CN104117672B - Method for preparing/forming amorphous alloy and composite material of amorphous alloy - Google Patents
Method for preparing/forming amorphous alloy and composite material of amorphous alloy Download PDFInfo
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- CN104117672B CN104117672B CN201410375063.5A CN201410375063A CN104117672B CN 104117672 B CN104117672 B CN 104117672B CN 201410375063 A CN201410375063 A CN 201410375063A CN 104117672 B CN104117672 B CN 104117672B
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Abstract
The invention discloses a method for preparing/forming an amorphous alloy and a composite material of the amorphous alloy. By means of the method, the amorphous alloy which is large in size, complex in shape, high in strength, uniform in component and little in crystallization and a composite material part of the amorphous alloy can be prepared. The method includes the specific following steps that firstly, amorphous power is prepared; secondly, amorphous composite powder is prepared; thirdly, a part model is prepared; fourthly, a substrate is installed; fifthly, atmosphere protection is conducted; sixthly, red light positioning is conducted; seventhly, laser processing is conducted; eighthly, heat treatment is conducted. According to the method, a selective laser melting technology is applied to manufacturing of the amorphous alloy and the composite material part of the amorphous alloy, complex three-dimensional processing is transformed into simple two-dimensional processing, the manufacturing difficulty of complex components is lowered, and parts which cannot be finished through a traditional processing technology are achieved.
Description
Technical field
The invention belongs to non-crystaline amorphous metal preparation and figuration manufacture field and in particular to one kind prepare/shaping of amorphous alloy and
Its composite.
Background technology
Non-crystaline amorphous metal (also known as metal glass) is a kind of new metallic material growing up the middle of last century, because it has
The weird atom structure of longrange disorder and have a series of mechanics being substantially better than crystalline material, process based prediction model.Thus
Assume wide application prospect in fields such as machinery, the energy, chemical industry and military affairs.
However, non-crystaline amorphous metal is limited by its glass forming ability (or preparation size) not only as structural material applications, and
And meet with the bottleneck of figuration manufacture.At present, only alloy part system can prepare millimeter and centimeter scale non-crystaline amorphous metal, so far
The non-crystaline amorphous metal full-size that can prepare in the world is only diameter about 80mm, and the maximum of most of non-crystaline amorphous metal system shapes chi
Very little still it is confined to centimetre, even below mm size, which greatly limits the industrial applicability of non-crystaline amorphous metal.Further, since it is non-
Peritectic alloy has high intensity, and forming performance difference is it is difficult to carry out the machining of conventional meanses at room temperature.At present, amorphous
The manufacture of alloy part mainly adopts copper mold cast form and thermoplastic forming, but both approaches are difficult to large scale and three
The figuration manufacture of dimension complex parts.
How to prepare/to shape the non-crystaline amorphous metal that amorphous purity is high, no obvious fault of construction, geometry are complete and its answer
Condensation material is the important key of this technology.
Document 1 (nobuyuki nishiyama, kana takenaka, haruko miura, noriko saidoh,
yuqiao zeng,akihisa inoue.the world's biggest glassy alloy ever made,
Intermetallics, 2012,30,19-24) diameter is maximum in the world to disclose a kind of method preparation of employing water quenching
pd42.5cu30ni7.5p20Non-crystaline amorphous metal.But, the pd base that the method is suitable only for critical cooling rate relatively low (0.067 k/s) closes
Gold, is not suitable for the preparation of other system non-crystaline amorphous metals.
Document 2 (jan schroers.processing of bulk metallic glass, advance
Material, 2009,21,1 32) disclose using copper mold cast form and thermoplastic forming method, non-crystaline amorphous metal is carried out plus
Work, but this method is difficult to large scale and the figuration manufacture of 3 D complex part.
Invention is held
Disadvantages described above for prior art or Improvement requirement, the present invention provide one kind prepare/shaping of amorphous alloy and its
The method of composite, it can be prepared/shape, and size is larger, complex-shaped, geometry is complete, no obvious fault of construction
Non-crystaline amorphous metal and its composite, overcome cannot prepare at present/shaping of amorphous purity is high, no substantially fault of construction, geometry knot
The problem of the complete and large-sized 3 D complex non-crystaline amorphous metal part of structure.
According to a first aspect of the present invention, provide a kind of prepare the/method of shaping of amorphous alloy and/or its composite,
It prepares non-crystaline amorphous metal or its composite by selective laser fusing it is characterised in that the method specifically includes following step
Rapid:
(1) amorphous powdered alloy preparation
According to selected non-crystaline amorphous metal system, raw metal is carried out proportioning by certain atomic ratio, melting uniformly adopts afterwards
Water fog method or gas atomization obtain pure amorphous powdered alloy, after sieve after powder is dry, obtain the powder of required particle diameter.
(2) amorphous composite powder preparation
Above-mentioned pure amorphous powdered alloy is waited particle diameter metal powder in certain ratio to mix with commercially available, low speed ball milling mixing is equal
Amorphous base composite powder is obtained after even.
(3) part geometry structure design
Geometry needed for being drawn using Three-dimensional Design Software, is saved as stl form and imports slm control system.
