CN108149127B - A kind of aluminum-base nano titanium carbonitride crystal seed alloy and preparation method thereof - Google Patents

A kind of aluminum-base nano titanium carbonitride crystal seed alloy and preparation method thereof Download PDF

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CN108149127B
CN108149127B CN201711476048.XA CN201711476048A CN108149127B CN 108149127 B CN108149127 B CN 108149127B CN 201711476048 A CN201711476048 A CN 201711476048A CN 108149127 B CN108149127 B CN 108149127B
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aluminum
titanium carbonitride
crystal seed
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alloy
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CN108149127A (en
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刘相法
李�杰
许庆飞
杨化冰
刘桂亮
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Shandong University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0089Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with other, not previously mentioned inorganic compounds as the main non-metallic constituent, e.g. sulfides, glass
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/10Alloys containing non-metals
    • C22C1/1036Alloys containing non-metals starting from a melt
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/10Alloys containing non-metals
    • C22C1/1036Alloys containing non-metals starting from a melt
    • C22C1/1047Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
    • C22C1/1052Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites by mixing and casting metal matrix composites with reaction
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium

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Abstract

The present invention relates to a kind of aluminum-base nano titanium carbonitride crystal seed alloys and preparation method thereof.The aluminium base crystal seed alloy is characterized in: the in-situ authigenic nano-scale carbon titanium nitride in aluminum substrate containing Dispersed precipitate;Titanium carbonitride plays a dual role of strengthening aluminum substrate and refines aluminium grain as a kind of second-phase strength and seed particles.The present invention uses liquid-solid reaction method fabricated in situ nano-carbon titanium nitride particle in aluminum melt, its specific method is: matching to obtain raw material by certain mass percent, aluminium powder, nitridation titanium valve, graphene are dried, then degasification jacket after mixing, in vacuum furnace (vacuum degree 1 × 10–3~5 × 10–3Pa it is heated to 700~900 DEG C, 1~3h of fusant reaction in), obtains a kind of aluminum-base nano titanium carbonitride crystal seed alloy.Preparation process of the invention is easy, environmentally friendly, raw material availability is high, can both prepare aluminium base titanium carbonitride crystal seed alloy, and can also prepare aluminum matrix composite, has good prospects for commercial application.

