CN106825547B - The method of the increasing material manufacturing metal polyporous material of selective laser melting metal micro-nano hybrid particles solution under air environment - Google Patents
The method of the increasing material manufacturing metal polyporous material of selective laser melting metal micro-nano hybrid particles solution under air environment Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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- Y02P10/00—Technologies related to metal processing
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Abstract
The method of the increasing material manufacturing metal polyporous material of selective laser melting metal micro-nano hybrid particles solution, belongs to metal polyporous material preparation technical field under a kind of air environment.The method comprises the following steps: configuration dispersion solution；Configure metal micro nanometer mixed solution；It cleans stainless steel base and dries；Stainless steel base plane is put near 40 microns of positions of selective laser melting manufacturing device laser facula；Laser scanning is carried out, stainless steel powder and micron and Nano metal powder is melted with stainless steel base and links together；Metal porous structure is cleaned.The invention has the advantages that having many advantages, such as that environmental requirement is low, at low cost, controllability is strong, equipment requirement is low, flexible new peak, simple process compared to existing method of manufacturing technology.Meanwhile surface is evenly equipped with nano particle, and the structure is caused to have the superoleophobic characteristic of super-hydrophilic and underwater.
Description
Technical field
The invention belongs to metal polyporous material preparation technical fields, and in particular to selective laser is molten under a kind of air environment
Change the method for the increasing material manufacturing metal polyporous material of metal micro-nano hybrid particles solution.
Background technique
Metal material increases material manufacturing technology is studied at present based on discrete-accumulation principle, is driven by part three-dimensional data
The science system of direct manufacturing parts.Existing metal increases material manufacturing technology is mainly selective laser melting, selectivity
It is laser sintered, three kinds of laser melting coating.Metal increases material manufacturing technology is the graphics process for combining computer, digital information and control
The advantage of the multinomial high-tech such as system, laser technology, mechanical & electrical technology and material technology.Metal increases material manufacturing technology is known as to bring
The new technology of " the third time industrial revolution ".
Selective laser melting technology is completely melt under the heat effect of laser beam using metal powder, through cooled and solidified
And a kind of molding technology.In order to be completely melt metal powder.Under the effect of high laser energy density, metal powder is completely molten
Change, can be achieved to form with the soldering of solid metal metallurgy after cooling.Selective laser melting technology is exactly based on this process,
Accumulation molds the rapid shaping technique of 3D solid layer by layer.
Metal material used in selective laser sintering is treated and low-melting-point metal or high molecular material
Mixed-powder, the material of low melting point melts during processing but dystectic metal powder is infusible.Using being melt
Molding is cohered in the material realization of change, so entity, there are hole, poor mechanical property, words to be used will also pass through high temperature reflow.
Selective laser is namely completely melt powder with laser during processing, does not need adhesive, molding precision and
Mechanical property is all got well than selective laser sintering.
Laser melting coating refers to that the coating material placed and selected on by cladding matrix surface with different adding material modes passes through
Laser irradiation is allowed to and matrix surface a thin layer while melting, and it is extremely low to form dilution after quickly solidifying, with matrix at metallurgy
In conjunction with surface covering, significantly improve wear-resisting, anti-corrosion, heat-resisting, anti-oxidant and electrical characteristic the process of substrate surface, from
And achieve the purpose that surface is modified or repairs, the requirement to material surface particular characteristic was not only met, but also saved a large amount of expensive
Heavy element.
However, selective laser melting, selective laser sintering, laser melting and coating technique, the metal material as involved in process
The fusing and solidification of material to avoid causing being oxidized, therefore are required to gas shield or vacuum environment.This considerably increases equipment
Complexity and manufacturing cost.
