WO2018084056A1 - Metal powder, powder-sintered additively manufactured object, and manufacturing method for same - Google Patents
Metal powder, powder-sintered additively manufactured object, and manufacturing method for same Download PDFInfo
- Publication number
- WO2018084056A1 WO2018084056A1 PCT/JP2017/038623 JP2017038623W WO2018084056A1 WO 2018084056 A1 WO2018084056 A1 WO 2018084056A1 JP 2017038623 W JP2017038623 W JP 2017038623W WO 2018084056 A1 WO2018084056 A1 WO 2018084056A1
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- WO
- WIPO (PCT)
- Prior art keywords
- metal
- metal powder
- powder
- thin layer
- flux
- Prior art date
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- 239000000843 powder Substances 0.000 title claims abstract description 257
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 228
- 239000002184 metal Substances 0.000 title claims abstract description 225
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 82
- 239000002923 metal particle Substances 0.000 claims abstract description 164
- 230000004907 flux Effects 0.000 claims abstract description 93
- 239000002245 particle Substances 0.000 claims abstract description 87
- 238000005245 sintering Methods 0.000 claims abstract description 35
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 16
- 230000001678 irradiating effect Effects 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 19
- 239000007769 metal material Substances 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 238000009826 distribution Methods 0.000 claims description 12
- 229910021538 borax Inorganic materials 0.000 claims description 11
- 239000004328 sodium tetraborate Substances 0.000 claims description 11
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
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- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 229910000838 Al alloy Inorganic materials 0.000 claims description 6
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- 229910000881 Cu alloy Inorganic materials 0.000 claims description 6
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
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- 238000006722 reduction reaction Methods 0.000 claims description 6
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 11
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- 229910052718 tin Inorganic materials 0.000 description 1
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Images
Classifications
-
- 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
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- 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
-
- 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
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- 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
- B22F3/12—Both compacting and sintering
- B22F3/16—Both compacting and sintering in successive or repeated steps
-
- 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
-
- 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
- B33Y80/00—Products made by additive manufacturing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Definitions
- the present invention relates to a metal powder and a method for producing a powder sintered laminate model, and more specifically, a metal powder having a metal particle surface coated with a flux, a powder sintered laminate model using the metal powder, and the same. It relates to a manufacturing method.
- the three-dimensional model manufactured in this way (also referred to as “three-dimensional modeled model”, “three-dimensional modeled model”, or “3D modeled model”) manufactures a prototype for confirming the shape and properties of the final product. It is used in such fields.
- a material for producing a three-dimensional structure is also selected as appropriate according to the type of final product, the property desired to be confirmed by a prototype, and the like. For example, when the final product is a metal machine part or the like, a metal material (metal particles) may be used as a prototype material.
- metal bed fusion bonding method (hereinafter referred to as “powder fusion bonding method”, “powder sintering lamination method”) using particles composed of metal. Or “metal powder sintered additive manufacturing method”).
- the metal powder sintering additive manufacturing method for manufacturing a three-dimensional additive manufacturing object from this metal material is a process of forming a thin layer of powder and irradiating laser light to a shape corresponding to the cross-sectional shape of the object to be formed. This is a method of forming a layered object by sequentially combining a material and a step of forming a cross-sectional object.
- a metal material containing metal particles is laid flat to form a thin layer, and a target region to be shaped on the thin layer is irradiated with a laser beam,
- modeled object layer one layer of a thin layer (hereinafter also simply referred to as “modeled object layer”) obtained by finely dividing the three-dimensional modeled object in the thickness direction is formed.
- a powder material is further spread on the thin layer thus formed, and laser irradiation is performed to selectively sinter or melt bond the particles, thereby forming the next shaped article layer.
- the laser irradiation time of the metal powder is very short. Therefore, when the energy of the laser is not sufficiently transmitted to the metal powder, the powder is bonded in a state where the metal powder cannot have wettability, and the laminated surface is not flattened and uneven portions are formed. If the uneven portion is formed on the laminated surface, it becomes an obstacle to the formation of the powder thin layer of the next layer, resulting in a problem that the surface accuracy is lowered.
- Patent Document 1 discloses a method for forming a three-dimensional layered object (hereinafter, also referred to as “powder sintered layered object” or “metal powder sintered layered object”) by irradiating a metal powder with laser light.
- a metal powder containing Cr, Ni, Cu or the like as a metal that contains Fe as a main component and further constitutes an alloy is disclosed, and it is described that a molded article excellent in hardness, thermal conductivity, and corrosivity can be obtained. ing.
- Patent Document 2 discloses a laser sintering powder having a plurality of metal particles and a binder that binds the metal particles, and the binder is decomposed and vaporized by irradiation with laser light. ing.
- metal oxide has a high melting point and low thermal conductivity, so in the metal powder sintering lamination method that forms a three-dimensional object by laser irradiation, a thin oxidation is performed on the particle surface in a high temperature environment such as laser irradiation. A film is easily formed.
- a metal oxide has a high melting point and a low thermal conductivity, and therefore becomes a factor that hinders rapid heat transfer during laser sintering.
- the metal particles cannot be melted and reach a temperature region where the surface tension becomes small, and the particles themselves cannot spread. If the powder containing metal particles cannot be sufficiently wetted and spread, it will solidify while maintaining the particle shape, resulting in a concavo-convex structure on the surface of the thin layer formed by the metal particles. On top of that, there arise problems that it becomes difficult to lay the next thin layer flatly and that the planar accuracy of the surface is lowered. Since these problems become more conspicuous when laser irradiation is performed at a high speed, it is a major obstacle to increasing the speed of additive manufacturing.
- Patent Document 3 discloses a method of performing a sintering treatment in a high temperature environment of 1100 to 1400 ° C. in a vacuum atmosphere, and is formed on the surface of stainless steel powder.
- the flux is applied to the particle surface to remove the oxide film formed on the particle surface and prevent oxidation, thereby enabling high-density sintering of the stainless steel powder. A method is disclosed.
- Patent Document 3 is a method in which the metal particles filled in the sintering mold are sintered under a high temperature environment of 1100 to 1400 ° C. in a vacuum atmosphere.
- a metal that forms a layered object under atmospheric pressure by irradiating a thin layer corresponding to the cross-sectional shape of the object to be formed with laser light, bonding the metal material, and repeating the process of forming this cross-sectional object This is completely different from the powder sintering lamination method, and Patent Document 3 makes no mention of the above method.
- the present invention has been made in view of the above-described problems and situations, and the problem to be solved is to achieve a high-speed formation of a laminate and to form a three-dimensional layered object having excellent shape accuracy and flatness. It is to provide a metal powder that can be manufactured, a powder sintered laminate model using the metal powder, and a method for manufacturing the same.
- the present inventor is a metal powder used in the metal powder sintering additive manufacturing method, and the number average particle diameter is within a specific range.
- the metal powder is characterized in that the surface of the coating is coated with a flux with a thickness within a specific range. The inventors have found that a metal powder capable of forming an object can be realized, and have reached the present invention.
