis TiC Particle, it is characterized in that, described Superalloy Substrate is any one in Ni-Fe, Ni-Mo, Ni-Mo-Cr, Ni-Fe-Co, Ni-Cr-Fe, Ni-Mo-Ti and Ni-Mo-Nb.
7. the preparation method of the composite according to any one of a claim 1 to 6, it is characterised in that comprise the following steps:
(1) TiC powder, Ti powder, C powder and foundry alloy are weighed according to the mass percent of each design of components；
(2) after TiC powder, Ti powder and C powder mix homogeneously, it is pressed into TiC-Ti-C precast body；
(3) foundry alloy is placed in above TiC-Ti-C precast body, carries out adding heat fusing pressureless penetration.
Preparation method the most according to claim 7, it is characterised in that in TiC-Ti-C precast body, TiC particle diameter is 5～10 μm, purity >=99.5%；Ti powder footpath is 1～5 μm, purity >=99.9%；C powder footpath be 1～5 μm, purity >=99.9%, and the mol ratio of Ti powder and C powder be 1:1；The porosity of described TiC-Ti-C precast body is 40～50%.
9., according to the preparation method described in claim 7 or 8, it is characterised in that the environment of pressureless penetration is inert atmosphere or vacuum, the temperature of pressureless penetration is 1400 DEG C～1600 DEG C, and temperature retention time is 10～60 minutes.
10. the composite according to any one of a claim 1 to 6 is used as the metallic interconnection materials of intermediate temperature solid oxide fuel cell.
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| CN107116217A (en) * | 2017-04-27 | 2017-09-01 | 哈尔滨理工大学 | Selective laser melting forming process, which prepares TiC, strengthens the method for nickel-base composite material |
| CN108504886A (en) * | 2017-02-24 | 2018-09-07 | 中国科学院上海硅酸盐研究所 | A kind of preparation method of TiC-C nickel-base alloys self-lubricating composite |
| CN109112436A (en) * | 2018-10-10 | 2019-01-01 | 北京科技大学 | A kind of method of in-situ preparation fiber reinforcement high temperature alloy composite material |
| CN110229969A (en) * | 2019-07-05 | 2019-09-13 | 西安交通大学 | A kind of the nano-TiC particle reinforced aluminum matrix composites and method of melting-reaction method preparation |
| CN111270103A (en) * | 2020-03-18 | 2020-06-12 | 北京交通大学 | TiC particle reinforced Ni composite porous material and preparation process thereof |
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