Metal polyporous material is a kind of particulate metal material.By its unique design feature, the material have density it is small,
Heat-proof quality is good, sound insulation value is good and can a series of good advantages such as electromagnetic wave absorption, be as mankind's science and technology is gradually sent out
A kind of new material that exhibition is got up, is usually used in a series of industrial developments such as aerospace, petrochemical industry.Metal polyporous material
Gas permeability is very high, hole large specific surface area, material bulk density very little, net for manufacturing in petrochemical industry, aerospace, environmental protection
The devices such as change, filtering, catalytic support, electrode.Since porous metal material is dispersed by metallic matrix skeleton continuous phase and stomata
Phase or the two-phase composite material of continuous phase composition, therefore its property depends on metallic matrix used, the porosity and air hole structure, and
It is influenced by preparation process.In general, the mechanical property of porous metals reduces, electric conductivity, thermal conductivity with the increase of the porosity
Also reduction is accordingly had exponent relation.When porous metals bear pressure, the forced area caused by stomata collapses increases and material
Strain hardening effect is expected, so that porous metal material has excellent absorption ability for impact energy.
Currently, common porous metal material preparation process is broadly divided into four kinds of methods: liquid metal straight forming, powder
Metallurgy, vapor deposited metal, electrochemical deposition.Liquid metal straight forming is using gas or other organic matters in liquid metal
Middle filling certain space (organic matter can volatilize during heating disappearance), after temperature reduces, forms porous metal material.
Powder metallurgy is heated after mixing metal powder with organic particle, and metallic particles is mutually interconnected due to part fusing after heating
It connects, organic matter can then be melted from sintering structure to be evaporated, and porous material is ultimately formed.Vapor deposited metal is in vacuum ring
Under border, metallic vapour covers organic matter surface, forms the metal polyporous material of certain thickness and density.Electrochemical deposition method
It is similar with vapor deposition principle, it is that ionic state metal is deposited on organic matter precursor surface by electrochemical means.Deposition
Afterwards, by method for subsequent processing, presoma is removed in the composite.However, above method is required to vacuum environment or gas
Body environmental protection, complex process.
Summary of the invention
The purpose of the present invention is to solve the above-mentioned problems in the prior art, proposes and selected under a kind of air environment
The method that selecting property laser melts the increasing material manufacturing metal polyporous material of metal micro-nano hybrid particles solution.
The present invention utilizes selective laser melting technology sintered stainless steel powder and micron and copper nano under the protection of solution
The mixed powder of the two realizes the manufacture of metal porous structure under air environment.Metal porous structure surface after manufacture has
Nanoscale structures, so that the structure has super hydrophilic, underwater superoleophobic characteristic.Since this method combines selective laser melting
Manufacturing technology is, it can be achieved that under air environment, increasing material manufacturing (3D printing) technique of metal micro-nano particle three-dimensional structure.Due to table
There is certain roughness and surface adhesion to have nano particle in face, and the structure of manufacture has unique super hydrophilic, underwater superoleophobic
Characteristic.
To achieve the above object, the technical solution adopted by the present invention is as follows:
The increasing material manufacturing of selective laser melting metal micro-nano hybrid particles solution is metal porous under a kind of air environment
The method of material, specific step is as follows for the method:
Step 1: configuration dispersion solution, by the polyvinylpyrrolidone of 1wt% ~ 20wt% and 10wt% ~ 80wt% nano metal
Powder is dispersed in the solvent of 10wt% ~ 80wt%, and ultrasonic disperse is uniform, obtains dispersion solution；
Step 2: the stainless steel powder and micron of 10wt% ~ 80wt% is added in the dispersion solution in step 1, continues ultrasound vibration
Dynamic 10min, vibration frequency 40Hz, form metal micro nanometer mixed solution；
Step 3: successively it is cleaned by ultrasonic stainless steel base with dehydrated alcohol, acetone, sodium hydroxide solution and secondary water and dries in the air
It is dry；
Step 4: it is coated with one layer of metal micro nanometer mixed solution in stainless steel base, then equals stainless steel base
Face is placed near 40 microns of positions of selective laser melting manufacturing device laser facula；
Step 5: laser is successively scanned under control of the computer, and stainless steel powder and micron and Nano metal powder are in institute
Under the protection for stating solvent, link together with the fusing of stainless steel base, while itself is mutually fused by the heat effect of laser
To metal porous structure；
Step 6: the metal porous structure that step 5 is obtained is placed in supersonic cleaning machine, will not participate in the residual of reaction
Object and product is stayed to clean up.