(4) substrate is installed, is filled powder
Metal basal board is fixed on working cylinder table top, adjustment working cylinder height, makes powder feeding rod and substrate tangent.By amorphous
Alloy or amorphous -- composite metal powder adds powder feeding cylinder or powder falling bucket.
(5) atmosphere protection
Evacuation after cavity airtight, then it is passed through high-purity ar gas.
(6) HONGGUANG positioning
Scan simulated laser scanning pattern with HONGGUANG, in adjustment HONGGUANG scanning area substrate geometric ranges.
(7) laser machine
Initially with laser to substrate multiple scanning, preheating, then powdering, carry out slm printing-forming.After shaping terminates, but
Take out to after room temperature.
(8) heat treatment
Print part to 3d to make annealing treatment, discharge residual stress, promote microcrack healing, eliminate fault of construction.
It is another aspect of this invention to provide that providing a kind of non-crystaline amorphous metal of utilization said method preparation and/or its composite wood
Material.
In general, by the contemplated above technical scheme of the present invention compared with prior art, there is following beneficial effect
Really:
In the present invention, slm technology not only has energy density height, and laser facula is little, molten bath little (molten bath is about 120 μm) etc.
Feature, and cooldown rate is up to 104-105k/s.To most of non-crystaline amorphous metal system, this cooldown rate is enough to ensure that molten bath
In alloy melt be completely transformed into amorphous.
Complicated Three-dimension process is changed into simply two dimension processing by 3d printing technique by the present invention, greatly reduces multiple
The figuration manufacture difficulty of miscellaneous part.
, in slm forming process, molten bath yardstick is little, setting rate is fast, temperature is terraced for the amorphous of the present invention and its composite powder
Degree is big, and molten bath is not stopping to move, thus easily producing big residual stress in formation of parts, this is to cause knot in slm part
The main cause that structure defect produces.The present invention passes through the method applying furnace cooling and supercooling liquid phase region annealing, and release slm shapes
Residual stress in non-crystaline amorphous metal and its composite, promotes microcrack healing, eliminates fault of construction.
Brief description
Fig. 1 is pure non-crystaline amorphous metal and amorphous base composite powder xrd figure；
Fig. 2 is powdering, laser sintered schematic diagram；
Fig. 3 is for obtaining the slm drip molding section sem figure of no fault of construction after heat treatment.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, below in conjunction with the accompanying drawings and be embodied as
The invention will be further described for example.It should be appreciated that specific embodiment described herein is only in order to explain the present invention, not
For limiting the present invention.
A kind of application precinct laser fusion preparation/shaping of amorphous alloy of the present embodiment and its new side of composite
Method, specifically comprises the following steps that
(1) preparation of amorphous powdered alloy:
Selection have high laser absorption rate, amorphous formation ability general (maximum form diameter is less than 1mm), have excellent
The fe base noncrystal alloy system of mechanical property and cheap cost of material is (as fe49.7cr18mn1.9mo7.4w1.6b15.2c3.8si2.4).
According to selected amorphous system, high pure metal raw material is carried out proportioning according to atomic ratio, vacuum melting uniformly adopts afterwards
Water fog method or gas atomization obtain pure amorphous powder.After powder is dried, then powder is sieved with 450 mesh sieve, obtain 33 μm
Following powder, the xrd figure of this fe based amorphous alloy powder is as shown in Figure 1.In the present embodiment preferably
fe49.7cr18mn1.9mo7.4w1.6b15.2c3.8si2.4Amorphous alloy system, but the method for the present invention does not have to the type of non-crystaline amorphous metal
There is restriction, for example, other fe bases, al base, ni base, zr base, au base, cu base, pd base, mg base, co base, rare earth base etc. also may be selected
Non-crystaline amorphous metal system.
(2) preparation of amorphous -- composite metal powder
Above-mentioned pure amorphous powdered alloy is waited particle diameter 316l powder of stainless steel, the ratio of 9:1 mixing in mass ratio with commercially available
Afterwards, put into low speed ball milling 4 hours in agate pot, obtain fe base noncrystal alloy -- 316l rustless steel composite powder, this composite powder
Xrd figure as shown in Figure 1.Select 316l rustless steel in the present embodiment as interpolation powder, but the method for the present invention does not limit
Composite metal powder is only the above-mentioned type, and pure fe, 304 rustless steels, mould steel, pure ni, ni alloy, pure cu, cu conjunction also may be selected
Golden, pure cr, cr alloy, pure ti, ti alloy, pure mn, mn alloy, pure co, co alloy, pure zn, zn alloy, pure zr, zr alloy, pure
Metal dusts such as mo, mo alloy, pure ag, ag alloy, pure sn, sn alloy, pure w, w alloy etc..
(3) part geometry structure design
According to the shape of required part, go out three-dimensional geometrical structure figure with solidworks Software on Drawing, be converted into stl
Form, (quick manufacturing center of the such as Central China University of Science and Technology develops to import precinct laser fusion rapid molding apparatus control system
Hrpm- system) in, read using machining software.
