CN1557585A - Method for preparing Si-Al alloy using spray deposition forming process - Google Patents

Method for preparing Si-Al alloy using spray deposition forming process Download PDF

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CN1557585A
CN1557585A CNA2004100390579A CN200410039057A CN1557585A CN 1557585 A CN1557585 A CN 1557585A CN A2004100390579 A CNA2004100390579 A CN A2004100390579A CN 200410039057 A CN200410039057 A CN 200410039057A CN 1557585 A CN1557585 A CN 1557585A
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alloy
alloys
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CN100534673C (en
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滨 杨
杨滨
张济山
尧军平
陈美英
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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Abstract

The present invention provides the preparation process of jetting and depositing molded Si-Al alloy, and features that intermediate 25-50 wt% Si-Al alloy ingot is first prepared and then jetted and deposited to prepare 50-70 wt% Si-Al alloy. The technological parameters of jetting and depositing process includes: nitrogen used as atomizing gas, atomizing pressure of 0.6-0.8 MPa, depositing distance of 400-600 mm and guide pipe diameter of 3.2-4.0 mm. The present invention has the advantages of adjustable expansion coefficient of the Si-Al alloy in (6-13)E(-6)/K, heat conductivity of 110-150 W/Mk, and density of 2.4-2.5 g/cu cm, and may be used widely as packing and heat dissipating material for electronic elements in telecomm, aeronautics, astronautics and other industry.