The beneficial effect of the present invention compared with the existing technology is:
(1) present invention is to use a laser as heat source, the mixing of selective laser sintering metal micro-nano under air environment
Solution powder.Compared to existing method of manufacturing technology, have that environmental requirement is low, controllability is strong, flexible new peak, simple process etc.
Advantage.Meanwhile surface is evenly equipped with nano particle, and the structure is caused to have the superoleophobic characteristic of super-hydrophilic and underwater.
(2) precinct laser fusion metal micro-nano hybrid particles solution increasing material manufacturing side under air environment proposed by the present invention
Method has the advantages such as at low cost, strong flexibility, equipment requirement be low compared to currently used increases material manufacturing technology；Meanwhile it should
Technology can directly manufacture metal polyporous material, and the material manufactured has super hydrophilic characteristic and underwater superoleophobic characteristic.
Detailed description of the invention
Fig. 1 is porous material section SEM produced by the present invention figure；
Fig. 2 is the surface topography map of porous material produced by the present invention；
Fig. 3 is the XRD diagram of porous material produced by the present invention；
Fig. 4 is the tomograph of porous material produced by the present invention；
Fig. 5 is the picture presentation of the structure angle of test metal porous structure prepared by the present invention and water；
Fig. 6 is the picture presentation for testing the contact angle of metal porous structure prepared by the present invention and oil under water；
Fig. 7 is the picture presentation of surface oil dripping in metal porous structure water prepared by the present invention.
Specific embodiment
However, it is not limited to this, all right to be further illustrated to the technical solution of invention with reference to the accompanying drawings and examples
Technical solution of the present invention is modified or equivalent replacement, without departing from the spirit of the technical scheme of the invention range, should all cover
Among protection scope of the present invention.
Specific embodiment 1: under a kind of air environment selective laser melting metal micro-nano hybrid particles solution increasing
The method that material manufactures metal polyporous material, the manufacturing method of present embodiment are that first to configure a kind of mixing of metal micro nanometer molten
Liquid, and it is sintered after one layer of metal substrate surface even spread using laser selective, obtain the porous knot of 3-dimensional metal
Structure；Specific step is as follows for the method:
Step 1: configuration dispersion solution, by polyvinylpyrrolidone (viscosity K30, the relative molecular mass of 1wt% ~ 20wt%
Mr 10000) and 10wt% ~ 80wt% Nano metal powder (particle diameter is dispersed in the solvent of 10wt% ~ 80wt% less than 100nm),
Ultrasonic disperse is uniform, obtains dispersion solution；
Step 2: the stainless steel powder and micron of 10wt% ~ 80wt% is added in the dispersion solution in step 1, continues ultrasound vibration
Dynamic 10min, vibration frequency 40Hz, form metal micro nanometer mixed solution；
Step 3: successively it is cleaned by ultrasonic stainless steel base with dehydrated alcohol, acetone, sodium hydroxide solution and secondary water and dries in the air
It is dry；
Step 4: it is coated with one layer of metal micro nanometer mixed solution in stainless steel base, then equals stainless steel base
Face is placed near 40 microns of positions of selective laser melting manufacturing device laser facula；
Step 5: laser is successively scanned under control of the computer, and stainless steel powder and micron and Nano metal powder are in institute
Under the protection for stating solvent, link together with the fusing of stainless steel base, while itself is mutually fused by the heat effect of laser
To metal porous structure；
Step 6: the metal porous structure that step 5 is obtained is placed in supersonic cleaning machine, will not participate in the residual of reaction
Object and product is stayed to clean up.