- Metal powder used in the metal powder sintering additive manufacturing method A metal powder characterized in that the surface of a metal particle having a number average particle diameter in the range of 5 to 100 ⁇ m is coated with a flux having an average thickness in the range of 5 to 30 nm.
- the coefficient of variation (CV value) in the particle size distribution of the metal particles is 15% or less.
- metal particles contain a metal material selected from iron, iron alloy, nickel, nickel alloy, cobalt, cobalt alloy, copper, copper alloy, aluminum and aluminum alloy. Metal powder as described in any one of these.
- the energy density E represented by the following formula (1) of the laser beam to be irradiated Item 7.
- the cross-sectional shape forming step of irradiating the metal powder with a laser beam in a shape pattern corresponding to the cross-sectional shape of the object to be shaped includes a first laser light irradiation step of accelerating a reduction reaction on the surface of the metal powder with a flux, and the metal 8.
- a metal powder capable of achieving a high-speed formation of a laminate and forming a three-dimensional laminate model having excellent shape accuracy and flatness, and a powder sintering laminate model using the metal powder A method for manufacturing a product can be provided.
- the thin layer is irradiated with laser light in a desired pattern, and the metal powder is sintered or melt-bonded with the laser light to form a modeled object layer
- the outermost surface of the metal particles constituting the metal powder becomes an interface with the environmental atmosphere and is thinly oxidized. A film will be formed. Since such a metal oxide film generally has a high melting point and low thermal conductivity, it impedes rapid heat transfer during sintering by laser light irradiation.
- the surface tension of molten metal decreases with increasing temperature, but if the thermal energy due to laser light irradiation is not transmitted quickly, the surface tension of molten metal decreases as a result of melting. Since the temperature range to be reached cannot be reached, the property of spreading and spreading becomes insufficient. As a result, since the metal powder cannot sufficiently wet and spread when forming a thin layer, it will solidify while maintaining the particle shape, and an uneven pattern is formed on the surface of the thin layer. When laminating thin layers, it becomes impossible to spread a second thin layer that is uniform and highly smooth. Eventually, the surface accuracy of the three-dimensional layered object to be formed is lowered, and a three-dimensional layered object with a desired formation cannot be obtained. This problem has become a major obstacle in speeding up the formation of a three-dimensional layered object because the laser irradiation is more likely to be manifested more remarkably.
- the present inventors have determined that the average thickness of the metal powder having a number average particle diameter in the range of 5 to 100 ⁇ m as the metal powder applied to the formation of the three-dimensional layered object is By applying a metal powder with a flux coating within a range of 5 to 30 nm, when the metal powder is irradiated with laser light, the oxide forming the metal particle surface is reduced to reduce the flux, etc. Can be removed. As a result, obstruction factors such as a decrease in heat conduction due to the metal oxide are removed, and the energy of the laser beam can be transmitted to the metal particles in a short time.
- the metal powder can be stably spread in a short time, and the surface of the thin layer is flat. Therefore, the three-dimensional layered object can be stably formed at high speed and with high accuracy without hindering the formation of the next thin layer formed thereon.
- the main action of the flux according to the present invention described above on the metal particles is to remove the metal oxide formed on the surface of the metal particles.
- reaction product metal salt
- Schematic sectional view showing an example of the configuration of the metal powder of the present invention Schematic diagram showing an example of a conventional method for forming a three-dimensional layered object
- Schematic diagram showing an example of a method for forming a three-dimensional layered object and its characteristics in the present invention Schematic which shows an example of the whole structure of the formation apparatus of the three-dimensional laminate modeling thing applicable to this invention
- the block diagram which shows an example of the control method in the formation apparatus of the three-dimensional laminate modeling thing applicable to this invention
- the metal powder of the present invention is a metal powder used in the metal powder sintering additive manufacturing method, and has an average thickness of 5 to 30 nm on the surface of metal particles having a number average particle diameter in the range of 5 to 100 ⁇ m. It is characterized by being coated with a flux within the range. This feature is a technical feature common to or corresponding to the claimed invention.
- spherical metal particles having an average circularity in the range of 0.90 to 0.98 can be applied as the metal particles from the viewpoint of more manifesting the intended effect of the present invention. It is preferable in that a thin layer excellent in surface uniformity can be formed under conditions close to close-packing, and a three-dimensional layered object having better shape accuracy and flatness can be formed.
- the coefficient of variation (CV value) in the particle size distribution of the metal particles is 15% or less, so that a thin layer that is one unit of the laminate It is preferable in that it can suppress unevenness when formed and can form a thin layer with excellent smoothness.
- the applied flux is at least one inorganic flux selected from boric acid, borate, borax, fluoride and chloride, and the oxide on the metal particle surface is efficiently removed by laser irradiation. It is preferable from the viewpoint that laser energy can be transmitted to the metal particles in a short time.
- the metal particles to be applied are metal particles containing a metal material selected from iron, iron alloy, nickel, nickel alloy, cobalt, cobalt alloy, copper, copper alloy, aluminum, and aluminum alloy. It is preferable in that it has conductivity, is excellent in suitability for sintering, and can stably form a sintered metal powder layer.
- the method for producing a powder sintered laminate model of the present invention is a method of manufacturing a three-dimensional model using the metal powder of the present invention, and at least a thin layer forming step of developing the metal powder into a thin layer,
- the metal powder constituting the thin layer has a cross-sectional shape forming step of irradiating a laser beam with a shape pattern corresponding to the cross-sectional shape of the object to be modeled to combine the metal powder, and the thin layer forming step and the A three-dimensional layered object is manufactured by sequentially repeating the cross-sectional shape forming step.
- the metal powder sintered body can be efficiently formed by setting the energy density E of the laser light applied to the metal powder within the range of 45 to 150 J / mm 2. This is preferable.
- the laser irradiation method is divided into a first laser light irradiation step that promotes a reduction reaction on the surface of the metal powder by a flux and a second laser light irradiation step that combines the metal powder. Irradiation is preferable in that a three-dimensional layered object having a finer surface property can be obtained.
- the metal powder of the present invention is characterized in that the surface of metal particles having a number average particle diameter in the range of 5 to 100 ⁇ m is coated with a flux having an average thickness in the range of 5 to 30 nm.
- FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a metal powder in which the surface of metal particles according to the present invention is coated with a flux.
- the core part is composed of metal particles (2) having a number average particle diameter d, and the surface of the metal particle (2) has a thickness as a shell part.
- This is a configuration in which a flux (3) of length h is coated.
- the flux (3) may be configured to cover the entire surface of the metal particles (2), or may be a discontinuous configuration having an uncoated portion in part.
- the configuration is preferable from the viewpoint that the objective effect of the present invention can be sufficiently exhibited.
- the average thickness of the flux is the thickness when assuming that the particle surface is uniformly coated with the total volume of the discontinuous flux. And define.
- the metal particles (2) according to the present invention are composed mainly of a metal that is a material of a three-dimensional structure to be shaped, and have a number average particle diameter in the range of 5 to 100 ⁇ m.
