CN108031854A - A kind of method of modifying at the metal dust interface for 3D printing - Google Patents
A kind of method of modifying at the metal dust interface for 3D printing Download PDFInfo
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- CN108031854A CN108031854A CN201711276457.5A CN201711276457A CN108031854A CN 108031854 A CN108031854 A CN 108031854A CN 201711276457 A CN201711276457 A CN 201711276457A CN 108031854 A CN108031854 A CN 108031854A
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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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
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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
- B22F1/16—Metallic particles coated with a non-metal
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Abstract
The present invention provides a kind of method of modifying at the metal dust interface for 3D printing.Rotation electrode rod is made in metal, argon gas is ionized using transferred arc formula plasma gun, make metal molten under the extreme temperature of arc light, drop is ejected under the action of the centrifugal force and is cooled to powder, pre-fixed again in weak acid liquid with titanium source, the further reaction generation nanometer titanium dioxide-coated metal dust in dust technology liquid, finally carries out millisecond laser welding, you can realize the interface modification to metal dust.This method passes through the titanium dioxide nanocrystalline fixed in metal powder surface dispersed substantial, it not only ensure that modified effect, the metal product that more importantly overcomes 3D printing is easy to crack, unbalanced stress phenomenon, improve the precision and intensity of 3D printing, and whole preparation method technical process is simple, easy to control, cost is relatively low, can large-scale promotion.
Description
Technical field
The present invention relates to metal material field, and in particular to the interface modification of metal dust, is used for more particularly to one kind
The method of modifying at the metal dust interface of 3D printing.
Background technology
Since information age, the appearance using network technology and digital technology as the new technology of representative is profoundly changing
The every aspect of human society.And 3D printing technique quickly changes traditional mode of production as strategic emerging industries
And life style, countries in the world are paid much attention to and actively promote the technology.Many experts think, with digitlization, networking, a
Property, customize with the characteristics of 3D printing technique for representative coming of new technology will promote the third time industrial revolution.With science and technology
Development and the demand promoted and applied, metal function part is directly manufactured using rapid shaping becomes the main development of rapid shaping
Direction.
Metal builds 3D printing technique as forward position and most potential technology the most in whole 3D printing system, is advanced
The important development direction of manufacturing technology, is widely used in the fields such as aerospace, automobile and motorcycle, household electrical appliances.From metal 3D printing
Implementation is classified, and is mainly had two kinds, is sintered type and cladding formula respectively：Sintering process is divided into laser sintered and electron beam and burns
Knot, this kind of product major advantage is that molding precision is higher, and shortcoming is that shaping speed is low, and compact dimensions are limited in 300mm or so；
It is mainly used in medical treatment and small mould manufacture；The major advantage of laser cladding forming technique is that metallurgical quality is good, shaping speed
Hurry up, compact dimensions it is big, but precision is relatively low, need to subsequently machine, and typical case is aviation high-strength structure part, vane manufacturing, each
The straight forming of kind metal die.Regardless of whether be to use which kind of technique, the direct manufacturing technology of high-performance metal component and supporting material
The development of material is inseparable, therefore hardware directly high-performance metal powder used in manufacture quickly manufactures as metal product
Key.
The research and development and breakthrough of hardware 3D printed materials are the bases that hardware 3D printing technique promotes and applies,
Be meet printing basic assurance, including single metal dust, alloy powder and with metalline some infusibility chemical combination
Thing powder.3D printing metal powder materials include cochrome, stainless steel, Industrial Steel, bell metal, titanium alloy and nickel aluminium and close
Gold etc., in addition to it need to possess good plasticity, it is necessary to meet that tiny powder diameter, narrower particle size distribution, sphericity are high, flow
Property the requirement such as good and apparent density height.The developing direction that 3D prints metal material at present mainly has 3 aspects：When how
The existing relation research using on the basis of material between reinforcement material structure and attribute, further optimizes according to the property of material
Technological parameter, increases print speed, reduces porosity and oxygen content, improves surface quality；Second, research and development new material is applicable in it
In 3D printing, corrosion-resistant, high temperature resistant and the excellent new material of comprehensive mechanical property are such as developed；Third, revise and improve 3D printing powder
Body material technology standards system, realizes the institutionalization and normalization of metal material printing technique standard.Wherein by material
It is modified and optimizes and improve the main direction of studying that its performance is domestic and international researcher.
Chinese invention patent application number 201510400382.1 discloses a kind of titanium alloy laser 3D printing improved method, tool
Body method is：Titanium or titanium alloy powder and improvement material powder ball milling are mixed into powder equal, laser 3D printing.What the invention was prepared swashs
Metallographic structure is tiny in light 3D printing titanium product；And subsequent heat treatment window can be significantly widened, make high annealing shape
It is achieved into statenchyma, long-time solution treatment or annealing can be carried out, so as to obtains uniform metallographic structure, significantly
Improve its mechanical property.
