CN108031854B - Method for modifying metal powder interface for 3D printing - Google Patents
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Abstract
The invention provides a method for modifying a metal powder interface for 3D printing. The method comprises the steps of manufacturing metal into a rotary electrode rod, ionizing argon by adopting a transferred arc type plasma gun, melting the metal at the extreme temperature of arc light, spraying liquid drops under the action of centrifugal force, cooling the liquid drops into powder, pre-fixing the powder with a titanium source in weak acid liquid, further reacting the powder in dilute nitric acid liquid to generate nano titanium dioxide coated metal powder, and finally performing millisecond laser welding to realize interface modification of the metal powder. According to the method, the titanium dioxide nanocrystals which are firmly fixed are dispersed on the surface of the metal powder, so that the modification effect is ensured, more importantly, the phenomena that a 3D printed metal product is easy to crack and uneven in stress are overcome, the 3D printing precision and strength are improved, and the whole preparation method is simple in process, convenient to control, low in cost and capable of being popularized in a large scale.
Description
Technical Field
The invention relates to the field of metal materials, in particular to interface modification of metal powder, and particularly relates to a method for modifying a metal powder interface for 3D printing.
Background
Since the information age, the emergence of new technologies, represented by network technologies and digital technologies, is profoundly changing aspects of human society. The 3D printing technology is rapidly changing the traditional production and life styles as a strategic emerging industry, and is highly valued and actively promoted in all countries in the world. Many experts believe that new manufacturing technologies, typified by 3D printing technologies characterized by digitization, networking, personalization, customization, will drive a third industrial revolution. With the requirements of scientific and technological development and popularization and application, the main development direction of rapid prototyping is to directly manufacture metal functional parts by rapid prototyping.
The metal construction 3D printing technology is the most advanced and potential technology in the whole 3D printing system, is an important development direction of advanced manufacturing technology, and is widely applied to the fields of aerospace, automobiles, motorcycles, household appliances and the like. From metal 3D printing implementation classification, there are two main types, sintering formula and cladding formula respectively: the sintering process is divided into laser sintering and electron beam sintering, and the products have the main advantages of higher molding precision and low molding speed and have the molding size limited to about 300 mm; the method is mainly applied to medical treatment and small-sized mold manufacturing; the laser cladding forming process has the main advantages of good metallurgical quality, high forming speed, large forming size, but low precision, and needs subsequent machining, and typical applications are aviation high-strength structural members, blade manufacturing and direct forming of various metal molds. No matter what kind of process is adopted, the development of the direct manufacturing technology of the high-performance metal component and the matched material is inseparable, so the high-performance metal powder used for directly manufacturing the metal component becomes the key for quickly manufacturing the metal product.
The research, development and breakthrough of the metal component 3D printing material are the basis of popularization and application of the metal component 3D printing technology and the fundamental guarantee of meeting the printing, and comprise single metal powder, alloy powder and certain refractory compound powder with metal property. The 3D printing metal powder material comprises cobalt-chromium alloy, stainless steel, industrial steel, bronze alloy, titanium alloy, nickel-aluminum alloy and the like, and the requirements of fine powder particle size, narrow particle size distribution, high sphericity, good fluidity, high apparent density and the like are met besides good plasticity. At present, 3D prints the development direction of metal material and mainly has 3 aspects: firstly, on the basis of the existing used materials, the relation research between the structure and the attribute of the materials is strengthened, the process parameters are further optimized according to the properties of the materials, the printing speed is increased, the porosity and the oxygen content are reduced, and the surface quality is improved; secondly, new materials are researched and developed to be suitable for 3D printing, such as new materials with corrosion resistance, high temperature resistance and excellent comprehensive mechanical properties; and thirdly, revising and perfecting a 3D printing powder material technical standard system, and realizing institutionalization and normalization of the metal material printing technical standard. The improvement of the performance of the material through modification and optimization is the main research direction of researchers at home and abroad.
The Chinese patent application No. 201510400382.1 discloses an improved method for titanium alloy laser 3D printing, which comprises the following steps: and (3) ball-milling and mixing the titanium or titanium alloy powder and the improved raw material powder uniformly, and performing laser 3D printing. The metallographic structure of the laser 3D printing titanium metal product prepared by the method is fine; and the subsequent heat treatment window can be greatly widened, the formation of a balanced structure by high-temperature annealing can be realized, and long-time solution treatment or annealing treatment can be carried out, so that a uniform metallographic structure is obtained, and the mechanical property of the metallographic structure is greatly improved.
The Chinese patent application No. 201410134451.4 discloses a metal powder material for 3D printing, which is prepared by taking magnesium powder wrapped with a rosin film as a basic material, adding a certain proportion of nickel powder wrapped with the rosin film as a supporting material, adding a certain proportion of aluminum powder as an intermediate material, and fully stirring and uniformly mixing the three metal powders to obtain magnesium-based metal powder for 3D printing.