- metal material which comprises a metal particle (2) For example, aluminum, chromium, cobalt, copper, gold, iron, magnesium, silicon, molybdenum, nickel, palladium, platinum, rhodium, silver, tin, Titanium, tungsten, zinc, and the like, and alloys containing these metal elements are included.
- the metal elements it is particularly preferable to include at least one metal material selected from iron, iron alloy, nickel, nickel alloy, cobalt, cobalt alloy, copper, copper alloy, aluminum, and aluminum alloy.
- the metal particles (2) are preferably composed of one kind of material from the viewpoint that the composition of the finally obtained three-dimensional structure can be easily made uniform, but the metal powder (1) can be configured. As long as it does, you may use in combination of 2 or more types of materials.
- the ratio of the metal element as the main component is preferably 75% by mass or more, more preferably 85% by mass or more, further preferably 95% by mass or more, particularly Preferably, the metal particles are composed only of metal elements.
- the metal material contained as a main component is the largest amount among the metal materials specified by a known method such as fluorescent X-ray analysis. Further, the metal particles (2) and the flux (3) are separated from the metal powder by a known method such as ultrasonic treatment in an aqueous solution containing a surfactant, and the resulting metal particles (2) are obtained. On the other hand, a metal material contained as a main component in the metal particles (2) may be specified by performing fluorescent X-ray analysis or ICP emission spectroscopic analysis.
- the number average particle diameter of the metal particles (2) is in the range of 5 to 100 ⁇ m, preferably in the range of 10 to 80 ⁇ m, more preferably in the range of 20 to 60 ⁇ m. Particularly preferably in the range of 30 to 50 ⁇ m.
- the number average particle diameter of the metal particles (2) is less than 5 ⁇ m, the fluidity of the metal particles is insufficient, the molding speed is slow, and the metal powder is spread more uniformly when the metal powder is formed. Since it becomes difficult to form a thin layer, the formation accuracy of the three-dimensional structure is lowered, and furthermore, it becomes difficult to irradiate a large amount of laser light to the metal particles, and the melting and sintering efficiency of the metal particles is lowered. It becomes difficult to make the modeling speed faster. Furthermore, when the thickness is less than 5 ⁇ m, the difficulty of producing metal particles increases, and the production cost of the metal powder to be formed increases.
- the uneven pattern is excessively emphasized, and it becomes difficult to produce a high-definition three-dimensional object.
- the number average particle diameter of the metal particles (2) is the average value of the particle diameters of 50 metal particles (2) arbitrarily selected in the cross-sectional view of the metal powder (1) imaged with a transmission electron microscope (TEM). can do. At this time, each particle diameter is expressed as a diameter when the projected area of each particle is converted into a circle, and an arithmetic average value of particle diameters measured for 50 metal particles is obtained. The number average particle size.
- the metal powder (1) is dispersed in an aqueous solution containing a surfactant by using a known dispersing device such as ultrasonic treatment, and the flux (3 ), And the obtained metal particles (2) were measured with a laser diffraction / scattering particle size distribution measuring apparatus (for example, Partica LA-960 manufactured by Horiba, Ltd.).
- a laser diffraction / scattering particle size distribution measuring apparatus for example, Partica LA-960 manufactured by Horiba, Ltd.
- the number average particle diameter may be calculated assuming that the particles are spherical.
- the average circularity is preferably in the range of 0.90 to 0.98.
- the circularity referred to in the present invention is an image obtained by imaging the circumference of a circle having an area equal to the particle area of a metal particle projected two-dimensionally, as shown by the following equation, with a transmission electron microscope (TEM).
- the average circularity is represented by an arithmetic average value of the measured values obtained by measuring the circularity according to the above method for 50 metal particles.
- Circularity (perimeter of circle equal to projected area of metal particle) / (perimeter of metal particle)
- the coefficient of variation (CV value) in the particle size distribution is preferably 15% or less.
- the lower limit is not particularly limited, but is practically 0.1% or more, and more practically 1.0% or more.
- the metal powder containing the metal particles can be more uniformly spread when the thin layer is formed, and the accuracy of the three-dimensional layered object to be manufactured can be further increased. .
- the CV value of the metal particles is preferably 10% or less from the viewpoint of further increasing the modeling speed and further improving the formation accuracy of the three-dimensional layered object to be manufactured, and is 8% or less. More preferably.
- the CV value here is determined from the particle diameter (average value of major axis and minor axis) of arbitrarily selected 50 metal particles in a cross-sectional photograph of the metal powder imaged with a transmission electron microscope (TEM).
- the standard deviation ⁇ and the average particle diameter D are calculated as ( ⁇ / D) ⁇ 100.
- the standard deviation ⁇ and the average particle diameter D of the metal particles are determined according to a known method such as ultrasonic treatment in an aqueous solution containing a surfactant.
- a laser diffraction / scattering particle size distribution measuring device for example, Partica LA-960, manufactured by Horiba, Ltd.
- a value calculated assuming a spherical shape may be used.
- the CV value is a value indicating how wide the particle size distribution is, and the smaller the CV value, the narrower the particle size distribution.
- the metal particles according to the present invention can be produced by known atomization methods including, for example, a gas atomization method, a water atomization method, a plasma atomization method, and a centrifugal atomization method.
- atomization methods including, for example, JP 2001-181703 A, JP 2007-113107 A, JP 2010-090421 A, JP 2010-144197 A, JP 2015-059253 A, and the like.
- the metal particles can be produced by appropriately selecting and applying the methods described in JP-A-2015-096646.
- the metal powder of the present invention is characterized in that the surface of the metal particles described above is coated with a flux having an average thickness in the range of 5 to 30 nm.
- the oxide film formed on the surface of the metal particles is removed (also referred to as cleaning action) by the flux reducing action, etc., and the anti-oxidation function at the time of laser irradiation is expressed.
- the effect of reducing the surface tension of the metal particles is expressed, and the obstruction factors such as the decrease in heat conduction due to the metal oxide are removed, and the energy of the laser beam can be transmitted to the metal particles in a short time.
- a high-quality three-dimensional laminated structure can be formed.
- the average thickness of the flux on the surface of the metal particles is characterized by being in the range of 5 to 30 nm, but is preferably in the range of 10 to 20 nm.
- the average thickness of the flux is less than 5 nm, it becomes difficult to exhibit the effect of removing the oxide film on the surface of the metal particles and the effect of preventing reoxidation. On the other hand, if it exceeds 30 nm, the flux remains excessively on the particle surface, which is not preferable from the viewpoint of post-treatment and the like.
- the average thickness of the flux according to the present invention can be obtained by the following method.
- the center part of the metal powder was cut using a focused ion beam processing apparatus (manufactured by Hitachi High-Tech Science Co., Ltd., SMI2050) to produce particle flakes.
- a transmission electron microscope manufactured by JEOL Ltd., JEM-2010F
- the thickness of the coated flux was measured at 10 locations on the center line cross-sectional image of the particles imaged at a magnification of 10,000 times. An average value of 1 was determined.