Chinese invention patent application number 201410134451.4 discloses a kind of metal powder material of 3D printing, with bag
The magnesium powder for being wrapped with rosin thin film is basic material, adds a certain proportion of nickel powder for being enclosed with rosin thin film as support material,
It is intermediate materials to add a certain proportion of aluminium powder, three kinds of metal powders by being sufficiently stirred, become be used for 3D printing after mixing
Magnesium-base metal powder.
Chinese invention patent application number 201710114877.7 disclose a kind of 3D printing nano metal alloy powder and
Its preparation method, the ELECTRODE WITH BILAYER POLYMERIC thing in the invention coat nano metal alloy powder using nano metal alloy powder as kernel, and by
It is interior and outer, sulfonated polyether amine layer is coated with successively and polyetheramine-hyperbranched poly pyrrole throat copolymer layer, polyquaternium are modified oxidized
Graphene.
The surface that Chinese invention patent application number 201410331454.7 discloses a kind of flake metal powder is modified preparation
Method, mainly comprises the following steps：Spherical metal powder, metal-chelator, surface conditioning agent, solvent naphtha and abrasive media are added to ball milling
Slurry progress separation of solid and liquid is taken out in machine, after ball milling and obtains paste metal powder, gained paste metal powder is dried and is classified
Processing, that is, obtain having metal-chelator and the modified sheeted metal-powder of surface conditioning agent double-coating.
According to above-mentioned, in existing scheme, due to the property such as metal powder particle diameter, sphericity, oxygen content, mobility, apparent density
The limitation of energy so that using the hardware poor-performing of metal increasing material manufacturing, also there are more defect compared with casting and manufacturing.
Wherein, it is a variety of to be related to solid-liquid phase change, diffusion into the surface and the heat transfer of metal etc. for the 3D printing manufacturing technology of metal material
Physical process, because the uniformity is there are problem, easily cracks, and the scheme solved at present mainly by control 3D laser into
The technique of type, the translational speed of power and Energy distribution, laser focus point such as laser and path, charging rate, protection air pressure,
External temperature etc., but exist control complex process and it is unmanageable the problem of.In consideration of it, the present invention propose it is a kind of innovative
The method of 3D printing metal dust interface modification, can effectively solve above-mentioned technical problem.
The content of the invention
For the wider 3D printing metal powder material of current application there are stress defect, it is easy to crack the problems such as so that
Obtained hardware poor-performing, and it is extremely complex generally directed to the technique of the control 3D laser formations of problems, and
Process is difficult to control, and the present invention proposes a kind of method of modifying at metal dust interface for 3D printing, so as to effectively increase
The performance of metal powder material, and process is simple and cost is relatively low.
Concrete technical scheme of the present invention is as follows：
A kind of method of modifying at metal dust interface for 3D printing, the process of the metal dust interface modification are：
（1）Metal is made bar, and finish for can high-speed rotating plasma gun electrode bar, using plasma rotating electrode
Flour mill group, startup power supply, introduces argon gas, high speed rotation electrode rod after being vacuumized to furnace body, and uses plasma gun to argon gas
Striking twice is carried out, argon gas ionizes, and up to 3600 DEG C of arc light extreme temperature, anode stub material head are set up between cathode and anode
Fusing, ejects drop under the action of the centrifugal force, and drop is frozen into powder through the forced convertion instantaneous cooling of argon gas stream, and
Fall and collect under gravity, obtain nano level metal dust；
（2）Weak acid liquid is made into using phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexa, sldium lauryl sulfate and water, is added
Step（1）Metal dust, add titanium source, be heated to 50 ~ 60 DEG C of reactions, titanium source is scattered in metal powder surface and pre- solid
It is fixed, stop reaction after 1 ~ 1.5h, filtering, is cleaned with clear water；The addition of the metal dust is the 5 ~ 8% of weak acid liquid quality；Institute
The addition for stating titanium source is the 4 ~ 6% of weak acid liquid quality；
（3）By step（2）Gained powder is added in dust technology liquid, is heated to 60 ~ 80 DEG C of reactions, is stopped reaction after 40 ~ 60min,
Filtering, clear water are cleaned, and obtain the metal dust by nanometer titanium dioxide-coated；The addition of the powder is dust technology liquid quality
3 ~ 5%；
（4）Using millisecond pulse laser to step（3）The metal dust of coated by titanium dioxide welded, make nanometer titanium dioxide
Titanium is fixedly secured on the surface of metal dust with nanometer crystalline form, you can realizes the interface modification to metal dust.
Preferably, the metal is one kind in titanium alloy, albronze, magnesium alloy or stainless steel.
Preferably, the titanium source is at least one of titanium tetrachloride, tetrabutyl titanate or isopropyl titanate.
Preferably, the total mass fraction of each component is in terms of 100 parts in the weak acid liquid, wherein 20 ~ 25 parts of phosphoric acid, phosphoric acid hydrogen
20 ~ 25 parts of ammonium, 3 ~ 6 parts of hydrofluoric acid, 1 ~ 3 part of hexa, 0.1 ~ 0.3 part of sldium lauryl sulfate, 40 ~ 55 parts of water.