The Chinese patent application No. 201710114877.7 discloses a nano metal alloy powder for 3D printing and a preparation method thereof, wherein the nano metal alloy powder coated by a double-layer polymer takes the nano metal alloy powder as a core, and is sequentially coated with a sulfonated polyether amine layer, a polyether amine-hyperbranched polypyrrolone copolymer layer and polyquaternary ammonium salt modified graphene oxide from inside to outside.
The Chinese patent application No. 201410331454.7 discloses a surface modification preparation method of sheet metal powder, which mainly comprises the following steps: adding spherical metal powder, a metal chelating agent, a surface treating agent, solvent oil and a grinding medium into a ball mill, taking out slurry after ball milling, carrying out solid-liquid separation to obtain pasty metal powder, and drying and carrying out grading treatment on the obtained pasty metal powder to obtain the modified sheet metal powder coated with the metal chelating agent and the surface treating agent in a double-layer mode.
According to the above, in the conventional scheme, due to the limitations of the metal powder particle size, sphericity, oxygen content, fluidity, apparent density and other properties, the metal member manufactured by adopting the metal additive has poor properties, and has more defects compared with the metal member manufactured by casting. The 3D printing manufacturing technology of the metal material relates to various physical processes of solid-liquid phase change, surface diffusion, heat conduction and the like of metal, cracking is easy to occur due to the problem of uniformity, and the existing solution mainly controls the 3D laser forming process, such as the power and energy distribution of laser, the moving speed and path of a laser focusing point, the feeding speed, the protective air pressure, the external temperature and the like, but has the problems of complex control process and difficulty in control. In view of this, the invention provides an innovative method for modifying the interface of 3D printing metal powder, which can effectively solve the above technical problems.
Disclosure of Invention
Aiming at the problems of stress defect, easiness in cracking and the like of a widely-applied 3D printing metal powder material at present, the performance of a manufactured metal component is poor, the process for controlling 3D laser forming aiming at the problems is very complex, and the process is difficult to control, the invention provides the method for modifying the metal powder interface for 3D printing, so that the performance of the metal powder material is effectively improved, the process is simple, and the cost is low.
The invention relates to a specific technical scheme as follows:
a method for modifying a metal powder interface for 3D printing comprises the following steps:
(1) making metal into a bar, finely processing the bar into a plasma gun electrode bar capable of rotating at a high speed, starting a power supply by adopting a plasma rotating electrode powder making machine set, vacuumizing a furnace body, introducing argon, rotating the electrode bar at the high speed, carrying out arc striking on the argon twice by using a plasma gun, ionizing the argon, establishing an arc light extreme temperature as high as 3600 ℃ between a cathode and an anode, melting a stub of the anode bar, ejecting liquid drops under the action of centrifugal force, instantly cooling the liquid drops by forced convection of argon flow to solidify the liquid drops into powder, and falling and collecting the powder under the action of gravity to obtain nanoscale metal powder;
(2) preparing weak acid liquid from phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexamethylenetetramine, sodium lauryl sulfate and water, adding the metal powder obtained in the step (1), adding a titanium source, heating to 50-60 ℃ for reaction, dispersing the titanium source on the surface of the metal powder, pre-fixing, stopping the reaction after 1-1.5 hours, filtering, and cleaning with clear water; the adding amount of the metal powder is 5-8% of the mass of the weak acid liquid; the adding amount of the titanium source is 4-6% of the mass of the weak acid liquid;
(3) adding the powder obtained in the step (2) into dilute nitric acid, heating to 60-80 ℃ for reaction, stopping the reaction after 40-60 min, filtering, and washing with clear water to obtain metal powder coated with nano titanium dioxide; the adding amount of the powder is 3-5% of the mass of the dilute nitric acid liquid;
(4) and (3) welding the titanium dioxide-coated metal powder in the step (3) by adopting millisecond pulse laser, so that the nano titanium dioxide is firmly fixed on the surface of the metal powder in a nano crystal form, and the interface modification of the metal powder can be realized.
Preferably, the metal is one of titanium alloy, copper aluminum alloy, magnesium aluminum alloy or stainless steel.
Preferably, the titanium source is at least one of titanium tetrachloride, n-butyl titanate or isopropyl titanate.
Preferably, the weak acid liquid comprises, by mass, 100 parts of total components, 20-25 parts of phosphoric acid, 20-25 parts of ammonium hydrogen phosphate, 3-6 parts of hydrofluoric acid, 1-3 parts of hexamethylenetetramine, 0.1-0.3 part of sodium lauryl sulfate and 40-55 parts of water.
Preferably, the mass concentration of the dilute nitric acid solution is 10-15%.
Preferably, the plasma gun is a transferred arc type plasma gun, the power is 60-100 kW, the current is 1600-2200A, and the voltage is 40-70V.
Preferably, the rotating speed of the metal electrode bar is 10000-20000 r/min.
Preferably, the degree of vacuum is 3X 10-3~5×10-3Pa。
Preferably, the cooling speed of the metal liquid drops is 100-120 ℃/s.