- this measurement was performed on 50 metal powders, the total average of the obtained average values 1 was determined, and this was determined as the average thickness of the flux, which was defined as the average thickness of the flux.
- the flux applicable to the present invention is not particularly limited as long as it is a material that exhibits a cleaning action on an oxide film or the like formed on the surface of metal particles and a reoxidation preventing function during laser irradiation, Each flux shown below can be appropriately selected and applied.
- the flux according to the present invention can be broadly classified into 1) resin flux, 2) water-soluble organic flux, 3) inorganic flux, and the like.
- Resin-based flux examples include rosin (pine resin) and its modified resin or synthetic resin.
- Rosin which is a natural resin, is composed mainly of organic acids such as abietic acid, parastrinic acid, dehydroabietic acid, neoabietic acid, isopimaric acid, and pimaric acid. Further, natural rosin has a low softening point (70 to 80 ° C.) and is brittle, so rosin derivatives are used.
- hydrogenated rosin (trade name: Hyper CH manufactured by Arakawa Chemical Co., Ltd.), polymerized rosin ( Arakawa Chemical Co., Ltd. (trade name: Aradim R-140, softening point: 140 ° C.), acid-modified rosin (Arakawa Chemical Co., Ltd., trade name: Marquide No. 33, softening point: 150 ° C.), ultra light rosin (Arakawa Chemical Co. Trade name: Vine Crystal KR-85, softening point: 85 ° C.).
- Resin flux can be applied to the surface of metal particles and then melted to form a coating, or after adding an activator or other additive, it can be dissolved in a solvent such as alcohol or glycol ethers. Then, a known wet coating method such as a spray coating method or a rolling fluidized bed (multiplex) can be applied to apply a method for forming a flux film as the shell portion. There are no restrictions.
- Water-soluble organic flux examples include organic acids, organic amines / hydrohalides, and organic acids / amine salts. Organic acids are preferred. Furthermore, from the viewpoint of excellent cleaning action of the oxide film etc. on the metal particle surface and re-oxidation preventing function, it should contain monocarboxylic acid or polycarboxylic acid such as dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid, etc. Is preferred. In the present invention, it is preferable that a polyvalent carboxylic acid is contained from the viewpoint of enhancing the active action on the surface of the metal particles.
- dicarboxylic acid examples include oxalic acid, glutaric acid, adipic acid, succinic acid, sebacic acid, malonic acid, maleic acid, fumaric acid, phthalic acid, pimelic acid, suberic acid, azelaic acid, citraconic acid, ⁇ -ketoglutaric acid , Diglycolic acid, thiodiglycolic acid, dithiodiglycolic acid, 4-cyclohexene-1,2-dicarboxylic acid and the like.
- Examples of the tricarboxylic acid include trimellitic acid, citric acid, isocitric acid, cyclohexane-1 1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid and the like, and examples of the tetracarboxylic acid include ethylenetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid and the like. Can be mentioned.
- inorganic flux examples include inorganic acids, borides, and halides.
- a boride is a general term for an electrolyte (compound) between boron and an element having a lower electronegativity.
- boric acid H 3 BO 3
- borax Na 2 B 4 O 7
- boron oxide B 2 OB
- potassium borate K 2 B 4 O 7
- borate there are orthoborate, diborate, metaborate, tetraborate, pentaborate and octaborate, and as salts thereof, lithium, sodium, potassium And borate salts of metals such as magnesium, calcium, barium, chromium, iron, cobalt, nickel, manganese, silicon, lead, copper, titanium and aluminum.
- metals such as magnesium, calcium, barium, chromium, iron, cobalt, nickel, manganese, silicon, lead, copper, titanium and aluminum.
- fluorides such as potassium fluoride (KF), sodium fluoride (NaF), acidic sodium fluoride (NaHF 2 ), Potassium borofluoride (KBF 4 ), sodium borofluor
- chloride examples include potassium chloride (KCl), zinc chloride (ZnCl), and ammonium chloride (NH 4 Cl).
- bromide examples include hydrobromic acid (HBr) and potassium bromide (KBr), and examples of iodide include ammonium iodide (NH 4 I).
- an inorganic flux is preferably used as the flux, and at least one selected from boric acid, borate, borax, fluoride, and chloride is preferable.
- inorganic flux it can be applied to the surface of the metal particles as it is and then melted to form a film, or after adding an activator or other additive, it is added to a solvent such as alcohol or glycol ethers. After dissolution, a known wet coating method such as spray coating or rolling fluidized bed (multiplex) can be applied, and a method of forming a flux film as a shell part can be applied. There are no particular restrictions.
- the metal powder is produced by coating the surface of the metal particles with a thin layer of flux having a thickness in the range of 5 to 30 nm.
- the metal powder can be manufactured by 1) a step of preparing metal particles and a flux to be coated, and 2) a step of fixing the flux to the surface of the metal particles.
- Step of preparing metal particles and flux metal particles having a number average particle diameter in the range of 5 to 100 ⁇ m and a flux are prepared.
- the metal particles preferably have an average circularity in the range of 0.90 to 0.98 or a variation coefficient (CV value) in the particle size distribution of 15% or less.
- the metal particles preferably include at least one metal material selected from iron, iron alloy, nickel, nickel alloy, cobalt, cobalt alloy, copper, copper alloy, aluminum, and aluminum alloy.
- the flux is preferably at least one selected from boric acid, boride, fluoride and chloride.
- metal particles and flux may be purchased, or may be produced by a known method such as an atomizing method. Moreover, you may use what classified the particle
- the ratio of the flux with respect to the metal particles is not particularly limited, and the amount of flux to be prepared with respect to the metal particles is set so that the thickness specified above is in the range of 5 to 30 nm.
- the metal particles and the low thermal conductive particles may be purchased commercially or may be produced by a known method such as an atomizing method. Moreover, you may use what classified the particle
- Step of coating flux on metal particle surface This step is a step of fixing flux on the surface of metal particles.
- a known method used for fixing other particles to the surface of the metal particles can be selected as appropriate.
- a wet coating method using a coating solution in which a flux is dissolved with a solvent for example, a spray coating method, a rolling fluidized bed method, etc.
- a dry coating method in which metal particles and a flux are stirred and bonded by mechanical impact Or it can carry out by the combination of these methods.
- a coating solution containing a flux may be spray-coated on the surface of the metal particles, or the metal particles may be immersed in the coating solution.
- the metal particles and the flux are stirred and mixed uniformly with a normal mixing and stirring device, and the resulting mixture is stirred and mixed for about 5 to 40 minutes with a normal rotary blade type mixing and stirring device. It can be a method.
- the metal powder may further include a laser light absorber.
- the laser light absorber may be a material that absorbs laser light having a wavelength to be used and generates heat. Examples of such laser light absorbers include carbon powder, nylon resin powder, pigments and dyes. These laser light absorbers may be used alone or in combination of two kinds.
- the amount of the laser light absorber can be appropriately set within a range in which the metal powder can be easily melted and bonded. Can be set.