Preferably, the mass concentration of the dust technology liquid is 10 ~ 15%.
Preferably, the plasma gun is transferred arc formula plasma gun, and power is 60 ~ 100kW, electric current for 1600 ~
2200A, voltage are 40 ~ 70V.
Preferably, the rotary speed of the metal electrode bar is 10000 ~ 20000r/min.
Preferably, the vacuum is 3 × 10-3~5×10-3Pa。
Preferably, the speed of the molten drop cooling is 100 ~ 120 DEG C/s.
Preferably, the particle diameter of the nano level metal dust is 5 ~ 10nm；
Preferably, the millisecond pulse laser is produced by high pulse energy optical fiber laser, and pulse frequency is 8 ~ 12Hz, and pulsewidth is
8 ~ 12ms, single pulse energy are 12 ~ 18J, and the power density of laser is 3 × 109~8×109W/m2。
Plasma rotating electrode process is to prepare one of ideal mode of high-purity clear height dense spherical dusty material, application
There is significant advantage in terms of 3D printing material powder：Powder is solid, be not in print procedure hollow ball bring air gap,
The defects of being involved in property and Precipitating gas hole, crackle；Powder diameter is small, narrow particle size distribution, nodularization in print procedure, agglomeration compared with
It is few, surface smoothness higher, and the uniformity printed can be to be fully ensured with uniformity；Powder sphericity is high, mobility
Good, apparent density is high, the product consistency higher printed；Powder flowbility is good, and powdering uniformity is good；Oxygen content in power
Low, surface-active is small, and wetability is good, and spherodization is few, and fusing effect is good.Therefore plasma rotating electrode process is used in the present invention
Manufacture 3D printing metal dust.
The laser beam of pulse laser welding is assembled to form luminous point, can heat, melt and frozen metal within the millisecond time, right
Material and parts other parts influence small.Therefore titanium dioxide nanocrystalline is welded on gold by the present invention using millisecond pulse Laser Welding
Belong on powder, the excellent of process can effectively be controlled in the processing of nano structural material by taking full advantage of millisecond pulse laser
Characteristic, while played Laser Welding and welded superperformance in primary structural component dissimilar materials, it ensure that the stability of products obtained therefrom.
By modified 3D printing metal dust produced by the present invention and airflow milling comminuting method, HDH method and laminar flow atomization
Obtained 3D printing metal dust compares, in powder property（Particle diameter, sphericity, oxygen content, mobility）And product properties（Beat
Print precision, anti-cracking ability）Aspect, has obvious advantage, as shown in table 1.
Table 1：
The present invention provides a kind of method of modifying at the metal dust interface for 3D printing, and compared with prior art, it is protruded
The characteristics of and excellent effect be：
1st, the method being modified using titanium dioxide nanocrystalline cladding to 3D printing metal powder surface is proposed.
2nd, by the titanium dioxide nanocrystalline disperseed to metal powder surface, metal metallographic is uniform raw when guiding 3D printing
It is long, overcome it is quick, drastically, product cracking, unbalanced stress phenomenon caused by the growth of uneven metallographic, improve the precision of 3D printing
And intensity.
3rd, overcoming nano-titanium dioxide can not be fixedly secured with nanometer crystalline form the metal powder surface the problem of, be avoided
Metal powder surface be modified not exclusively and it is unstable the defects of.
4th, preparation method of the invention, technical process is simple, easy to control, reduces manufacturing cost, can large-scale promotion.
Embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Scope be only limitted to following example.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）Metal is made bar, and finish for can high-speed rotating plasma gun electrode bar, using plasma rotating electrode
Flour mill group, startup power supply, introduces argon gas, high speed rotation electrode rod after being vacuumized to furnace body, and uses plasma gun to argon gas
Striking twice is carried out, argon gas ionizes, and up to 3600 DEG C of arc light extreme temperature, anode stub material head are set up between cathode and anode
Fusing, ejects drop under the action of the centrifugal force, and drop is frozen into powder through the forced convertion instantaneous cooling of argon gas stream, and
Fall and collect under gravity, obtain nano level metal dust；Metal is titanium alloy；Plasma gun is transferred arc formula plasma
Rifle, power 80kW, electric current 2000A, voltage 70V；The rotary speed of metal electrode bar is 19000r/min；Vacuum is 5
×10-3Pa；The speed of molten drop cooling is 115 DEG C/s；The particle diameter of metal dust prepared by rotation electrode is 8nm；
（2）Weak acid liquid is made into using phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexa, sldium lauryl sulfate, adds step
（1）Metal dust, add titanium source, be heated to 60 DEG C reaction, titanium source is scattered in metal powder surface and pre-fix, 1.3h
Stop reaction afterwards, filtering, is cleaned with clear water；The addition of metal dust is the 6% of weak acid liquid quality；Titanium source is titanium tetrachloride；Titanium
The addition in source is the 5% of weak acid liquid quality；The total mass fraction of each component is in terms of 100 parts in weak acid liquid, wherein 25 parts of phosphoric acid,
20 parts of ammonium hydrogen phosphate, 4.7 parts of hydrofluoric acid, 2 parts of hexa, 0.3 part of sldium lauryl sulfate, 48 parts of water；
（3）By step（2）Gained powder is added in dust technology liquid, is heated to 70 DEG C of reactions, is stopped reaction after 60min, filter, clearly
Water is cleaned, and obtains the metal dust by nanometer titanium dioxide-coated；The addition of powder is the 4% of dust technology liquid quality；Dust technology
The mass concentration of liquid is 12%；
（4）Using millisecond pulse laser to step（3）The metal dust of coated by titanium dioxide welded, make nanometer titanium dioxide
Titanium is fixedly secured on the surface of metal dust with nanometer crystalline form, you can realizes the interface modification to metal dust；Millisecond pulse
Laser is produced by high pulse energy optical fiber laser, pulse frequency 10Hz, pulsewidth 10ms, single pulse energy 15J, laser
Power density be 7 × 109W/m2。
Modified 3D printing metal powder material, its powder property made from embodiment 1（Particle diameter, sphericity, oxygen content, stream
Dynamic property）And product properties（Printing precision, anti-cracking ability）As shown in table 2.
Embodiment 2
（1）Metal is made bar, and finish for can high-speed rotating plasma gun electrode bar, using plasma rotating electrode
Flour mill group, startup power supply, introduces argon gas, high speed rotation electrode rod after being vacuumized to furnace body, and uses plasma gun to argon gas
Striking twice is carried out, argon gas ionizes, and up to 3600 DEG C of arc light extreme temperature, anode stub material head are set up between cathode and anode
Fusing, ejects drop under the action of the centrifugal force, and drop is frozen into powder through the forced convertion instantaneous cooling of argon gas stream, and
Fall and collect under gravity, obtain nano level metal dust；Metal is albronze；Plasma gun for transferred arc formula etc. from
Sub- rifle, power 60kW, electric current 2200A, voltage 50V；The rotary speed of metal electrode bar is 18000r/min；Vacuum
For 3 × 10-3Pa；The speed of molten drop cooling is 100 DEG C/s；The particle diameter of metal dust prepared by rotation electrode is 7nm；
（2）Weak acid liquid is made into using phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexa, sldium lauryl sulfate, adds step
（1）Metal dust, add titanium source, be heated to 53 DEG C reaction, titanium source is scattered in metal powder surface and pre-fix, after 1h
Stop reaction, filtering, is cleaned with clear water；The addition of metal dust is the 5% of weak acid liquid quality；Titanium source is tetrabutyl titanate；Titanium
The addition in source is the 4% of weak acid liquid quality；The total mass fraction of each component is in terms of 100 parts in weak acid liquid, wherein 23 parts of phosphoric acid,
24 parts of ammonium hydrogen phosphate, 3.8 parts of hydrofluoric acid, 3 parts of hexa, 0.2 part of sldium lauryl sulfate, 46 parts of water；
（3）By step（2）Gained powder is added in dust technology liquid, is heated to 70 DEG C of reactions, is stopped reaction after 45min, filter, clearly
Water is cleaned, and obtains the metal dust by nanometer titanium dioxide-coated；The addition of powder is the 4.5% of dust technology liquid quality；Dilute nitre
The mass concentration of acid solution is 12%；
（4）Using millisecond pulse laser to step（3）The metal dust of coated by titanium dioxide welded, make nanometer titanium dioxide
Titanium is fixedly secured on the surface of metal dust with nanometer crystalline form, you can realizes the interface modification to metal dust；Millisecond pulse
Laser is produced by high pulse energy optical fiber laser, pulse frequency 9Hz, pulsewidth 11ms, single pulse energy 12J, laser
Power density be 8 × 109W/m2。
Modified 3D printing metal powder material, its powder property made from embodiment 2（Particle diameter, sphericity, oxygen content, stream
Dynamic property）And product properties（Printing precision, anti-cracking ability）As shown in table 2.