Preferably, the particle size of the nanoscale metal powder is 5-10 nm;
preferably, the millisecond pulse laser is generated by a high-pulse-energy fiber laser, the pulse frequency is 8-12 Hz, the pulse width is 8-12 ms, the single-pulse energy is 12-18J, and the power density of the laser is 3 multiplied by 109~8×109W/m2。
The plasma rotating electrode method is one of the more ideal ways for preparing high-purity high-density spherical powder materials, and has remarkable advantages when being applied to the aspect of 3D printing material milling: the powder is solid, and the defects of air gaps, entrainment, precipitation air holes, cracks and the like caused by the hollow spheres can not exist in the printing process; the powder has small particle size, narrow particle size distribution, less spheroidization and agglomeration phenomena in the printing process, higher surface smoothness and fully guaranteed printing consistency and uniformity; the powder has high sphericity, good fluidity and high apparent density, and the printed product has higher density; the powder has good fluidity and good powder spreading uniformity; low oxygen content in powder, low surface activity, good wettability, less spheroidization and good melting effect. Therefore, the 3D printing metal powder is manufactured by adopting a plasma rotating electrode method in the invention.
The laser beams of the pulsed laser welding are focused to form a spot, which can heat, melt and solidify metal in milliseconds with little effect on the material and other parts of the part. Therefore, the invention adopts millisecond pulse laser welding to weld the titanium dioxide nanocrystalline on the metal powder, fully utilizes the excellent characteristic that millisecond pulse laser can effectively control the processing process in the processing of the nanostructure material, simultaneously exerts the good welding performance of laser welding in the small member heterogeneous material and ensures the stability of the obtained product.
Compared with the 3D printing metal powder prepared by the jet milling method, the hydrogenation dehydrogenation method and the laminar atomization method, the modified 3D printing metal powder prepared by the method has obvious advantages in powder performance (particle size, sphericity, oxygen content and fluidity) and product performance (printing precision and cracking resistance), as shown in Table 1.
Table 1:
the invention provides a method for modifying a metal powder interface for 3D printing, which has the outstanding characteristics and excellent effects compared with the prior art:
1. a method for modifying the surface of 3D printing metal powder by titanium dioxide nanocrystalline coating is provided.
2. Through the titanium dioxide nanocrystalline dispersed on the surface of the metal powder, the uniform growth of a metal metallographic phase is guided during 3D printing, the phenomena of product cracking and stress nonuniformity caused by rapid, sharp and nonuniform metallographic growth are overcome, and the precision and the strength of 3D printing are improved.
3. The problem that the nano titanium dioxide can not be firmly fixed on the surface of the metal powder in a nano crystal form is solved, and the defects of incomplete and unstable surface modification of the metal powder are overcome.
4. The preparation method disclosed by the invention is simple in process, convenient to control, low in preparation cost and suitable for large-scale popularization.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Making metal into a bar, finely processing the bar into a plasma gun electrode bar capable of rotating at a high speed, starting a power supply by adopting a plasma rotating electrode powder making machine set, vacuumizing a furnace body, introducing argon, rotating the electrode bar at the high speed, carrying out arc striking on the argon twice by using a plasma gun, ionizing the argon, establishing an arc light extreme temperature as high as 3600 ℃ between a cathode and an anode, melting a stub of the anode bar, ejecting liquid drops under the action of centrifugal force, instantly cooling the liquid drops by forced convection of argon flow to solidify the liquid drops into powder, and falling and collecting the powder under the action of gravity to obtain nanoscale metal powder; the metal is titanium alloy; the plasma gun is a transferred arc type plasma gun, the power is 80kW, the current is 2000A, and the voltage is 70V; the rotating speed of the metal electrode bar is 19000 r/min; vacuum degree of 5X 10-3Pa; the cooling speed of the metal liquid drop is 115 ℃/s; the particle size of the metal powder prepared by the rotary electrode is 8 nm;
(2) preparing weak acid liquor from phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexamethylenetetramine and sodium lauryl sulfate, adding the metal powder obtained in the step (1), adding a titanium source, heating to 60 ℃ for reaction, dispersing the titanium source on the surface of the metal powder and pre-fixing, stopping the reaction after 1.3h, filtering, and cleaning with clear water; the adding amount of the metal powder is 6% of the mass of the weak acid liquid; the titanium source is titanium tetrachloride; the adding amount of the titanium source is 5 percent of the mass of the weak acid liquid; the total mass parts of all components in the weak acid liquid are calculated by 100 parts, wherein 25 parts of phosphoric acid, 20 parts of ammonium hydrogen phosphate, 4.7 parts of hydrofluoric acid, 2 parts of hexamethylenetetramine, 0.3 part of sodium lauryl sulfate and 48 parts of water are used;
(3) adding the powder obtained in the step (2) into dilute nitric acid solution, heating to 70 ℃ for reaction, stopping the reaction after 60min, filtering, and washing with clear water to obtain metal powder coated with nano titanium dioxide; the adding amount of the powder is 4 percent of the mass of the dilute nitric acid liquid; the mass concentration of the dilute nitric acid solution is 12 percent;
(4) welding the titanium dioxide-coated metal powder in the step (3) by adopting millisecond pulse laser, so that the nano titanium dioxide is firmly fixed on the surface of the metal powder in a nano crystal form, and the interface modification of the metal powder can be realized; the millisecond pulse laser is generated by a high pulse energy fiber laser, the pulse frequency is 10Hz, the pulse width is 10ms, the single pulse energy is 15J, and the power density of the laser is 7 multiplied by 109W/m2。
The powder properties (particle size, sphericity, oxygen content, flowability) and article properties (printing accuracy, crack resistance) of the modified 3D-printed metal powder material prepared in example 1 are shown in table 2.