- the metal powder may contain a flow aid.
- the flow aid is a material having a small coefficient of friction and a self-lubricating property, and examples of such flow aid include silicon dioxide and boron nitride. These flow aids may be used alone or in combination of two or more. Even if the fluidity of the metal powder is increased by the flow aid, the metal powder is difficult to be charged, and the metal powder can be filled more densely when forming a thin layer.
- the amount of the flow aid can be appropriately set within the range in which the fluidity of the metal powder is further improved and the melt bonding of the metal powder is sufficiently generated. It can be more than 1% by mass and less than 2.0% by mass.
- the method for producing a powder sintered laminate model of the present invention is a method for producing a powder sintered model by using the metal powder of the present invention described above, and specifically, at least, A thin layer forming step of developing the metal powder into a thin layer, and irradiating the metal powder constituting the thin layer with a laser beam in a shape pattern corresponding to a cross-sectional shape of the object to be modeled to combine the metal powder
- the method for producing a powder sintered laminate model of the present invention includes a thin layer forming step 1 in which a metal powder containing metal particles is developed into a thin layer, and a shape corresponding to the cross-sectional shape of the modeling target in the formed thin layer. And a step of forming a cross-sectional shape in which the metal powder is bonded by sequentially irradiating with laser light.
- FIG. 2A and FIG. 2B are production flow diagrams for explaining the features of the conventional method and the method for producing a powder sintered laminate model using metal powder in the present invention.
- FIG. 2A is a diagram illustrating an example of a conventional method for forming a three-dimensional layered object.
- first thin layer forming step that is the first step (a)
- the formed first thin layer (5B) is irradiated with laser light (L) to sinter the metal powder.
- a shaped article layer (5C) is formed from the sintered metal powder (1C).
- the metal powder (1B) is irradiated with laser light (L) under an atmospheric pressure environment, the outermost surface of the metal particles (2) constituting the metal powder (1B) comes into contact with the atmosphere. Therefore, a thin metal oxide film (4) is formed on the particle surface.
- the metal oxide film (4) Since the metal oxide film (4) has a higher melting point than the metal particles (2) and has a low thermal conductivity, heat cannot be transferred quickly during sintering by irradiation with the laser beam (L).
- the surface tension of the molten metal has a characteristic that it decreases as the temperature rises. However, if the thermal energy due to the irradiation with the laser beam (L) is not rapidly transmitted, the surface tension of the molten metal as a metal particle (2) is reduced by melting. Since it is not possible to reach the temperature range in which the deteriorating characteristic is expressed, the characteristic of spreading and spreading becomes insufficient.
- the metal powder aggregates particles to form a secondary particle lump, so that a concavo-convex pattern is formed on the surface of the thin layer, and the shaped object layer (5C) having poor planarity Become.
- the second thin layer is formed by the metal powder (1B) on the shaped article layer (5C) having a concavo-convex structure on the surface. Since the same uneven pattern is also reflected on the surface of the layer (8B), the surface accuracy of the three-dimensional layered object to be finally formed is lowered, and the three-dimensional layered object having a desired formation is formed. You can't get things.
- the formation of these concavo-convex patterns has become a problem in speeding up the formation of a three-dimensional layered object, since it becomes more prominent when the laser beam (L) is irradiated at high speed.
- FIG. 2B shows a method for forming a three-dimensional layered object to which the metal powder of the present invention is applied.
- the average circularity is 0.90 to 0.98 using the powder recoater (7) on the modeling stage (6).
- spherical metal particles (2) within a range and having a coefficient of variation (CV value) of 15% or less, and metal powder (1) covering the surface with flux (3), A first thin layer (5) excellent in surface uniformity is formed under conditions close to close packing.
- the thickness of one thin layer is preferably in the range of 0.01 to 0.3 mm, and more precise. In order to obtain a shaped article, it is preferably within a range of 0.01 to 0.1 mm.
- the method of developing the thin layer there is no particular limitation on the method of developing the thin layer, but for example, there is a method of spraying a metal powder sintered material from above. There is also a method in which the supplied metal powder sintered material is leveled with a roller to form a thin layer with a uniform thickness.
- the method of leveling with a roller can be preferably used because a thin layer with a uniform thickness and a low porosity can be formed with good reproducibility.
- the first thin layer (5) formed is irradiated with laser light (L) to sinter the metal powder (1).
- a model layer (5A) is formed from the sintered metal powder (1A).
- the metal powder (1) containing the metal particles (2) can quickly reach the temperature range where the surface tension is lowered, and the metal powder (1) can be stably spread in a short time. There is not, and a modeling thing layer (5A) excellent in surface smoothness can be formed.
- the second thin layer (8A) is formed by the metal powder (1) on the model layer (5A) excellent in flatness even in the second thin layer forming step which is the third step (c). Even when formed, since the excellent planarity of the modeled object layer (5A) as the lower layer is reflected, it is possible to finally form a three-dimensional layered modeled object at high speed and with high accuracy.
- the thickness of the thin layer to be formed is the same as the thickness of one layer of the model layer constituting the three-dimensional laminate model.
- the thickness of the thin layer can be arbitrarily set according to the shape of the three-dimensional layered object to be manufactured, but it is usually preferably in the range of 0.01 to 0.30 mm, and more precise. In order to obtain a simple shaped article, it is preferably in the range of 0.05 to 0.10 mm.
- the thickness of the thin layer 0.01 mm or more, it is possible to prevent the metal particles of the lower thin layer from being sintered or melt-bonded again by laser light irradiation for forming the next thin layer. it can.
- the laser light is conducted to the lower part of the thin layer, and the metal particles included in the metal powder constituting the thin layer are spread over the entire thickness direction. It can be fully sintered or melt bonded.
- the thickness of the thin layer is more preferably in the range of 0.02 to 0.30 mm, further preferably in the range of 0.03 to 0.20 mm, and 0.05 to 0. It is particularly preferable that it is within the range of 10 mm.
- the thickness of the thin layer is determined by the laser beam spot described later. It is preferable to set so that the difference from the diameter is within 0.10 mm.
- the wavelength of the laser beam may be set within a range in which the metal material contained as a main component in the metal particles can efficiently absorb the laser beam.
- the energy density E represented by the following formula (1) of the laser beam to be irradiated is preferably within a range of 45 to 150 J / mm 2 .
- the power at the time of laser beam output may be set within a range where the metal particles constituting the metal powder are sufficiently sintered or melt bonded at the scanning speed of the laser beam. Specifically, it is preferably in the range of 5.0 to 1000 W. Regardless of the type of metal material, the metal powder can easily sinter or melt bond the metal particles even with low-energy laser light, and can produce a three-dimensional layered object. From the viewpoint of reducing the energy of the laser beam, reducing the manufacturing cost, and simplifying the configuration of the manufacturing apparatus, the power at the time of laser beam output is more preferably 500 W or less, and 300 W or less. More preferably.