Embodiment 3
（1）Metal is made bar, and finish for can high-speed rotating plasma gun electrode bar, using plasma rotating electrode
Flour mill group, startup power supply, introduces argon gas, high speed rotation electrode rod after being vacuumized to furnace body, and uses plasma gun to argon gas
Striking twice is carried out, argon gas ionizes, and up to 3600 DEG C of arc light extreme temperature, anode stub material head are set up between cathode and anode
Fusing, ejects drop under the action of the centrifugal force, and drop is frozen into powder through the forced convertion instantaneous cooling of argon gas stream, and
Fall and collect under gravity, obtain nano level metal dust；Metal is magnesium alloy；Plasma gun for transferred arc formula etc. from
Sub- rifle, power 80kW, electric current 1900A, voltage 50V；The rotary speed of metal electrode bar is 17000r/min；Vacuum
For 3.5 × 10-3Pa；The speed of molten drop cooling is 105 DEG C/s；The particle diameter of metal dust prepared by rotation electrode is 9nm；
（2）Weak acid liquid is made into using phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexa, sldium lauryl sulfate, adds step
（1）Metal dust, add titanium source, be heated to 58 DEG C reaction, titanium source is scattered in metal powder surface and pre-fix, after 1h
Stop reaction, filtering, is cleaned with clear water；The addition of metal dust is the 5% of weak acid liquid quality；Titanium source is isopropyl titanate；Titanium
The addition in source is the 6% of weak acid liquid quality；The total mass fraction of each component is in terms of 100 parts in weak acid liquid, wherein 23 parts of phosphoric acid,
22 parts of ammonium hydrogen phosphate, 6 parts of hydrofluoric acid, 1.9 parts of hexa, 0.1 part of sldium lauryl sulfate, 47 parts of water；
（3）By step（2）Gained powder is added in dust technology liquid, is heated to 70 DEG C of reactions, is stopped reaction after 45min, filter, clearly
Water is cleaned, and obtains the metal dust by nanometer titanium dioxide-coated；The addition of powder is the 5% of dust technology liquid quality；Dust technology
The mass concentration of liquid is 14%；
（4）Using millisecond pulse laser to step（3）The metal dust of coated by titanium dioxide welded, make nanometer titanium dioxide
Titanium is fixedly secured on the surface of metal dust with nanometer crystalline form, you can realizes the interface modification to metal dust；Millisecond pulse
Laser is produced by high pulse energy optical fiber laser, pulse frequency 8Hz, pulsewidth 8ms, single pulse energy 14J, laser
Power density is 6 × 109W/m2。
Modified 3D printing metal powder material, its powder property made from embodiment 3（Particle diameter, sphericity, oxygen content, stream
Dynamic property）And product properties（Printing precision, anti-cracking ability）As shown in table 2.
Embodiment 4
（1）Metal is made bar, and finish for can high-speed rotating plasma gun electrode bar, using plasma rotating electrode
Flour mill group, startup power supply, introduces argon gas, high speed rotation electrode rod after being vacuumized to furnace body, and uses plasma gun to argon gas
Striking twice is carried out, argon gas ionizes, and up to 3600 DEG C of arc light extreme temperature, anode stub material head are set up between cathode and anode
Fusing, ejects drop under the action of the centrifugal force, and drop is frozen into powder through the forced convertion instantaneous cooling of argon gas stream, and
Fall and collect under gravity, obtain nano level metal dust；Metal is stainless steel；Plasma gun is transferred arc formula plasma
Rifle, power 70kW, electric current 1800A, voltage 50V；The rotary speed of metal electrode bar is 16000r/min；Vacuum is
3.5×10-3Pa；The speed of molten drop cooling is 110 DEG C/s；The particle diameter of metal dust prepared by rotation electrode is 6nm；
（2）Weak acid liquid is made into using phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexa, sldium lauryl sulfate, adds step
（1）Metal dust, add titanium source, be heated to 55 DEG C reaction, titanium source is scattered in metal powder surface and pre-fix,
Stop reaction after 1.5h, filtering, is cleaned with clear water；The addition of metal dust is the 7% of weak acid liquid quality；Titanium source is four chlorinations
Titanium；The addition of titanium source is the 5% of weak acid liquid quality；The total mass fraction of each component is in terms of 100 parts in weak acid liquid, wherein phosphoric acid
25 parts, 24 parts of ammonium hydrogen phosphate, 4 parts of hydrofluoric acid, 2.8 parts of hexa, 0.2 part of sldium lauryl sulfate, 44 parts of water；
（3）By step（2）Gained powder is added in dust technology liquid, is heated to 60 DEG C of reactions, is stopped reaction after 55min, filter, clearly
Water is cleaned, and obtains the metal dust by nanometer titanium dioxide-coated；The addition of powder is the 3.5% of dust technology liquid quality；Dilute nitre
The mass concentration of acid solution is 11%；
（4）Using millisecond pulse laser to step（3）The metal dust of coated by titanium dioxide welded, make nanometer titanium dioxide
Titanium is fixedly secured on the surface of metal dust with nanometer crystalline form, you can realizes the interface modification to metal dust；Millisecond pulse
Laser is produced by high pulse energy optical fiber laser, pulse frequency 9Hz, pulsewidth 10ms, single pulse energy 13J, laser
Power density be 5 × 109W/m2。
Modified 3D printing metal powder material, its powder property made from embodiment 4（Particle diameter, sphericity, oxygen content, stream
Dynamic property）And product properties（Printing precision, anti-cracking ability）As shown in table 2.