Example 2
(1) Making metal into a bar, finely processing the bar into a plasma gun electrode bar capable of rotating at a high speed, starting a power supply by adopting a plasma rotating electrode powder making machine set, vacuumizing a furnace body, introducing argon, rotating the electrode bar at the high speed, carrying out arc striking on the argon twice by using a plasma gun, ionizing the argon, establishing an arc light extreme temperature as high as 3600 ℃ between a cathode and an anode, melting a stub of the anode bar, ejecting liquid drops under the action of centrifugal force, instantly cooling the liquid drops by forced convection of argon flow to solidify the liquid drops into powder, and falling and collecting the powder under the action of gravity to obtain nanoscale metal powder; the metal is copper-aluminum alloy; the plasma gun is a transferred arc type plasma gun, the power is 60kW, the current is 2200A, and the voltage is 50V; the rotating speed of the metal electrode bar is 18000 r/min; vacuum degree of 3X 10-3Pa; the cooling speed of the metal liquid drops is 100 ℃/s; the particle size of the metal powder prepared by the rotary electrode is 7 nm;
(2) preparing weak acid liquor from phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexamethylenetetramine and sodium lauryl sulfate, adding the metal powder obtained in the step (1), adding a titanium source, heating to 53 ℃ for reaction, dispersing the titanium source on the surface of the metal powder and pre-fixing, stopping the reaction after 1h, filtering, and cleaning with clear water; the adding amount of the metal powder is 5 percent of the mass of the weak acid liquid; the titanium source is tetrabutyl titanate; the adding amount of the titanium source is 4 percent of the mass of the weak acid liquid; the total mass parts of the components in the weak acid liquid are calculated by 100 parts, wherein 23 parts of phosphoric acid, 24 parts of ammonium hydrogen phosphate, 3.8 parts of hydrofluoric acid, 3 parts of hexamethylenetetramine, 0.2 part of sodium lauryl sulfate and 46 parts of water are used;
(3) adding the powder obtained in the step (2) into dilute nitric acid solution, heating to 70 ℃ for reaction, stopping the reaction after 45min, filtering, and washing with clear water to obtain metal powder coated with nano titanium dioxide; the adding amount of the powder is 4.5 percent of the mass of the dilute nitric acid liquid; the mass concentration of the dilute nitric acid solution is 12 percent;
(4) welding the titanium dioxide-coated metal powder in the step (3) by adopting millisecond pulse laser, so that the nano titanium dioxide is firmly fixed on the surface of the metal powder in a nano crystal form, and the interface modification of the metal powder can be realized; the millisecond pulse laser is generated by a high pulse energy fiber laser, the pulse frequency is 9Hz, the pulse width is 11ms, the single pulse energy is 12J, and the power density of the laser is 8 multiplied by 109W/m2。
The powder properties (particle size, sphericity, oxygen content, flowability) and article properties (printing accuracy, crack resistance) of the modified 3D-printed metal powder material prepared in example 2 are shown in table 2.
Example 3
(1) Making metal into bar material, fine-processing into plasma gun electrode bar capable of rotating at high speed, adopting plasma rotating electrode powder-making machine set, starting power supply, vacuumizing furnace body, introducing argon gas, high-speed rotating electrode bar, using plasma gun to make twice arc striking on argon gas, argon gas ionization, establishing arc light extreme temperature up to 3600 deg.C between cathode and anode, melting anode bar stub, spraying liquid drop under the action of centrifugal force, instantly cooling liquid drop by forced convection of argon gas flow to solidify into powder, and under the action of gravity making it implement high-speed rotation of electrode barFalling down and collecting to obtain nano metal powder; the metal is magnesium-aluminum alloy; the plasma gun is a transferred arc type plasma gun, the power is 80kW, the current is 1900A, and the voltage is 50V; the rotating speed of the metal electrode bar is 17000 r/min; the degree of vacuum was 3.5X 10-3Pa; the cooling speed of the metal liquid drops is 105 ℃/s; the particle size of the metal powder prepared by the rotary electrode is 9 nm;
(2) preparing weak acid liquor from phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexamethylenetetramine and sodium lauryl sulfate, adding the metal powder obtained in the step (1), adding a titanium source, heating to 58 ℃ for reaction, dispersing the titanium source on the surface of the metal powder and pre-fixing, stopping the reaction after 1h, filtering, and cleaning with clear water; the adding amount of the metal powder is 5 percent of the mass of the weak acid liquid; the titanium source is isopropyl titanate; the adding amount of the titanium source is 6 percent of the mass of the weak acid liquid; the total mass parts of the components in the weak acid liquid are calculated by 100 parts, wherein 23 parts of phosphoric acid, 22 parts of ammonium hydrogen phosphate, 6 parts of hydrofluoric acid, 1.9 parts of hexamethylenetetramine, 0.1 part of sodium lauryl sulfate and 47 parts of water are used;
(3) adding the powder obtained in the step (2) into dilute nitric acid solution, heating to 70 ℃ for reaction, stopping the reaction after 45min, filtering, and washing with clear water to obtain metal powder coated with nano titanium dioxide; the adding amount of the powder is 5 percent of the mass of the dilute nitric acid liquid; the mass concentration of the dilute nitric acid solution is 14 percent;
(4) welding the titanium dioxide-coated metal powder in the step (3) by adopting millisecond pulse laser, so that the nano titanium dioxide is firmly fixed on the surface of the metal powder in a nano crystal form, and the interface modification of the metal powder can be realized; the millisecond pulse laser is generated by a high pulse energy fiber laser, the pulse frequency is 8Hz, the pulse width is 8ms, the single pulse energy is 14J, and the power density of the laser is 6 multiplied by 109W/m2。
The powder properties (particle size, sphericity, oxygen content, flowability) and article properties (printing accuracy, crack resistance) of the modified 3D-printed metal powder material prepared in example 3 are shown in table 2.