Description

A kind of preparation method of jet deposition formation Si-Al alloy
Technical field
The invention belongs to silumin technology of preparing and electronic package material field, the preparation method of a kind of reaction-injection moulding low thermal coefficient of expansion, high thermoconductivity, low density and machinable silumin particularly is provided, has been widely used in telecommunication, Aeronautics and Astronautics, national defence and other related industries electronic devices and components required novel encapsulated or heat sink material.
Background technology
In recent years, along with Electronic Packaging industry develops to high-density, high-speed direction, the material that exploitation has a good heat conductive ability improves the heat radiation that brings and requires to become the task of top priority to satisfy integrated level.
The advanced electronic package material of ideal should have with typical semiconductor materials such as gallium arsenide and silicon and is complementary, or slightly high thermal expansivity (Coefficient of thermal expansion, be called for short CTE), high thermal conductivity (＞100W/mK) and low density (＜3g/cm 3).In addition, wish packaged material have rational rigidity (＞100GPa), can provide enough mechanical support for parts and substrate to the mechanical effect sensitivity.It also needs to be easy to carry out precision sizing and is shaped, and can utilize economic industry standard approach, as electroplating etc., carries out application and handles.Metal Packaging makes the variation of encapsulation shape, rapid heat dissipation because of its shell can combine together with some parts (as mixing integrated A/D or D/A converter), volume is little, cost is low, but also helps reducing inductance, the electric capacity between signal and crosstalk etc., and becomes the important packaged material of a class.
Traditional metal electron packaged material (not comprising particles reiforced metal-base composition) and key property thereof are as shown in table 1.Wherein, fine aluminium and copper are often used as the heat radiating type electronic package material, because their thermal conductivity is up to 200～390W/mK.But these material coefficient of thermal expansion coefficients are bigger, and are poor with the hot matched performance of ceramic substrate, unfavorable to improving the device whole reliability.In order to reduce the material coefficient of thermal expansion coefficient, Mo and the W that Cu and thermal expansivity is less mixes (powder metallurgy or cold rolling) and forms matrix material, can obtain higher heat-conducting effect, but the weight of encapsulating structure increases obviously, this is a fatal weakness to the aerospace package application.And wettability is poor between Cu-Mo and the Cu-W, and the matrix material resistance to air loss is bad, and densification degree is low, and encapsulation performance is affected.The material that contains Be has toxicity, has limited the application of this material.Other material, as Kovar (Fe-29Ni-17Co) and Invar (Ni-Fe) alloy, though have lower thermal expansivity, resistance is big, the capacity of heat transmission is relatively poor, can only as the heat radiation of small power rectifier be connected material.W, Mo have the linear expansivity close with Si, and thermal conductivity is better than Kovar and Invar alloy, therefore are usually used in the propping material of semi-conductor Si sheet.But because the wetting property of W, Mo and Si is bad, weldability is poor, often need or apply basic alloy of special Ag or Ni, make technology become complexity and poor reliability in the surface plating.And W, Mo price are comparatively expensive, and density is big, is not suitable for a large amount of uses.This shows that traditional metal electron packaged material can't satisfy the requirement of hyundai electronics encapsulation over-all properties at present.
The key property data of table 1 typical metal electronic package material
Material Thermal expansivity (20 ℃) * 10 -6/K Thermal conductivity (k) W/mK Density (ρ) g/cm 3
??Al ????23.6 ????230 ????2.7
??Cu ????17.6 ????391 ????8.9
??Cu-75％W ????8.8 ????190 ????14.6
??Cu-85％W ????7.2 ????180 ????16.1
??Cu-85％Mo ????6.7 ????160 ????10
??Be ????7.2 ????260 ????2.9
The Kovar alloy ????5.8 ????17 ????8.2
The Invar alloy ????0.4 ????11 ????8.1
??W ????4.45 ????168 ????19.3
??Mo ????5.1 ????140 ????10.2
The over-all properties that the Si-Al alloy has been proved to be satisfies material system (the M.Jacobson and S.P.S.Sangha that advanced Electronic Packaging requires, Future trends in materials for lightweightmicrowave packaging, Microelectronics Int., 1998,15, No3:47.S.P.S.Sangha，NovelAluminum?Silicon?Alloys?for?Electronics?packaging，Journal?of?Engineering?Scienceand?Education，1997，No?11：195)。Among the present invention, silicon is as one of basal component of alloy, and (CTE is 4.1 * 10 to have low thermal coefficient of expansion -6/ K), high heat conductance (150W/mK), low density (2.34g/cm 3), advantage such as chemical property is stable, with low cost, the source is abundant.Its main drawback is that the fragility of fusing point height (1414 ℃), material is big.By in Si, adding an amount of low melting point Al, can reduce the fusing point of alloy effectively, improve the fracture toughness property of material, improve the processability of material.
The Si-Al alloy that silicon content is lower can be shaped by castmethod.But in 50～70 weight %Si composition ranges, Si-Al alloy casting state microstructure mainly is made up of a Si crystal of big and isolated, many-sided and high aspect ratio, and this is obviously unfavorable to the mechanical property and the processing characteristics of material.Usually a silicon phase of needle-like particulate is of a size of the millimeter level, easily causes extremely anisotropy of material structure, is not suitable for the application of Electronic Packaging.For example, the sheet metal thickness that is used for Electronic Packaging is generally 1-5mm, if adopt cast material, one Si crystal might penetrate whole thickness of slab.This will make, and material is extremely difficult to be worked into the required high precision quality of external coating, because the Si particle is easy to learn the plane along preferential crystallographic, folk prescription takes place to cracking.In addition, because large size Si particulate exists, make that partial CTE of material and thermal conductivity will take place to change significantly.It is generally acknowledged that the alloy with such microstructure does not have the engineering using value.
By adopting powder metallurgy technology to help to form tiny, isotropic microstructure.But powder metallurgy technology often relates to complicated step, causes the increase of cost, so fail the application that puts it in the preparation of Si-Al alloy always.Another industrialization technology that can reach above purpose is exactly the jet deposition formation technology.In the reaction-injection moulding process, molten metal is atomized with the high speed rare gas element by spraying gun, produce tiny droplet (general diameter is～40 μ m).These droplets deposit on the substrate of a cold conditions rotation, form the blank with tiny isotropy tissue behind the experience rapid solidification.In flight course, promptly begin to form the crystal of Si through the Si-Al alloy molten drop of atomizing, be broken mutually in the deposit preform surface solidification and produced a large amount of Si phase nucleation sites, the growth process that these cores are grown up and collision has limited the Si phase mutually, make it to form the Si particle of isolated, height-oriented property such in the cast structure, and formed Si crystal random orientation, solved the anisotropic problem of microstructure and performance.The result makes on the deposit preform structure and realizes continuity, produces isotropic alloy structure and performance, and helps the retrofit on surface.After a small amount of the loosening that forms in the suitable subsequent disposal elimination deposition process, these deposition blanks just can be used for making various high performance packaged unit.Obviously, low density, low-thermal-expansion, high thermal conduction and can process the Si-Al alloy and belong to controlled thermal expanding material (can be as required, by the composition adjustment, the thermal expansivity of control alloy) have good comprehensive packaging process performance advantage.