Embodiment 5
（1）Metal is made bar, and finish for can high-speed rotating plasma gun electrode bar, using plasma rotating electrode
Flour mill group, startup power supply, introduces argon gas, high speed rotation electrode rod after being vacuumized to furnace body, and uses plasma gun to argon gas
Striking twice is carried out, argon gas ionizes, and up to 3600 DEG C of arc light extreme temperature, anode stub material head are set up between cathode and anode
Fusing, ejects drop under the action of the centrifugal force, and drop is frozen into powder through the forced convertion instantaneous cooling of argon gas stream, and
Fall and collect under gravity, obtain nano level metal dust；Metal is titanium alloy；Plasma gun is transferred arc formula plasma
Rifle, power 90kW, electric current 1800A, voltage 70V；The rotary speed of metal electrode bar is 19000r/min；Vacuum is
5×10-3Pa；The speed of molten drop cooling is 120 DEG C/s；The particle diameter of metal dust prepared by rotation electrode is 10nm；
（2）Weak acid liquid is made into using phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexa, sldium lauryl sulfate, adds step
（1）Metal dust, add titanium source, be heated to 60 DEG C reaction, titanium source is scattered in metal powder surface and pre-fix, 1.2h
Stop reaction afterwards, filtering, is cleaned with clear water；The addition of metal dust is the 7% of weak acid liquid quality；Titanium source is tetrabutyl titanate；
The addition of titanium source is the 5% of weak acid liquid quality；The total mass fraction of each component is in terms of 100 parts in weak acid liquid, wherein phosphoric acid 25
Part, 22 parts of ammonium hydrogen phosphate, 5.7 parts of hydrofluoric acid, 2 parts of hexa, 0.3 part of sldium lauryl sulfate, 45 parts of water；
（3）By step（2）Gained powder is added in dust technology liquid, is heated to 60 DEG C of reactions, is stopped reaction after 60min, filter,
Clear water is cleaned, and obtains the metal dust by nanometer titanium dioxide-coated；The addition of powder is the 5% of dust technology liquid quality；Dilute nitre
The mass concentration of acid solution is 15%；
（4）Using millisecond pulse laser to step（3）The metal dust of coated by titanium dioxide welded, make nanometer titanium dioxide
Titanium is fixedly secured on the surface of metal dust with nanometer crystalline form, you can realizes the interface modification to metal dust；Millisecond pulse
Laser is produced by high pulse energy optical fiber laser, pulse frequency 12Hz, pulsewidth 12ms, single pulse energy 18J, laser
Power density be 8 × 109W/m2。
Modified 3D printing metal powder material, its powder property made from embodiment 5（Particle diameter, sphericity, oxygen content, stream
Dynamic property）And product properties（Printing precision, anti-cracking ability）As shown in table 2.
Embodiment 6
（1）Metal is made bar, and finish for can high-speed rotating plasma gun electrode bar, using plasma rotating electrode
Flour mill group, startup power supply, introduces argon gas, high speed rotation electrode rod after being vacuumized to furnace body, and uses plasma gun to argon gas
Striking twice is carried out, argon gas ionizes, and up to 3600 DEG C of arc light extreme temperature, anode stub material head are set up between cathode and anode
Fusing, ejects drop under the action of the centrifugal force, and drop is frozen into powder through the forced convertion instantaneous cooling of argon gas stream, and
Fall and collect under gravity, obtain nano level metal dust；Metal is albronze；；Plasma gun is transferred arc formula etc.
Ion gun, power 80kW, electric current 1800A, voltage 50V；The rotary speed of metal electrode bar is 16000r/min；Vacuum
Spend for 4 × 10-3Pa；The speed of molten drop cooling is 110 DEG C/s；The particle diameter of metal dust prepared by rotation electrode is 9nm；
（2）Weak acid liquid is made into using phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexa, sldium lauryl sulfate, adds step
（1）Metal dust, add titanium source, be heated to 60 DEG C reaction, titanium source is scattered in metal powder surface and pre-fix, 1.4h
Stop reaction afterwards, filtering, is cleaned with clear water；The addition of metal dust is the 7% of weak acid liquid quality；Titanium source is isopropyl titanate；
The addition of titanium source is the 4% of weak acid liquid quality；The total mass fraction of each component is in terms of 100 parts in weak acid liquid, wherein phosphoric acid 21
Part, 22 parts of ammonium hydrogen phosphate, 3.9 parts of hydrofluoric acid, 1 part of hexa, 0.1 part of sldium lauryl sulfate, 52 parts of water；
（3）By step（2）Gained powder is added in dust technology liquid, is heated to 70 DEG C of reactions, is stopped reaction after 50min, filter, clearly
Water is cleaned, and obtains the metal dust by nanometer titanium dioxide-coated；The addition of powder is the 3% of dust technology liquid quality；Dust technology
The mass concentration of liquid is 10%；
（4）Using millisecond pulse laser to step（3）The metal dust of coated by titanium dioxide welded, make nanometer titanium dioxide
Titanium is fixedly secured on the surface of metal dust with nanometer crystalline form, you can realizes the interface modification to metal dust；Millisecond pulse
Laser is produced by high pulse energy optical fiber laser, pulse frequency 11Hz, pulsewidth 10ms, single pulse energy 15J, laser
Power density be 7 × 109W/m2。
Modified 3D printing metal powder material, its powder property made from embodiment 6（Particle diameter, sphericity, oxygen content, stream
Dynamic property）And product properties（Printing precision, anti-cracking ability）As shown in table 2.