(4) substrate is installed, is filled powder
Select the 316l stainless steel substrate of certain size and surface smoothness, be locked on working cylinder table top with screw, adjust
Full employment cylinder height, makes powder feeding rod and substrate just tangent.316l stainless steel substrate is selected in the present embodiment, but the side of the present invention
Method does not simultaneously limit to this, 04 rustless steel, cu alloy, ti alloy etc. also may be selected as substrate.
After substrate leveling, by amorphous powdered alloy to be processed or amorphous -- metal material composite powder adds powder falling bucket
In.
(5) atmosphere protection
Open vacuum pump evacuation after cavity airtight, then be passed through high-purity ar gas and atmosphere protection is carried out to cavity.
(6) HONGGUANG positioning
Open laser instrument red switch, scan simulated laser scanning pattern with HONGGUANG, by adjusting the scanning area of HONGGUANG,
Guarantee that scanning area fully falls in several size ranges of substrate.
(7) laser machine
After the completion of HONGGUANG positioning, close HONGGUANG.Open laser, to substrate multiple monolayer multiple scanning, make basal plate preheating, then
Open continuous manufacture.
As shown in Fig. 2 specifically including: (a) powder falling bucket 1 moves from left to right to the right side of working cylinder 2, falls 30 μ m thick
Powder 3；B () powder falling bucket 1 powdering finishes after, move to the left side of working cylinder 2 from right to left, laser instrument 4 starts bisque is carried out
Scanning.After the end of scan, repeat above-mentioned (a), (b) process, carry out powdering, laser scanning, successively pile up and form required part,
After machining, it is cooled to after room temperature with cavity after part and takes out.
(8) heat treatment
In order to eliminate part residual stress and microstructural defects, by the non-crystaline amorphous metal processing or metallic glass composite
(component/part) is placed in vacuum heat treatment furnace, is warming up to a certain design temperature of its supercooled liquid (as right
fe49.7cr18mn1.9mo7.4w1.6b15.2c3.8si2.4Non-crystaline amorphous metal is warming up to 595 DEG C) made annealing treatment, final structure is intact
Non-crystaline amorphous metal and its composite, such as Fig. 3 are for obtaining the slm drip molding section sem figure of no fault of construction after heat treatment.
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, not in order to
Limit the present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc., all should comprise
Within protection scope of the present invention.
Claims (5)
1. a kind of prepare the/method of shaping of amorphous alloy composite materials, it is prepared amorphous by selective laser fusing (slm) and closes
Metal/composite material part is it is characterised in that the method specifically includes following steps:
(1) amorphous powdered alloy preparation
According to selected non-crystaline amorphous metal system, raw metal is carried out proportioning, melting uniformly adopts water fog method or gas atomization afterwards
Obtain pure amorphous powdered alloy, after sieve after powder is dry, obtain the powder of required particle diameter；
(2) amorphous composite powder preparation
Above-mentioned pure amorphous powdered alloy is mixed with waiting particle diameter metal dust, low speed ball milling mixing uniformly obtains amorphous base afterwards and is combined
Powder；
Wherein, described metal dust be pure fe, 316l rustless steel, 304 rustless steels, mould steel, pure ni, ni alloy, pure cu, cu close
Golden, pure cr, cr alloy, pure ti, ti alloy, pure mn, mn alloy, pure co, co alloy, pure zn, zn alloy, pure zr, zr alloy, pure
One or more of mo, mo alloy, pure ag, ag alloy, pure sn, sn alloy, pure w and w alloy；
(3) metal basal board is fixed on the working cylinder table top of slm control system, adjustment working cylinder height, makes powder feeding rod and base
Plate is tangent, and non-crystaline amorphous metal composite powder is added powder feeding cylinder or powder falling bucket；
(4) evacuation after cavity airtight, then it is passed through high-purity ar gas, and scan simulated laser scanning pattern with HONGGUANG, adjust HONGGUANG
Scanning area is in substrate geometric ranges；
(5) laser machine, i.e. the geometric model according to amorphous alloy composite material part, slm control system initially with
Laser is to substrate multiple scanning and preheating, then powdering carry out slm printing-forming；
Amorphous alloy composite material part can be obtained by said process.
2. according to claim 1 a kind of prepare the/method of shaping of amorphous alloy composite materials, wherein, described step
(5) also execute heat treatment step after carrying out slm printing-forming, the amorphous alloy composite material part that will process is placed in vacuum
In stove, made annealing treatment, to eliminate part residual stress and microstructural defects.
3. according to claim 1 and 2 a kind of prepare the/method of shaping of amorphous alloy composite materials, wherein, described amorphous
The geometric model of alloy composite materials part imports to described slm control system beforehand through after Three-dimensional Design Software generation
In.
4. according to claim 1 and 2 a kind of prepare the/method of shaping of amorphous alloy composite materials, wherein, described is non-
Peritectic alloy is: fe base, al base, ni base, zr base, au base, cu base, pd base, the amorphous state of mg base, co base or rare earth matrix system are closed
Gold.
5. the method institute of the preparation any one of a kind of utilization the claims 1-4/shaping of amorphous alloy composite materials
The amorphous alloy composite material of preparation/shaping.
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