Specific embodiment 2: selective laser melting metal micro-nano under air environment described in specific embodiment one
The method of the increasing material manufacturing metal polyporous material of hybrid particles solution,
Step 1: configuration dispersion solution disperses the polyvinylpyrrolidone of 8.19wt% and 17.56wt% Nano metal powder
In the solvent of 27.4wt%, ultrasonic disperse is uniform, obtains dispersion solution；
Step 2: the stainless steel powder and micron of 46.85wt% is added in the dispersion solution in step 1, ultrasonic vibration is continued
10min, vibration frequency 40Hz form metal micro nanometer mixed solution.
Specific embodiment 3: selective laser melting metal is micro- under air environment described in specific embodiment one or two
The increasing material manufacturing method of nanometer hybrid particles solution, in step 1, the Nano metal powder is copper, gold, silver, titanium, nickel or oxidation
Copper.
Specific embodiment 4: selective laser melting metal micro-nano under air environment described in specific embodiment three
The increasing material manufacturing method of hybrid particles solution, in step 1, the solvent is ethylene glycol, ethyl alcohol or glycerine.
The principle of the present invention is: by taking copper metal as an example, for copper metal nano particle due to dimensional effect, fusing point is lower, by copper
Nano particle is scattered in ethylene glycol under the effect of polyvinylpyrrolidone dispersing agent, is formed solution, can be prevented nanometer in this way
The reunion and precipitating of grain.After ultrasonic disperse is uniform, stainless steel powder and micron is added according to a certain percentage.Due to Nanometer Copper in solution
The finely dispersed reason of powder, copper nano are evenly dispersed in around stainless steel micron particles.Mixed solution is equably layered on
On stainless steel substrate, under the effect of the laser, copper nano-particle and stainless steel micro particles are acted on by infrared radiation, generate heat
Effect and melt.Since the fusing point of copper is lower than stainless steel, particle size is small, and copper is less than the absorptivity of near-infrared wavelength light stainless
Steel, molten state copper is different from stainless steel density, surface tension, wetability, and synthesis results in sintered material and wrapped up in by copper-clad.Together
When, due to the capillary and wetting action of molten metal, sintered porous structure surface has the nano particle of fritting solidification, from
And form the surface of micro-nano secondary structure.Although sintering reaction has occurred, inevitably causes under the protection of solution
The evaporation of solution, causes molten copper to contact with air and be oxidized generation copper oxide.Copper oxide can connect with unreacted solution
Touching, to be reduced to copper.But there are still one layer of surface partial oxidation copper.By layer-by-layer powdering and be sintered, by stainless steel and
Copper mutually melts connection, ultimately forms three-dimensional structure, realizes the manufacture of three-dimensional structure under air environment.
Embodiment:
The performance of superoleophobic superhydrophilic surface prepared by the present invention is detected and analyzed by specifically testing.
Detecting instrument: XRD uses (D/Max-rB) of Rigaku Co., Ltd. production；SEM is public using Dutch Philip
The field emission type scanning electron microscope (Helios NanoLab 600i) of department；Contact angle instrument is public using Germany's Dataphysics instrument
It takes charge of (OCA20).
7 width figures are obtained by experiment, as can be known from Fig. 1, the material surface of formation is wrapped up in by copper-clad, to realize copper and stainless
Steel is not oxidized；As can be seen from Figure 2, surface is covered with nano-sized particles.Meanwhile structure is porous structure, therefore capillarity
Significantly；Peak value appears in the position of copper and iron to XRD as the result is shown as can be seen from Figure 3, does not occur copper oxide peak value, illustrates the technique system
The porous structure made only surface due to solution evaporation and be oxidized, interior metal is not oxidized.As can be seen from Figure 4, which can
Realize the manufacture of metal material three-dimensional structure under air environment.As can be seen from Figure 5, which is porous structure, in the work of capillary force
Under, which has super hydrophilic characteristic.From Fig. 6, Fig. 7 it is found that due to the micro-nano secondary structure that surface has, thus it is manufactured
Porous material has underwater superoleophobic characteristic.