Comparative example 1
（1）Metal is made bar, and finish for can high-speed rotating plasma gun electrode bar, using plasma rotating electrode
Flour mill group, startup power supply, introduces argon gas, high speed rotation electrode rod after being vacuumized to furnace body, and uses plasma gun to argon gas
Striking twice is carried out, argon gas ionizes, and up to 3600 DEG C of arc light extreme temperature, anode stub material head are set up between cathode and anode
Fusing, ejects drop under the action of the centrifugal force, and drop is frozen into powder through the forced convertion instantaneous cooling of argon gas stream, and
Fall and collect under gravity, obtain nano level metal dust；Metal is albronze；；Plasma gun is transferred arc formula etc.
Ion gun, power 80kW, electric current 1800A, voltage 50V；The rotary speed of metal electrode bar is 16000r/min；Vacuum
Spend for 4 × 10-3Pa；The speed of molten drop cooling is 110 DEG C/s；The particle diameter of metal dust prepared by rotation electrode is 9nm；
（2）Weak acid liquid is made into using phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexa, sldium lauryl sulfate, adds step
（1）Metal dust, add titanium source, be heated to 60 DEG C reaction, titanium source is scattered in metal powder surface and pre-fix, 1.4h
Stop reaction afterwards, filtering, is cleaned with clear water；The addition of metal dust is the 7% of weak acid liquid quality；Titanium source is isopropyl titanate；
The addition of titanium source is the 4% of weak acid liquid quality；The total mass fraction of each component is in terms of 100 parts in weak acid liquid, wherein phosphoric acid 21
Part, 22 parts of ammonium hydrogen phosphate, 3.9 parts of hydrofluoric acid, 1 part of hexa, 0.1 part of sldium lauryl sulfate, 52 parts of water；
（3）By step（2）Gained powder is added in dust technology liquid, is heated to 70 DEG C of reactions, is stopped reaction after 50min, filter, clearly
Water is cleaned, and obtains the metal dust by nanometer titanium dioxide-coated；The addition of powder is the 3% of dust technology liquid quality；Dust technology
The mass concentration of liquid is 10%；
Modified 3D printing metal powder material, its powder property made from comparative example 1（Particle diameter, sphericity, oxygen content, mobility）
And product properties（Printing precision, anti-cracking ability）As shown in table 2.
Comparative example 2
（1）Metal is made bar, and finish for can high-speed rotating plasma gun electrode bar, using plasma rotating electrode
Flour mill group, startup power supply, introduces argon gas, high speed rotation electrode rod after being vacuumized to furnace body, and uses plasma gun to argon gas
Striking twice is carried out, argon gas ionizes, and up to 3600 DEG C of arc light extreme temperature, anode stub material head are set up between cathode and anode
Fusing, ejects drop under the action of the centrifugal force, and drop is frozen into powder through the forced convertion instantaneous cooling of argon gas stream, and
Fall and collect under gravity, obtain nano level metal dust；Metal is albronze；；Plasma gun is transferred arc formula etc.
Ion gun, power 80kW, electric current 1800A, voltage 50V；The rotary speed of metal electrode bar is 16000r/min；Vacuum
Spend for 4 × 10-3Pa；The speed of molten drop cooling is 110 DEG C/s；The particle diameter of metal dust prepared by rotation electrode is 9nm；
（2）Weak acid liquid is made into using phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexa, sldium lauryl sulfate, adds step
（1）Metal dust, add titanium dioxide, be heated to 60 DEG C of reactions, titanium dioxide is scattered in metal powder surface and pre-
It is fixed, stop reaction after 1.4h, filtering, is cleaned with clear water；The addition of metal dust is the 7% of weak acid liquid quality；In weak acid liquid
The total mass fraction of each component is in terms of 100 parts, wherein 21 parts of phosphoric acid, 22 parts of ammonium hydrogen phosphate, 3.9 parts of hydrofluoric acid, hexa-methylene four
1 part of amine, 0.1 part of sldium lauryl sulfate, 52 parts of water；
（3）By step（2）Gained powder is added in dust technology liquid, is heated to 70 DEG C of reactions, is stopped reaction after 50min, filter, clearly
Water is cleaned, and obtains the metal dust of coated by titanium dioxide；The addition of powder is the 3% of dust technology liquid quality；The matter of dust technology liquid
It is 10% to measure concentration；
（4）Using millisecond pulse laser to step（3）The metal dust of coated by titanium dioxide welded, make titanium dioxide with
Nanometer crystalline form is fixedly secured on the surface of metal dust, you can realizes the interface modification to metal dust；Millisecond pulse laser
Produced by high pulse energy optical fiber laser, pulse frequency 11Hz, pulsewidth 10ms, single pulse energy 15J, the work(of laser
Rate density is 7 × 109W/m2。
Modified 3D printing metal powder material, its powder property made from comparative example 2（Particle diameter, sphericity, oxygen content, stream
Dynamic property）And product properties（Printing precision, anti-cracking ability）As shown in table 2.