Description

A kind of aluminum-base nano titanium carbonitride crystal seed alloy and preparation method thereof
Technical field
The invention belongs to metal material field, in particular to a kind of aluminum-base nano titanium carbonitride (TiNC) crystal seed alloy and its system Preparation Method.
Background technique
TiNC is a kind of ternary compound between TiN and TiC, has face-centered cubic NaCl type lattice structure, simultaneous Has the advantages of TiN and TiC, the structural stability in aluminum melt is above the above two, density 5.08g/cm3, it is a kind of Typical non-oxide ceramic material, it has, and high-melting-point, high hardness and corrosion resistance is good, wearability is good and good anti-oxidant The advantages that property.At the same time, TiNC is the good conductor of heat, electricity again, so TiNC is widely used in automobile manufacture, mechanization The fields such as work, aerospace.TiNC has the characteristics that non-stoichiometry, changes with N content, can show different property.Example Such as: the hardness ratio TiC's of TiN is low, and thermal conductivity ratio TiC's is high, and with the increase of N content in TiNC, TiNC is shown under hardness Drop, the raised trend of thermal conductivity.For TiNC, the features such as researchers are laid particular emphasis on using its wearability, corrosion resistance, therefore apply Most or TiNC base ceramet tool bit.But the research of high-melting-point and its high-temperature stability to TiNC is few.
Currently, preparation TiNC intermediate alloy mainly passes through outer addition.Such as:
Document 1 (development [J] food scientific technology journal of Wang Changming .Al-Ti-CN intermediate alloy, 2007,25 (3): 30-32) method that TiNC particle refinement aluminium alloy crystal grain is added in aluminum melt is reported, but outer addition cannot well solve Wellability problem between TiNC particle and aluminum melt causes TiNC particle that aluminum melt out of reuniting or dissociate occurs.The present invention adopts With in-situ synthesis, the basic principle is that: control reaction condition, by graphene make titanium nitride occurs to change in aluminum melt or It develops, thus the in-situ preparation nano TiN C particle in aluminum substrate.The composite material prepared by this method, reinforcement surface Pollution-free, the wetability of aluminum melt and reinforcement is good, and interface bond strength is higher.Meanwhile unlike other composite materials, save Cumbersome reinforcement pretreatment process, simplifies preparation process.
(the duckweed .N doping type TiC of document 2xThe development of nucleating agent and its Shandong influence [D] to aluminium alloy correlated performance University, 2014.) report the TiC that micro N atom is adulterated using different nitrogen source preparationsxParticle is substantially to utilize TiCxCrystal The vacancy C present in structure allows N atom in TiCxUpper progress trace modification, but its essence or TiCx.This is utilized with the present invention The TiNC of in-situ synthesis synthesis is essentially different.
The Chinese patent of Publication No. CN101514493A disclose a kind of in-situ grown titanium carbonitride crystal whisker materials and Preparation method, using TiO236.4%~38.5%;C 11.5%~16.4%;NaCl 22.7%~24.0%;KCl 22.7%~24.0%;Titanium carbonitride crystal whisker precursor mixing in proportion is packed into cylinder formula ball milling by NiCl 1.8%~2.0% In machine, after alumina balls grinding machine 12h and 100 meshes, it is packed into crystal vessel, 50 DEG C of heating rate/min, N2Flow velocity 0.1~ 0.4Nm3/ h, 1250 DEG C~1500 DEG C of temperature, heat preservation 60min~120min synthesis.Although the patent also uses fabricated in situ Method, but the reaction system is related to a kind of ceramic material, and reaction product is titanium carbonitride crystal whisker materials, with the application patent Aluminium base crystal seed alloy has fundamental difference.
The Chinese patent of Publication No. CN103787407A discloses a kind of reaction ball milling method and prepares nano TiC N/Al2O3It is multiple The method for closing powder, using golden red mountain flour, aluminium powder, graphite powder and urea (analysis is pure), 3:4:2.7:0.15 is mixed in molar ratio It is fitted into ball grinder together with abrading-ball afterwards, ratio of grinding media to material is 20~30:1, and ball milling, Ball-milling Time 40 are carried out in high energy ball mill ~80h.Although the method that the patent also uses fabricated in situ, which is related to a kind of composite powder, reaction product It is TiCN/Al2O3Compound particle.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of aluminum-base nano titanium carbonitride crystal seed alloy and The synthesizing preparation method in situ of its simple and effective.
The present invention is achieved in the following ways:
A kind of aluminum-base nano titanium carbonitride crystal seed alloy, it is characterized in that: containing the in-situ authigenic of Dispersed precipitate in aluminum substrate Nanoscale TiNC;The mass percent of TiNC is 5.0~10.0, having a size of 20nm~300nm;TiNC is mutually strong as one kind second Change and seed particles play a dual role of strengthening aluminum substrate and refine aluminium grain.
A kind of preparation method of aluminum-base nano titanium carbonitride crystal seed alloy, it is characterized in that the following steps are included:
(1) raw material needed for preparing by following mass percent: the aluminium powder 90.00~95.00 of size≤50 μm, size≤1 μ Nitridation titanium valve 4.50~8.50, the graphene 0.50~1.50 of m;
(2) mixing, degasification jacket after drying aluminium powder, nitridation titanium valve, the graphene in step (1), in vacuum furnace (vacuum degree 1 × 10–3~5 × 10–3Pa 700~900 DEG C are heated in), 1~3h of fusant reaction obtains a kind of aluminum-base nano TiNC crystal seed alloy.
Compared with prior art, the present invention has the following advantages:
(1) it is in-situ authigenic that TiNC, which enhances particle, and purity is high, clean surface is pollution-free, boundary good with aluminum melt wetability Face bond strength is high.TiNC is a kind of good second-phase strength particle again simultaneously, can effectively hinder the movement of dislocation, move Dislocation when encountering the second phase particles on slide surface, or cut through, or bypass, such sliding deformation can just continue.This Process will consume additional energy, need to improve applied stress.
(2) present invention utilizes TiC and the very close feature of TiN lattice, by C atom it is gradual be doped with it is non-chemical The TiN for measuring ratio characteristic carry out reaction can at a lower temperature, reduce energy consumption of reaction, before having good industrial application Scape.
(3) C/N ratio and TiNC partial size can be regulated and controled by adjusting ratio, reaction temperature, the soaking time of TiN and C.
(4) preparation method green, environmental protection, safety, economy, convenient, raw material availability height.
Specific embodiment
Three most preferred embodiments of the invention are given below.
Embodiment 1
(1) required raw material: aluminium powder (size≤50 μm) 90.50, nitridation titanium valve (size is got out by following mass percent ≤ 1 μm) 8.00, graphene 1.50.
(2) mixing 6h after above-mentioned aluminium powder, nitridation titanium valve, graphene drying is subjected to degasification jacket again, in vacuum furnace (vacuum degree 1 × 10–3~5 × 10–3Pa 900 DEG C of fusant reaction 1h in) obtain in-situ authigenic nanoscale TiNC crystal seed alloy.Its Specific ingredient (mass percent) are as follows: Al -10TiN0.7C0.3, TiNC is having a size of 20nm~300nm.
Embodiment 2
(1) required raw material: aluminium powder (size≤50 μm) 92.45, nitridation titanium valve (size is got out by following mass percent ≤ 1 μm) 6.50, graphene 1.05.
(2) mixing 6h after above-mentioned aluminium powder, nitridation titanium valve, graphene drying is subjected to degasification jacket again, in vacuum furnace (vacuum degree 1 × 10–3~5 × 10–3Pa 800 DEG C of fusant reaction 2h in) obtain in-situ authigenic nanoscale TiNC crystal seed alloy.Its Specific ingredient (mass percent) are as follows: Al -5TiN0.75C0.25, TiNC is having a size of 20nm~200nm.
Embodiment 3
(1) required raw material: aluminium powder (size≤50 μm) 95.00, nitridation titanium valve (size is got out by following mass percent ≤ 1 μm) 4.50, graphene 0.50.
(2) mixing 6h after above-mentioned aluminium powder, nitridation titanium valve, graphene drying is subjected to degasification jacket again, in vacuum furnace (vacuum degree 1 × 10–3~5 × 10–3Pa 700 DEG C of fusant reaction 3h in) obtain in-situ authigenic nanoscale TiNC crystal seed alloy.Its Specific ingredient (mass percent) are as follows: Al -5TiN0.8C0.2, TiNC is having a size of 20nm~150nm.