- the scanning speed of the laser beam may be set within a range that does not increase the manufacturing cost and does not excessively complicate the apparatus configuration. Specifically, it is preferably set within the range of 5 to 10000 mm / sec, more preferably within the range of 100 to 8000 mm / sec, and even more preferably within the range of 2000 to 7000 mm / sec.
- the beam diameter of the laser beam can be appropriately set according to the shape of the three-dimensional layered object to be manufactured.
- the laser beam applicable to the production of the powder-sintered layered product of the present invention is not particularly limited, and examples thereof include a carbon dioxide laser, a YAG laser, an excimer laser, a He—Cd laser, a semiconductor excitation solid laser, and a fiber laser. Is mentioned.
- These lasers can be used alone or in combination of two or more.
- each step shown in FIG. 2B at least from the viewpoint of preventing the strength of the three-dimensional layered object from being reduced due to oxidation or nitridation of the metal material contained as a main component in the metal particles during sintering or fusion bonding.
- the two steps are preferably performed under reduced pressure or in an inert gas atmosphere.
- the pressure when the pressure is reduced is preferably 1 ⁇ 10 ⁇ 2 Pa or less, and more preferably 1 ⁇ 10 ⁇ 3 Pa or less.
- the inert gas applicable to the present invention include nitrogen gas and rare gas.
- nitrogen (N 2 ) gas, helium (He) gas, or argon (Ar) gas is preferable from the viewpoint of availability. From the viewpoint of simplifying the manufacturing process, it is preferable to perform all the steps shown in FIG. 2B under reduced pressure or in an inert gas atmosphere. In a special case, the laser beam can be irradiated in the atmosphere.
- the temperature at the time of irradiation is not particularly limited, and can be performed under cooling, at room temperature or under heating. Formation of a thin layer of metal powder sintered material and sintering by laser light irradiation are sequentially repeated as many times as necessary, and then a desired shaped object can be obtained by separating unsintered microspheres.
- FIG. 3 is a schematic diagram showing an overall configuration of an example of a three-dimensional layered object forming apparatus applicable to the present invention.
- a three-dimensional layered object forming apparatus 400 includes a modeling stage (6) located in an opening, and a thin layer (5) of metal powder (1) containing metal particles coated with flux. ) On the modeling stage (6), and a temperature adjusting unit (430) for heating or cooling the surface of the thin layer (5) formed on the modeling stage (6) or the inside of the apparatus.
- a stage support part (450) for supporting the modeling stage (6) and a support base (490) for supporting the above parts are provided.
- the stage support section (450) supports the modeling stage (6) variably in the vertical position. That is, the modeling stage (6) is configured to be precisely movable in the vertical direction by the stage support portion (450).
- Various configurations can be adopted as the stage support portion (450).
- a holding member that holds the modeling stage (6), a guide member that guides the holding member (6) in the vertical direction, and a guide member It can be configured by a ball screw or the like that engages with the provided screw hole.
- the thin layer (5) is formed by the thin layer forming part (420), the temperature is adjusted by the temperature adjusting part (430), and the laser light irradiation part (440) is irradiated with the laser light (L).
- a three-dimensional layered object (3DM) is formed by forming a three-dimensional object layer (5A) and laminating this three-dimensional object layer (5A).
- the thin layer forming part (420) includes, for example, an edge part of the opening on which the modeling stage (6) moves up and down, an opening having the edge part substantially on the same plane in the horizontal direction, and a metal extending vertically downward from the opening.
- the metal powder supply unit (421) includes a metal powder storage unit and a nozzle provided vertically above the modeling stage (6), and on the same plane in the horizontal direction as the modeling stage. It is good also as a structure which discharges metal powder.
- a temperature adjustment part (430) heats the area
- the temperature adjustment unit (430) may include a first temperature adjustment device (431) that can heat or cool the surface of the thin layer (5) formed on the modeling stage (6). It is good also as a structure further provided with the 2nd temperature control apparatus (432) which heats the metal powder (1) before being supplied on the modeling stage (6).
- region which should form the said molded article layer (5A) may be sufficient as the temperature adjustment part (430), or the whole inside of an apparatus is heated beforehand, and the said formation
- the structure which adjusts the temperature of the surface of the made thin layer (5) to predetermined temperature may be sufficient.
- Any temperature measuring device may be used as long as it can measure the surface temperature of the region where the shaped article layer (5A) is to be formed in a non-contact manner.
- an infrared sensor or an optical pyrometer can be applied. it can.
- the laser beam irradiation unit (440) mainly includes a laser light source (441) and a galvanometer mirror (442).
- the laser beam irradiator (440) further includes a laser beam window (443) that transmits the laser beam (L) and a lens for adjusting the focal length of the laser beam (L) to the surface of the thin layer (5). (Shown) may be provided.
- the laser light source (441) may be a light source that emits laser light (L) having a desired wavelength, for example, in the range of 45 to 150 J / mm 2 as the energy density E. Examples of the laser light source (441) include a carbon dioxide gas laser, a YAG laser, an excimer laser, a He—Cd laser, a semiconductor excitation solid laser, and a fiber laser as described above.
- the galvanometer mirror (442) includes an X mirror that reflects the laser light (L) emitted from the laser light source (441) and scans the laser light (L) in the X direction and a Y mirror that scans in the Y direction. Also good.
- the laser beam window (443) may be made of a material that transmits the laser beam (L).
- FIG. 4 is a block diagram showing an example of a control method in the three-dimensional layered object forming apparatus applicable to the present invention.
- the control system of the three-dimensional layered object forming apparatus (400) is mainly used.
- control unit (460) for controlling the lowering speed of the stage support unit (450) to repeatedly form the modeled object layer (5A) to control the formation of the three-dimensional layered object (3DM), various information
- a display unit (470) for displaying an image, an operation unit (475) including a pointing device for receiving an instruction from a user, and various types of information including a control program executed by the control unit (460) are stored. You may provide the data input part (485) containing the interface etc. for transmitting / receiving various information, such as modeling data of a three-dimensional laminate modeling thing (3DM), between a memory
- the formation apparatus (400) of a three-dimensional laminate modeling thing measures the temperature of the area
- a temperature measuring device (not shown) may be provided.
- a computer apparatus (500) for creating data for three-dimensional modeling may be connected to the three-dimensional modeled object forming apparatus (400).
- the control unit (460) includes a hardware processor such as a central processing unit, and controls the operation of the entire three-dimensional modeling apparatus (400) during the modeling operation of the three-dimensional layered object (3DM).
- control unit (460) converts, for example, the three-dimensional modeling data acquired from the computer device (500) by the data input unit (485) into a plurality of slice data sliced in the stacking direction of the modeling object layer (5A). It may be configured to do.
- Slice data is modeling data of each modeling object layer (5A) for modeling a three-dimensional laminate modeling object (3DM).
- the thickness of the slice data that is, the thickness of the modeled object layer (5A) matches the distance (lamination pitch) corresponding to the thickness of one layer of the modeled object layer (5A).
- the display unit (470) can be composed of, for example, a liquid crystal display, an organic electroluminescence display, or the like.