Example 4
(1) Making metal into bar material, and fine-machining it into high-speed rotary dieThe electrode bar of the plasma gun is rotated, a plasma rotating electrode powder making machine set is adopted, a power supply is started, argon is introduced after a furnace body is vacuumized, the electrode bar is rotated at a high speed, the plasma gun is used for carrying out arc striking on the argon twice, the argon is ionized, an arc light extreme temperature up to 3600 ℃ is established between a cathode and an anode, the stub of the anode bar is melted, liquid drops are ejected out under the action of centrifugal force, the liquid drops are instantly cooled by forced convection of argon flow to be solidified into powder, and the powder drops fall and are collected under the action of gravity, so that nanoscale metal powder is obtained; the metal is stainless steel; the plasma gun is a transferred arc type plasma gun, the power is 70kW, the current is 1800A, and the voltage is 50V; the rotating speed of the metal electrode bar is 16000 r/min; the degree of vacuum was 3.5X 10-3Pa; the cooling speed of the metal liquid drops is 110 ℃/s; the particle size of the metal powder prepared by the rotary electrode is 6 nm;
(2) preparing weak acid liquor from phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexamethylenetetramine and sodium lauryl sulfate, adding the metal powder obtained in the step (1), adding a titanium source, heating to 55 ℃ for reaction, dispersing the titanium source on the surface of the metal powder and pre-fixing, stopping the reaction after 1.5h, filtering, and cleaning with clear water; the adding amount of the metal powder is 7 percent of the mass of the weak acid liquid; the titanium source is titanium tetrachloride; the adding amount of the titanium source is 5 percent of the mass of the weak acid liquid; the total mass parts of all components in the weak acid liquid are calculated by 100 parts, wherein 25 parts of phosphoric acid, 24 parts of ammonium hydrogen phosphate, 4 parts of hydrofluoric acid, 2.8 parts of hexamethylenetetramine, 0.2 part of sodium lauryl sulfate and 44 parts of water are used;
(3) adding the powder obtained in the step (2) into dilute nitric acid solution, heating to 60 ℃ for reaction, stopping the reaction after 55min, filtering, and washing with clear water to obtain metal powder coated with nano titanium dioxide; the adding amount of the powder is 3.5 percent of the mass of the dilute nitric acid liquid; the mass concentration of the dilute nitric acid solution is 11 percent;
(4) welding the titanium dioxide-coated metal powder in the step (3) by adopting millisecond pulse laser, so that the nano titanium dioxide is firmly fixed on the surface of the metal powder in a nano crystal form, and the interface modification of the metal powder can be realized; the millisecond pulse laser is generated by a high-pulse-energy fiber laser, the pulse frequency is 9Hz, the pulse width is 10ms, and the single pulse energy13J, the power density of the laser is 5X 109W/m2。
The powder properties (particle size, sphericity, oxygen content, flowability) and article properties (printing accuracy, crack resistance) of the modified 3D-printed metal powder material prepared in example 4 are shown in table 2.