Summary of the invention
The objective of the invention is to: the preparation method of a kind of low thermal coefficient of expansion, high thermoconductivity, low density and machinable silumin is provided, is widely used in telecommunication, Aeronautics and Astronautics, national defence and other related industries electronic devices and components required novel encapsulated or heat sink material.
Formation of the present invention: adopt prefabricated 25～50 weight %Si-Al master alloys of medium-frequency induction furnace, obtain final 50～70 weight %Si-Al alloys by the mode of in master alloy, adding Si with the jet deposition formation method according to the ultimate aim composition then; Concrete grammar is as follows:
1, the preparation of master alloy:
To account for the pure Si of 25～50 weight %, all the other put into the medium-frequency induction furnace fusing that heats up for the starting material of industrial pure Al, and it is standby to be cast into intermediate alloy ingot.Pure Si and industrial pure Al are block.
2, the preparation of jet deposition formation 50～70 weight %Si-Al alloys: above-mentioned intermediate alloy ingot is put into the medium-frequency induction furnace crucible.According to 50～70 weight %Si-Al alloying constituent requirements, the pure Si that optionally adds 0～45 weight % heats up and melts (master alloy is 50 weight %Si-Al, when preparing jet deposition formation 50 weight %Si-Al alloys simultaneously, need add pure Si).Adopt jet deposition formation method preparation 50～70 weight %Si-Al alloys then.The spray deposition processing parameter is selected as follows: atomizing gas: nitrogen; Atomizing pressure: 0.6～0.8MPa; Deposition distance: 400～600mm; Draft-tube diameter: 3.2～4.0mm.
The invention has the advantages that:
(1) even, isotropic superior physical properties: low thermal coefficient of expansion (can be regulated scope: 6～13 * 10 according to demand -6/ K).Can be according to different encapsulation matching materialss, the Si-Al alloy material of design makes both matched coefficients of thermal expansion as far as possible; Low density (2.4～2.5g/cm 3), be particularly suitable for aerospace electronic devices and components package application; High heat conductance (110～150W/mK), satisfy integrated level and improve the heat radiation requirement that brings; Low electricity leads (＜10 -6Wm); High rigidity (specific rigidity＞44GPa cm 3/ g); Good thermo mechanical stability (use temperature can reach 500 ℃);
(2) good processing and the packaging process performance: adopt carbide or polycrystalline diamond cutter can more easily obtain higher processing precision; Be easy to be processed into different shape (comprising various grooves, narrow groove and corner etc.); Environmental friendliness does not contain harmful healthy element, is easy to circular treatment; Being easy to plate external coatings such as gold and silver and nickel handles; Good welding property.
Description of drawings
Fig. 1 is (a) reaction-injection moulding 60 weight %Si-Al alloys and (b) microstructure of reaction-injection moulding 70 weight %Si-Al alloys among the present invention.
Fig. 2 is the linear expansivity of the spray forming Si-Al alloy among the present invention and the experimental data figure of silicone content.X-coordinate is Si content, weight percent; Ordinate zou is a linear expansivity, and unit is 10 -6/ K.
Fig. 3 is the experimental data figure of the thermal conductivity and the temperature of the spray forming Si-Al alloy among the present invention.X-coordinate be temperature, ℃; Ordinate zou is a thermal conductivity, and unit is W/mK.
Fig. 4 is the resistivity of the spray forming Si-Al alloy among the present invention and the experimental data figure of silicone content.X-coordinate is Si content, weight percent; Ordinate zou is a resistivity, and unit is 10 -6/ Ω m.
Fig. 5 is reaction-injection moulding 50 weight %Si-Al alloy machining component (25 * 15 * 5mm) exemplary plot among the present invention.Part Surface Roughness R a≤ 1.6 μ m.
Embodiment
Embodiment 1
Prepare 50 weight %Si-Al alloys.Found 50 weight %Si-Al intermediate alloy ingot with 150 kilograms of medium-frequency induction furnaces.With lumpiness is that 4～6mm, weight are that 15 kilograms pure Si and 15 kilograms industrial pure Al are put into the medium-frequency induction furnace crucible, heats up to make its fusing, and it is standby to be cast into intermediate alloy ingot.With above-mentioned intermediate alloy ingot remelting, prepare 50 weight %Si-Al alloys with the jet deposition formation method.Processing parameter is selected as follows: atomizing gas: nitrogen; Atomizing pressure: 0.7MPa; Deposition distance: 550mm; Draft-tube diameter: 3.6mm.The material coefficient of thermal expansion coefficient is 10.6 * 10 -6/ K.Thermal conductivity is 121W/mK (150 ℃).Resistivity is 0.4 * 10 -6Ω m.
Embodiment 2
Prepare 60 weight %Si-Al alloys.Found 30 weight %Si-Al intermediate alloy ingot with 150 kilograms of medium-frequency induction furnaces.With lumpiness is that 4～6mm, weight are that 3 kilograms pure Si and 7 kilograms industrial pure Al are put into the medium-frequency induction furnace crucible, heats up to make its fusing, and it is standby to be cast into intermediate alloy ingot.With above-mentioned intermediate alloy ingot remelting, add 4.3 kilograms pure Si, prepare 60 weight %Si-Al alloys with the jet deposition formation method.Processing parameter is selected as follows: atomizing gas: nitrogen; Atomizing pressure: 0.8MPa; Deposition distance: 600mm; Draft-tube diameter: 3.8mm.The material coefficient of thermal expansion coefficient is 9.1 * 10 -6/ K.Thermal conductivity is 113W/mK (150 ℃).Resistivity is 0.9 * 10 -6Ω m.The density of deposition attitude 60 weight %Si-Al alloys is 2.3164g/cm 3, density is 2.4486g/cm behind the hot isostatic pressing 3, approach the theoretical density of this alloy.
Embodiment 3
Prepare 70 weight %Si-Al alloys.Found 30 weight %Si-Al intermediate alloy ingot with 150 kilograms of medium-frequency induction furnaces.With lumpiness is that 4～6mm, weight are that 6 kilograms pure Si and 14 kilograms industrial pure Al are put into the medium-frequency induction furnace crucible, heats up to make its fusing, and it is standby to be cast into intermediate alloy ingot.With above-mentioned intermediate alloy ingot remelting, add 13.3 kilograms pure Si, prepare 70 weight %Si-Al alloys with the jet deposition formation method.Processing parameter is selected as follows: atomizing gas: nitrogen; Atomizing pressure: 0.75MPa; Deposition distance: 590mm; Draft-tube diameter: 4.0mm.The material coefficient of thermal expansion coefficient is 8.1 * 10 -6/ K.Resistivity is 1.6 * 10 -6Ω m.