- the operation unit (475) can include, for example, a pointing device such as a keyboard and a mouse, and may include various operation keys such as a numeric keypad, an execution key, and a start key.
- the storage unit (480) may include various storage media such as a ROM, a RAM, a magnetic disk, an HDD, and an SSD.
- the three-dimensional layered object formation apparatus (400) receives the control of the control unit (460), and depressurizes the inside of the apparatus, such as a decompression unit (not shown) such as a decompression pump, or controls the control unit (460).
- a decompression unit such as a decompression pump
- An inert gas supply unit (not shown) that receives and supplies the inert gas into the apparatus may be provided.
- the control unit (460) converts the three-dimensional modeling data acquired from the computer device (500) by the data input unit (485) into a plurality of slice data sliced in the stacking direction of the modeled object layer (5A). Then, a control part (460) controls the following operation
- the metal powder supply unit (421) drives the motor and the drive mechanism (both not shown) according to the supply information output from the control unit (460), and moves the lifting lift (451) vertically upward (arrow in the figure).
- the metal powder (1) is extruded on the same horizontal plane as the modeling stage (6).
- the drive unit of the powder recoater (7) draws the powder recoater (7) from the position 1 (P1) in the horizontal direction (arrow direction in the figure) according to the thin layer formation information output from the control unit (460).
- the metal powder (1) is transported to the thin film forming part (420), and the thickness of the thin layer (5) is one layer of the shaped article layer (5A). Spread metal powder (1) to a thickness of 1 minute.
- the temperature adjustment unit (430) heats the surface of the thin layer (5) formed in accordance with the temperature information output from the control unit (460) or the entire apparatus.
- the temperature information is extracted from the storage unit (480) by the control unit (460) based on, for example, data on the temperature (Tmc) at which the material constituting the metal particles is input from the data input unit (485). It can be information for heating the surface of the thin layer (5) to a temperature at which the difference from the above temperature is in the range of 5 to 50 ° C.
- the temperature adjustment unit (430) may start heating after the thin layer (5) is formed, or the surface of the thin layer (5) to be formed before the thin layer (5) is formed. Heating may be performed at a location corresponding to or in the apparatus.
- the laser beam irradiation unit (440) is arranged on the thin layer (5) according to the laser beam irradiation information output from the control unit (460) in a region constituting the three-dimensional layered object (3DM) in each slice data.
- laser light (L) is emitted from the laser light source (441), and the galvano mirror is driven by the galvano mirror driving unit (442) to scan the laser light (L).
- the metal particles contained in the metal powder are melt-bonded by the irradiation of the laser beam (L), and the shaped article layer (5A) is formed.
- a cross-sectional shape forming step of irradiating the metal powder with a laser beam in a shape pattern corresponding to the cross-sectional shape of the object to be shaped a first laser light irradiation that promotes a reduction reaction on the surface of the metal powder with a flux, and a metal A method of performing second laser light irradiation for bonding powder is more preferable.
- the laser light irradiation conditions in the first laser light irradiation step are preferably in the range of 50 to 100 W as output, and the laser light irradiation in the second laser light irradiation step
- the irradiation conditions are preferably in the range of 100 to 400W.
- stage support unit (450) drives the motor and the drive mechanism (both not shown) according to the position control information output from the control unit (460), and moves the modeling stage (6) in the vertical direction by the stacking pitch. Move downward (arrow direction in the figure).
- the display unit (470) displays various information and messages to be recognized by the user under the control of the control unit (460) as necessary.
- the operation unit (475) receives various input operations by the user and outputs an operation signal corresponding to the input operation to the control unit (460). For example, a virtual three-dimensional object to be formed is displayed on the display unit (470) to check whether a desired shape is formed. If the desired shape is not formed, the operation unit (475) is used. Modifications may be made.
- the control unit (460) stores data in the storage unit (480) or extracts data from the storage unit (480) as necessary.
- a control part (460) receives the information of the temperature of the area
- model object layer (5A) is stacked, and a three-dimensional model object (3DM) is manufactured.
- Metal powders 1 to 30 were produced according to the following method.
- metal powders 2 to 8 In the production of the metal powder 1, copper particles (manufactured by Hikari Material Kogyo Co., Ltd., trade name: copper powder, number average particle diameter: 40 ⁇ m, CV value: 10%, circularity: 0.93) are described in Table I, respectively. Metal powders 2 to 8 were produced in the same manner except that the metal particles were changed to the above metal particles.
- the metal particles sold by Hikari Material Industry Co., Ltd., Adachi Shin Sangyo Co., Ltd., Kanto Chemical Co., Ltd., and Core Front Co., Ltd. are appropriately selected, and a plurality of metal particles are used. Classification operation using a seed membrane filter was performed, and the number average particle size and the CV value described in Table I were adjusted.
- metal powders 9 to 17 In the production of the metal powder 1, copper particles (manufactured by Hikari Material Kogyo Co., Ltd., trade name: copper powder, number average particle diameter: 40 ⁇ m, CV value: 10%, circularity: 0.93) are described in Table I, respectively. Metal powders 9 to 17 were produced in the same manner except that the number average particle diameter, CV value, and circularity of the copper particles were changed to copper particles.
- Each copper particle was selected from copper particles sold by Hikari Material Industry Co., Ltd., Kanto Chemical Co., Ltd., and Core Front Co., Ltd.
- metal powders 19 to 21 In the production of the metal powder 1, the metal powder was similarly obtained except that borax (Na 2 B 4 O 7 ) was changed to boric acid, potassium fluoride (KF), and zinc chloride (ZnCl), respectively. 19 to 21 were produced.
- borax Na 2 B 4 O 7
- KF potassium fluoride
- ZnCl zinc chloride
- metal powders 23 to 26 In the production of the metal powder 1, a flux with respect to copper particles that are metal particles (trade name: copper powder, number average particle diameter: 40 ⁇ m, CV value: 10%, circularity: 0.93, manufactured by Hikari Kogyo Kogyo Co., Ltd.)
- the metal powders 23 to 26 were produced in the same manner except that the mixing ratio of borax was changed to change the average thickness of the flux coating layer to 2 nm, 5 nm, 30 nm, and 45 nm, respectively.
- the number average particle diameter of the metal particles used for the production of the metal powder is an average of the particle diameters of 50 metal particles selected by photographing a projected image of the metal particles using a transmission electron microscope (TEM). Obtained as a value.
- the particle diameter of each metal particle is represented by the diameter when the projected area of each particle is converted into a circle, and the arithmetic average value of the particle diameters measured for each of the 50 metal particles is obtained.
- the number average particle diameter of 2) was used.
- ⁇ CV value coefficient of variation>
- the CV value of each metal particle was determined by measurement using a laser diffraction / scattering particle size distribution measuring device (Horiba, Ltd., Partica LA-960).