Example 5
(1) Making metal into a bar, finely processing the bar into a plasma gun electrode bar capable of rotating at a high speed, starting a power supply by adopting a plasma rotating electrode powder making machine set, vacuumizing a furnace body, introducing argon, rotating the electrode bar at the high speed, carrying out arc striking on the argon twice by using a plasma gun, ionizing the argon, establishing an arc light extreme temperature as high as 3600 ℃ between a cathode and an anode, melting a stub of the anode bar, ejecting liquid drops under the action of centrifugal force, instantly cooling the liquid drops by forced convection of argon flow to solidify the liquid drops into powder, and falling and collecting the powder under the action of gravity to obtain nanoscale metal powder; the metal is titanium alloy; the plasma gun is a transferred arc type plasma gun, the power is 90kW, the current is 1800A, and the voltage is 70V; the rotating speed of the metal electrode bar is 19000 r/min; vacuum degree of 5X 10-3Pa; the cooling speed of the metal liquid drops is 120 ℃/s; the particle size of the metal powder prepared by the rotary electrode is 10 nm;
(2) preparing weak acid liquor from phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexamethylenetetramine and sodium lauryl sulfate, adding the metal powder obtained in the step (1), adding a titanium source, heating to 60 ℃ for reaction, dispersing the titanium source on the surface of the metal powder and pre-fixing, stopping the reaction after 1.2h, filtering, and cleaning with clear water; the adding amount of the metal powder is 7 percent of the mass of the weak acid liquid; the titanium source is tetrabutyl titanate; the adding amount of the titanium source is 5 percent of the mass of the weak acid liquid; the total mass parts of all components in the weak acid liquid are calculated by 100 parts, wherein 25 parts of phosphoric acid, 22 parts of ammonium hydrogen phosphate, 5.7 parts of hydrofluoric acid, 2 parts of hexamethylenetetramine, 0.3 part of sodium lauryl sulfate and 45 parts of water are used;
(3) adding the powder obtained in the step (2) into dilute nitric acid solution, heating to 60 ℃ for reaction, stopping the reaction after 60min, filtering, and washing with clear water to obtain metal powder coated with nano titanium dioxide; the adding amount of the powder is 5 percent of the mass of the dilute nitric acid liquid; the mass concentration of the dilute nitric acid solution is 15 percent;
(4) welding the titanium dioxide-coated metal powder in the step (3) by adopting millisecond pulse laser, so that the nano titanium dioxide is firmly fixed on the surface of the metal powder in a nano crystal form, and the interface modification of the metal powder can be realized; the millisecond pulse laser is generated by a high pulse energy fiber laser, the pulse frequency is 12Hz, the pulse width is 12ms, the single pulse energy is 18J, and the power density of the laser is 8 multiplied by 109W/m2。
The powder properties (particle size, sphericity, oxygen content, flowability) and article properties (printing accuracy, crack resistance) of the modified 3D-printed metal powder material prepared in example 5 are shown in table 2.
Example 6
(1) Making metal into a bar, finely processing the bar into a plasma gun electrode bar capable of rotating at a high speed, starting a power supply by adopting a plasma rotating electrode powder making machine set, vacuumizing a furnace body, introducing argon, rotating the electrode bar at the high speed, carrying out arc striking on the argon twice by using a plasma gun, ionizing the argon, establishing an arc light extreme temperature as high as 3600 ℃ between a cathode and an anode, melting a stub of the anode bar, ejecting liquid drops under the action of centrifugal force, instantly cooling the liquid drops by forced convection of argon flow to solidify the liquid drops into powder, and falling and collecting the powder under the action of gravity to obtain nanoscale metal powder; the metal is copper-aluminum alloy; (ii) a The plasma gun is a transferred arc type plasma gun, the power is 80kW, the current is 1800A, and the voltage is 50V; the rotating speed of the metal electrode bar is 16000 r/min; vacuum degree of 4X 10-3Pa; the cooling speed of the metal liquid drops is 110 ℃/s; the particle size of the metal powder prepared by the rotary electrode is 9 nm;
(2) preparing weak acid liquor from phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexamethylenetetramine and sodium lauryl sulfate, adding the metal powder obtained in the step (1), adding a titanium source, heating to 60 ℃ for reaction, dispersing the titanium source on the surface of the metal powder and pre-fixing, stopping the reaction after 1.4h, filtering, and cleaning with clear water; the adding amount of the metal powder is 7 percent of the mass of the weak acid liquid; the titanium source is isopropyl titanate; the adding amount of the titanium source is 4 percent of the mass of the weak acid liquid; the weak acid liquid comprises, by mass, 100 parts of total components, 21 parts of phosphoric acid, 22 parts of ammonium hydrogen phosphate, 3.9 parts of hydrofluoric acid, 1 part of hexamethylenetetramine, 0.1 part of sodium lauryl sulfate and 52 parts of water;
(3) adding the powder obtained in the step (2) into dilute nitric acid solution, heating to 70 ℃ for reaction, stopping the reaction after 50min, filtering, and washing with clear water to obtain metal powder coated with nano titanium dioxide; the adding amount of the powder is 3 percent of the mass of the dilute nitric acid liquid; the mass concentration of the dilute nitric acid solution is 10 percent;
(4) welding the titanium dioxide-coated metal powder in the step (3) by adopting millisecond pulse laser, so that the nano titanium dioxide is firmly fixed on the surface of the metal powder in a nano crystal form, and the interface modification of the metal powder can be realized; the millisecond pulse laser is generated by a high pulse energy fiber laser, the pulse frequency is 11Hz, the pulse width is 10ms, the single pulse energy is 15J, and the power density of the laser is 7 multiplied by 109W/m2。
The powder properties (particle size, sphericity, oxygen content, flowability) and article properties (printing accuracy, crack resistance) of the modified 3D-printed metal powder material prepared in example 6 are shown in table 2.