Claims (1)

1. a kind of preparation method of aluminum-base nano titanium carbonitride crystal seed alloy, the in-situ authigenic containing Dispersed precipitate is received in aluminum substrate Meter level titanium carbonitride;The mass percent of titanium carbonitride is 5.0~10.0, having a size of 20nm~300nm;Titanium carbonitride is as one Kind second-phase strength and seed particles play a dual role of strengthening aluminum substrate and refine aluminium grain;It is characterized in that preparation method The following steps are included:
(1) required raw material: the aluminium powder 90.00~95.00 of size≤50 μm, size≤1 μm is got out by following mass percent Nitridation titanium valve 4.50~8.50, graphene 0.50~1.50;
(2) by mixing, degasification jacket after aluminium powder as described in step (1), nitridation titanium valve, graphene drying, in vacuum furnace In be heated to 700~900 DEG C, vacuum degree 1 × 10–3~5 × 10–3Pa, 1~3h of fusant reaction obtain aluminum-base nano titanium carbonitride Crystal seed alloy.
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CN112267048B (en) * 2020-09-02 2022-02-25 上海交通大学 Nano Ti-containing2Aluminum-based alloy of AlN particles and method for producing same
CN115341116B (en) * 2021-05-12 2023-04-18 中国科学院过程工程研究所 Aluminum-titanium-carbon-nitrogen intermediate alloy refiner and preparation method thereof
CN114606461B (en) * 2022-04-18 2023-02-28 东莞理工学院 Preparation method of Al-Ti-C-N nanocrystalline and application of Al-Ti-C-N nanocrystalline in aluminum alloy

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