Table 2：
Claims (10)
- A kind of 1. method of modifying at metal dust interface for 3D printing, it is characterised in that the metal dust interface modification Process be：（1）Metal is made bar, and finish for can high-speed rotating plasma gun electrode bar, using plasma rotating electrode Flour mill group, startup power supply, introduces argon gas, high speed rotation electrode rod after being vacuumized to furnace body, and uses plasma gun to argon gas Striking twice is carried out, argon gas ionizes, and up to 3600 DEG C of arc light extreme temperature, anode stub material head are set up between cathode and anode Fusing, ejects drop under the action of the centrifugal force, and drop is frozen into powder through the forced convertion instantaneous cooling of argon gas stream, and Fall and collect under gravity, obtain nano level metal dust；（2）Weak acid liquid is made into using phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexa, sldium lauryl sulfate and water, is added Step（1）Metal dust, add titanium source, be heated to 50 ~ 60 DEG C of reactions, titanium source is scattered in metal powder surface and pre- solid It is fixed, stop reaction after 1 ~ 1.5h, filtering, is cleaned with clear water；The addition of the metal dust is the 5 ~ 8% of weak acid liquid quality；Institute The addition for stating titanium source is the 4 ~ 6% of weak acid liquid quality；（3）By step（2）Gained powder is added in dust technology liquid, is heated to 60 ~ 80 DEG C of reactions, is stopped reaction after 40 ~ 60min, Filtering, clear water are cleaned, and obtain the metal dust by nanometer titanium dioxide-coated；The addition of the powder is dust technology liquid quality 3 ~ 5%；（4）Using millisecond pulse laser to step（3）The metal dust of coated by titanium dioxide welded, make nanometer titanium dioxide Titanium is fixedly secured on the surface of metal dust with nanometer crystalline form, you can realizes the interface modification to metal dust.
- A kind of 2. method of modifying at metal dust interface for 3D printing according to claim 1, it is characterised in that：It is described Metal is one kind in titanium alloy, albronze, magnesium alloy or stainless steel.
- A kind of 3. method of modifying at metal dust interface for 3D printing according to claim 1, it is characterised in that：It is described Plasma gun is transferred arc formula plasma gun, and power is 60 ~ 100kW, and electric current is 1600 ~ 2200A, and voltage is 40 ~ 70V.
- A kind of 4. method of modifying at metal dust interface for 3D printing according to claim 1, it is characterised in that：It is described The rotary speed of metal electrode bar is 10000 ~ 20000r/min.
- A kind of 5. method of modifying at metal dust interface for 3D printing according to claim 1, it is characterised in that：It is described Vacuum after being vacuumized to furnace body is 3 × 10-3~5×10-3Pa。
- A kind of 6. method of modifying at metal dust interface for 3D printing according to claim 1, it is characterised in that：It is described The speed of molten drop cooling is 100 ~ 120 DEG C/s；The particle diameter of the nano level metal dust is 5 ~ 10nm.
- A kind of 7. method of modifying at metal dust interface for 3D printing according to claim 1, it is characterised in that：It is described The total mass fraction of each component is in terms of 100 parts in weak acid liquid, wherein 20 ~ 25 parts of phosphoric acid, 20 ~ 25 parts of ammonium hydrogen phosphate, hydrofluoric acid 3 ~ 6 Part, 1 ~ 3 part of hexa, 0.1 ~ 0.3 part of sldium lauryl sulfate, 40 ~ 55 parts of water.
- A kind of 8. method of modifying at metal dust interface for 3D printing according to claim 1, it is characterised in that：It is described Titanium source is at least one of titanium tetrachloride, tetrabutyl titanate or isopropyl titanate.
- A kind of 9. method of modifying at metal dust interface for 3D printing according to claim 1, it is characterised in that：It is described The mass concentration of dust technology liquid is 10 ~ 15%.
- A kind of 10. method of modifying at metal dust interface for 3D printing according to claim 1, it is characterised in that：Institute State millisecond pulse laser to be produced by high pulse energy optical fiber laser, pulse frequency is 8 ~ 12Hz, and pulsewidth is 8 ~ 12ms, pulse Energy is 12 ~ 18J, and the power density of laser is 3 × 109~8×109W/m2。
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