Comparative example 1
(1) Making metal into a bar, finely processing the bar into a plasma gun electrode bar capable of rotating at a high speed, starting a power supply by adopting a plasma rotating electrode powder making machine set, vacuumizing a furnace body, introducing argon, rotating the electrode bar at the high speed, carrying out arc striking on the argon twice by using a plasma gun, ionizing the argon, establishing an arc light extreme temperature as high as 3600 ℃ between a cathode and an anode, melting a stub of the anode bar, ejecting liquid drops under the action of centrifugal force, instantly cooling the liquid drops by forced convection of argon flow to solidify the liquid drops into powder, and falling and collecting the powder under the action of gravity to obtain nanoscale metal powder; the metal is copper-aluminum alloy; (ii) a The plasma gun is a transferred arc type plasma gun, the power is 80kW, the current is 1800A, and the voltage is 50V; the rotating speed of the metal electrode bar is 16000 r/min; vacuum degree of 4X 10-3Pa; the cooling speed of the metal liquid drops is 110 ℃/s; particle size of metal powder produced by rotating electrodeIs 9 nm;
(2) preparing weak acid liquor from phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexamethylenetetramine and sodium lauryl sulfate, adding the metal powder obtained in the step (1), adding a titanium source, heating to 60 ℃ for reaction, dispersing the titanium source on the surface of the metal powder and pre-fixing, stopping the reaction after 1.4h, filtering, and cleaning with clear water; the adding amount of the metal powder is 7 percent of the mass of the weak acid liquid; the titanium source is isopropyl titanate; the adding amount of the titanium source is 4 percent of the mass of the weak acid liquid; the weak acid liquid comprises, by mass, 100 parts of total components, 21 parts of phosphoric acid, 22 parts of ammonium hydrogen phosphate, 3.9 parts of hydrofluoric acid, 1 part of hexamethylenetetramine, 0.1 part of sodium lauryl sulfate and 52 parts of water;
(3) adding the powder obtained in the step (2) into dilute nitric acid solution, heating to 70 ℃ for reaction, stopping the reaction after 50min, filtering, and washing with clear water to obtain metal powder coated with nano titanium dioxide; the adding amount of the powder is 3 percent of the mass of the dilute nitric acid liquid; the mass concentration of the dilute nitric acid solution is 10 percent;
the powder properties (particle size, sphericity, oxygen content, flowability) and article properties (printing accuracy, crack resistance) of the modified 3D-printed metal powder material prepared in comparative example 1 are shown in table 2.
Comparative example 2
(1) Making metal into a bar, finely processing the bar into a plasma gun electrode bar capable of rotating at a high speed, starting a power supply by adopting a plasma rotating electrode powder making machine set, vacuumizing a furnace body, introducing argon, rotating the electrode bar at the high speed, carrying out arc striking on the argon twice by using a plasma gun, ionizing the argon, establishing an arc light extreme temperature as high as 3600 ℃ between a cathode and an anode, melting a stub of the anode bar, ejecting liquid drops under the action of centrifugal force, instantly cooling the liquid drops by forced convection of argon flow to solidify the liquid drops into powder, and falling and collecting the powder under the action of gravity to obtain nanoscale metal powder; the metal is copper-aluminum alloy; (ii) a The plasma gun is a transferred arc type plasma gun, the power is 80kW, the current is 1800A, and the voltage is 50V; the rotating speed of the metal electrode bar is 16000 r/min; vacuum degree of 4X 10-3Pa; the cooling speed of the metal liquid drops is 110 ℃/s; the metal powder prepared by the rotary electrode has the particle size of 9nm；
(2) Preparing weak acid liquor from phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexamethylenetetramine and sodium lauryl sulfate, adding the metal powder obtained in the step (1), adding titanium dioxide, heating to 60 ℃ for reaction, dispersing the titanium dioxide on the surface of the metal powder and pre-fixing, stopping the reaction after 1.4h, filtering, and cleaning with clear water; the adding amount of the metal powder is 7 percent of the mass of the weak acid liquid; the weak acid liquid comprises, by mass, 100 parts of total components, 21 parts of phosphoric acid, 22 parts of ammonium hydrogen phosphate, 3.9 parts of hydrofluoric acid, 1 part of hexamethylenetetramine, 0.1 part of sodium lauryl sulfate and 52 parts of water;
(3) adding the powder obtained in the step (2) into dilute nitric acid solution, heating to 70 ℃ for reaction, stopping the reaction after 50min, filtering, and cleaning with clear water to obtain titanium dioxide coated metal powder; the adding amount of the powder is 3 percent of the mass of the dilute nitric acid liquid; the mass concentration of the dilute nitric acid solution is 10 percent;
(4) welding the titanium dioxide-coated metal powder in the step (3) by adopting millisecond pulse laser, so that the titanium dioxide is firmly fixed on the surface of the metal powder in a nanocrystalline form, and the interface modification of the metal powder can be realized; the millisecond pulse laser is generated by a high pulse energy fiber laser, the pulse frequency is 11Hz, the pulse width is 10ms, the single pulse energy is 15J, and the power density of the laser is 7 multiplied by 109W/m2。
The powder properties (particle size, sphericity, oxygen content, flowability) and article properties (printing accuracy, crack resistance) of the modified 3D-printed metal powder material prepared in comparative example 2 are shown in table 2.