In conclusion the present invention provides a kind of technique sides of selective laser melting increasing material manufacturing metal under air environment
Method.This method can realize under gas-protection-free environment, the manufacture of metal three-dimensional porous structure.Meanwhile the structure of manufacture is being not necessarily to
In the case where being further processed, there is super hydrophilic and underwater superoleophobic characteristic.
Claims (3)
1. the metal porous material of increasing material manufacturing of selective laser melting metal micro-nano hybrid particles solution under a kind of air environment
The method of material, it is characterised in that: specific step is as follows for the method:
Step 1: the polyvinylpyrrolidone of 8.19wt% and 17.56wt% Nano metal powder are dispersed in by configuration dispersion solution
In the solvent of 27.4wt%, ultrasonic disperse is uniform, obtains dispersion solution；
Step 2: the stainless steel powder and micron of 46.85wt% is added in the dispersion solution in step 1, ultrasonic vibration is continued
10min, vibration frequency 40Hz form metal micro nanometer mixed solution；
Above percentage meaning is as follows: in metal micro nanometer mixed solution, polyvinylpyrrolidone accounts for 8.19wt%, receives
Metal powder accounts for 17.56wt% to rice, solvent accounts for 27.4wt%, stainless steel powder and micron accounts for 46.85wt%；
Step 3: successively it is cleaned by ultrasonic stainless steel base with dehydrated alcohol, acetone, sodium hydroxide solution and secondary water and dries；
Step 4: it is coated with one layer of metal micro nanometer mixed solution in stainless steel base, then puts stainless steel base plane
It is placed near 40 microns of positions of selective laser melting manufacturing device laser facula；
Step 5: laser is successively scanned under control of the computer, and stainless steel powder and micron and Nano metal powder are described molten
Under the protection of agent, link together with the fusing of stainless steel base, while itself mutually being fused by the heat effect of laser and obtaining gold
Genus polyporus structure；
Step 6: the metal porous structure that step 5 is obtained is placed in supersonic cleaning machine, will not participate in the residue of reaction
It is cleaned up with product.
2. selective laser melting metal micro-nano hybrid particles solution under a kind of air environment according to claim 1
The method of increasing material manufacturing metal polyporous material, it is characterised in that: in step 1, the Nano metal powder is copper, gold, silver, titanium, nickel
Or copper oxide.
3. selective laser melting metal micro-nano hybrid particles solution under a kind of air environment according to claim 2
The method of increasing material manufacturing metal polyporous material, it is characterised in that: in step 1, the solvent is ethylene glycol, ethyl alcohol or glycerine.
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| CN108408685B (en) * | 2018-02-05 | 2019-04-23 | 杭州电子科技大学 | A kind of ultrasonic vibration etching device and nanoprocessing system |
| CN110449583B (en) * | 2019-08-19 | 2020-07-10 | 武汉大学 | Method for rapidly preparing metal nano porous material by laser |
| WO2021146634A1 (en) * | 2020-01-16 | 2021-07-22 | Entegris, Inc. | Porous sintered metal bodies and methods of preparing porous sintered metal bodies |
| CN111906312B (en) * | 2020-07-08 | 2022-06-14 | 广东工业大学 | Method for preparing flexible liquid absorption core by laser-induced reduction sintering of copper oxide ink |
| CN112793158A (en) * | 2020-12-28 | 2021-05-14 | 广东石油化工学院 | Butt-joint type underwater 3D printer arranged in parallel from top to bottom |
| CN114054772B (en) * | 2021-10-09 | 2024-01-02 | 季华实验室 | Metal part with micro-nano structure and preparation method and application thereof |
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| CN100418672C (en) * | 2007-02-12 | 2008-09-17 | 哈尔滨工业大学 | Preparation method of aluminium-based porous composite material with micro confined hole |
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