Claims (1)

1, a kind of preparation method of jet deposition formation Si-Al alloy, it is characterized in that: adopt prefabricated 25～50 weight %Si-Al master alloys of medium-frequency induction furnace, obtain final 50～70 weight %Si-Al alloys by the mode of in master alloy, adding Si with the jet deposition formation method according to the ultimate aim composition then; Concrete grammar is as follows:
The preparation of a, master alloy: will account for the pure Si of 25 ~ 50 weight %, all the other put into the medium-frequency induction furnace fusing that heats up for the starting material of industrial pure Al, and it is standby to be cast into intermediate alloy ingot, and pure Si and industrial pure Al are block;
The preparation of b, jet deposition formation 50～70 weight %Si-Al alloys: above-mentioned intermediate alloy ingot is put into the medium-frequency induction furnace crucible, according to 50～70 weight %Si-Al alloying constituent requirements, the pure Si that optionally adds 0～45 weight % heats up and melts, and adopts jet deposition formation method preparation 50 ~ 70 weight %Si-Al alloys then; The spray deposition processing parameter is selected as follows: atomizing gas: nitrogen; Atomizing pressure: 0.6～0.8MPa; Deposition distance: 400～600mm; Draft-tube diameter: 3.2～4.0mm.
CNB2004100390579A 2004-01-29 2004-01-29 Method for preparing Si-Al alloy using spray deposition forming process Expired - Fee Related CN100534673C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1304620C (en) * 2005-08-17 2007-03-14 北京科技大学 Method for jet deposition formation to preparing lanthanum matrix massive amorphous alloy
CN103740956A (en) * 2014-01-08 2014-04-23 镇江镨利玛新型材料科技有限公司 Preparation method of high-silicon aluminum alloy

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6096143A (en) * 1994-10-28 2000-08-01 Daimlerchrysler Ag Cylinder liner of a hypereutectic aluminum/silicon alloy for use in a crankcase of a reciprocating piston engine and process for producing such a cylinder liner
CN1078257C (en) * 1999-02-03 2002-01-23 北京科技大学 Melting-casting process of preparing metal-base composite material through in-situ reaction and spray formation
KR100353415B1 (en) * 2000-01-31 2002-09-18 (주) 두레에어메탈 Process for Making Al-Si Alloys for Vehicle Propeller Shaft
CN1184339C (en) * 2000-09-27 2005-01-12 北京科技大学 Method for spraying and depositing high silicon aluminium alloy
CN1184343C (en) * 2002-11-29 2005-01-12 上海宝钢集团公司 High-strength superhigh-carbon steel and its production process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1304620C (en) * 2005-08-17 2007-03-14 北京科技大学 Method for jet deposition formation to preparing lanthanum matrix massive amorphous alloy
CN103740956A (en) * 2014-01-08 2014-04-23 镇江镨利玛新型材料科技有限公司 Preparation method of high-silicon aluminum alloy

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