Table 2:
Claims (9)
1. a method for modifying a metal powder interface for 3D printing is characterized in that the process of modifying the metal powder interface is as follows:
(1) making metal into a bar, finely processing the bar into a plasma gun electrode bar capable of rotating at a high speed, starting a power supply by adopting a plasma rotating electrode powder making machine set, vacuumizing a furnace body, introducing argon, rotating the electrode bar at the high speed, carrying out arc striking on the argon twice by using a plasma gun, ionizing the argon, establishing an arc light extreme temperature as high as 3600 ℃ between a cathode and an anode, melting a stub of the anode bar, ejecting liquid drops under the action of centrifugal force, instantly cooling the liquid drops by forced convection of argon flow to solidify the liquid drops into powder, and falling and collecting the powder under the action of gravity to obtain nanoscale metal powder;
(2) preparing weak acid liquid from phosphoric acid, ammonium hydrogen phosphate, hydrofluoric acid, hexamethylenetetramine, sodium lauryl sulfate and water, adding the metal powder obtained in the step (1), adding a titanium source, heating to 50-60 ℃ for reaction, dispersing the titanium source on the surface of the metal powder, pre-fixing, stopping the reaction after 1-1.5 hours, filtering, and cleaning with clear water; the adding amount of the metal powder is 5-8% of the mass of the weak acid liquid; the adding amount of the titanium source is 4-6% of the mass of the weak acid liquid; the weak acid liquid comprises, by mass, 100 parts of total components, 20-25 parts of phosphoric acid, 20-25 parts of ammonium hydrogen phosphate, 3-6 parts of hydrofluoric acid, 1-3 parts of hexamethylenetetramine, 0.1-0.3 part of sodium lauryl sulfate and 40-55 parts of water;
(3) adding the powder obtained in the step (2) into dilute nitric acid, heating to 60-80 ℃ for reaction, stopping the reaction after 40-60 min, filtering, and washing with clear water to obtain metal powder coated with nano titanium dioxide; the adding amount of the powder is 3-5% of the mass of the dilute nitric acid liquid;
(4) and (3) welding the titanium dioxide-coated metal powder in the step (3) by adopting millisecond pulse laser, so that the nano titanium dioxide is firmly fixed on the surface of the metal powder in a nano crystal form, and the interface modification of the metal powder can be realized.
2. The method of claim 1, wherein the metal powder interface modification method for 3D printing is as follows: the metal is one of titanium alloy, copper aluminum alloy, magnesium aluminum alloy or stainless steel.
3. The method of claim 1, wherein the metal powder interface modification method for 3D printing is as follows: the plasma gun is a transferred arc type plasma gun, the power is 60-100 kW, the current is 1600-2200A, and the voltage is 40-70V.
4. The method of claim 1, wherein the metal powder interface modification method for 3D printing is as follows: the rotating speed of the metal electrode bar is 10000-20000 r/min.
5. The method of claim 1, wherein the metal powder interface modification method for 3D printing is as follows: the vacuum degree of the furnace body after vacuum pumping is 3 multiplied by 10-3~5×10-3Pa。
6. The method of claim 1, wherein the metal powder interface modification method for 3D printing is as follows: the cooling speed of the metal liquid drops is 100-120 ℃/s; the particle size of the nanoscale metal powder is 5-10 nm.
7. The method of claim 1, wherein the metal powder interface modification method for 3D printing is as follows: the titanium source is at least one of titanium tetrachloride, n-butyl titanate or isopropyl titanate.
8. The method of claim 1, wherein the metal powder interface modification method for 3D printing is as follows: the mass concentration of the dilute nitric acid solution is 10-15%.
9. The method of claim 1, wherein the metal powder interface modification method for 3D printing is as follows: the millisecond pulse laser is generated by a high pulse energy fiber laser, the pulse frequency is 8-12 Hz, the pulse width is 8-12 ms, the single pulse energy is 12-18J, and the power density of the laser is 3 multiplied by 109~8×109W/m2。
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| CN109014228A (en) * | 2018-10-09 | 2018-12-18 | 陕西科技大学 | A method of copper alloy powder is prepared based on plasma rotating electrode |
| CN109513944A (en) * | 2018-10-24 | 2019-03-26 | 中国人民解放军陆军装甲兵学院 | The method that plasma rotating electrode prepares copper alloy powder |
| CN112893764B (en) * | 2021-01-21 | 2022-04-12 | 大连理工大学 | 3D printing coated silica sand for optical fiber laser processing and preparation method thereof |
| CN113245544B (en) * | 2021-06-08 | 2021-10-01 | 西安欧中材料科技有限公司 | Device and method for preparing metal-ceramic coated powder |
| CN115090873A (en) * | 2022-07-07 | 2022-09-23 | 西北有色金属研究院 | Method for preparing titanium-based composite material from modified titanium or titanium alloy powder |
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