- the circularity of the metal particles used for the production of the metal powder is obtained by taking a projected image of the metal particles using a transmission electron microscope (TEM), and according to the following formula, the particle area of the metal particles projected in two dimensions
- the circumference of a circle with the same area was expressed by a numerical value obtained by dividing the circumference of the imaged metal particles, and the circularity of 50 metal particles was measured according to the above method. Subsequently, it calculated
- Circularity (perimeter of circle equal to projected area of metal particle) / (perimeter of metal particle) (Measurement of average thickness of flux)
- the center part of the produced metal powder was cut using a focused ion beam processing apparatus (manufactured by Hitachi High-Tech Science Co., Ltd., SMI2050) to produce particle flakes.
- a transmission electron microscope manufactured by JEOL Ltd., JEM-2010F
- the thickness of the coated flux was measured at 10 locations on the center line cross-sectional image of the particles imaged at a magnification of 10,000 times. An average value of 1 was determined. Subsequently, this measurement was performed for 50 metal powders, and the total average of the obtained average values 1 was determined, and this was determined as the average thickness of the flux.
- the metal powder supply part (421) was filled with the produced metal powder 1 (1), the lifting lift (451) was raised, and the metal powder (1) was pushed upward.
- the powder recoater (7) the metal powder is horizontally spread on the modeling stage (6) on the modeling stage (6) at the thin layer forming part (420) while controlling the thickness.
- a thin layer (5) was formed.
- the laser beam irradiation unit (440) includes a fiber laser (wavelength: 1.07 ⁇ m, 100% output: 300 W, energy density: 120 J / mm 2 ) as a laser light source (441), and a 3D galvano scan head (manufactured by ARGES). ), Composed of a single focus lens (f100), under the condition that the focal spot on the surface of the thin layer (5) of the metal powder is 30 ⁇ m, the scanning speed is 2000 mm / sec, the scanning pitch is 40 ⁇ m, and laser beam irradiation is 2 By dividing into stages, an area of 10 mm ⁇ 10 mm was irradiated and sintered to form a structure layer (5A). In the first irradiation step, the output of the laser light source was performed at 100 W, and then as the second irradiation step, the output condition was changed to 300 W.
- a fiber laser wavelength: 1.07 ⁇ m, 100% output: 300 W, energy density: 120 J / mm 2
- a second thin layer having a thickness of 0.2 mm is laminated on the formed first structural layer (5A) in the same manner as described above, and the sintering treatment by laser irradiation is repeated 50 times in total.
- a layered object 1 having a thickness of 10 mm was produced.
- the layered object 27 is formed in the same manner except that the laser beam irradiation to the thin layer formed of the metal powder 1 is changed to the single irradiation of the second step (output: 300 W). Produced.
- A The outermost surface of the layered object is extremely smooth due to only the irregularities due to the particle size of the metal particles.
- ⁇ The outermost surface of the layered object is smooth only due to the irregularities due to the particle size of the metal particles.
- ⁇ Slight irregularities due to aggregation of metal particles during sintering are observed, but acceptable in practical use.
- X Clear irregularities due to aggregation of metal particles during sintering have occurred.
- each sample for evaluation prepared above was observed using a digital microscope VHX-5000 manufactured by Keyence Corporation, and a defect larger than the size of the metal particles used for the production of each layered object (sintering by laser light) Is not sufficient, the structure is not formed, and the void portion is confirmed to be generated), the scanning speed of the laser beam that does not generate defects is obtained, and the modeling speed is determined according to the following criteria .
- the present invention is such that the surface of metal particles having a number average particle diameter in the range of 5 to 100 ⁇ m is coated with a flux having an average thickness in the range of 5 to 30 nm. It can be seen that the three-dimensional layered object formed using this metal powder has excellent surface roughness and forming accuracy and has a high forming speed as compared with the comparative example.
- metal particles constituting the metal powder metal particles having an average circularity in the range of 0.90 to 0.98 are applied, and the coefficient of variation (CV value) in the particle size distribution is 15% or less.
- As the flux at least one selected from boric acid, borax, rosin, fluoride and chloride is applied, or as a method for producing a powder sintered laminate model, the energy density E is 45 as laser light to be applied.
- the present invention can be divided into a first laser light irradiation step for promoting the reduction reaction on the surface of the metal powder by flux and a second laser light irradiation step for bonding the metal powder. It can be seen that this is preferable in that the objective effect can be exhibited more.
- the metal powder of the present invention can achieve a high-speed formation of a laminate and can form a three-dimensional layered product excellent in shape accuracy and flatness, and manufacture a large variety of final products and prototypes. In the field to do, a three-dimensional laminate modeling thing can be manufactured in a shorter time.
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Abstract
The present invention addresses the problem of providing a metal powder with which it is possible to speed up the formation of layered bodies and form additively manufactured objects with excellent shape accuracy and flatness, and providing a powder-sintered additively manufactured object using the same and a manufacturing method for the same. This metal powder is used in a powder-sintering additive manufacturing method comprising steps of selectively irradiating a thin layer of a plurality of metal powders with laser light to sinter or melt bond the metal powders, thereby forming a shaped layer, and layering shaped layers to form a three-dimensional additively manufactured object. The metal power is characterized in that a flux having an average thickness of 5-30 nm is coated on the surface of metal particles having a number average particle diameter of 5-100 µm.
Description
本発明は、金属粉末及び粉末焼結積層造形物の製造方法に関するものであり、更に詳しくは、金属粒子表面にフラックスが被覆されている金属粉末と、それを用いる粉末焼結積層造形物及びその製造方法に関するものである。
The present invention relates to a metal powder and a method for producing a powder sintered laminate model, and more specifically, a metal powder having a metal particle surface coated with a flux, a powder sintered laminate model using the metal powder, and the same. It relates to a manufacturing method.
近年、複雑な形状の立体造形物を比較的容易に製造できる様々な方法が開発されている。こうして製造された立体造形物(「三次元形状造形物」、「立体積層造形物」、又は「3D造形物」ともいう。)は、最終製品の形状や性質を確認するための試作品の製造などの分野に用いられている。このような用途においては、最終製品の種類や、試作品で確認したい性質等に応じて、立体造形物を製造するための材料も適宜選択される。たとえば、最終製品が金属製の機械部品などの場合には、試作品の材料として、金属材料(金属粒子)が用いられることがある。
In recent years, various methods have been developed that can manufacture a three-dimensional object having a complicated shape relatively easily. The three-dimensional model manufactured in this way (also referred to as “three-dimensional modeled model”, “three-dimensional modeled model”, or “3D modeled model”) manufactures a prototype for confirming the shape and properties of the final product. It is used in such fields. In such an application, a material for producing a three-dimensional structure is also selected as appropriate according to the type of final product, the property desired to be confirmed by a prototype, and the like. For example, when the final product is a metal machine part or the like, a metal material (metal particles) may be used as a prototype material.
これらの金属材料(金属粒子)からの立体造形物の製造は、金属で構成される粒子を用いた「粉末床溶融結合法」(以下、「粉末溶融結合法」、「粉末焼結積層法」、又は「金属粉末焼結積層造形法」ともいう。)によって行うことができる。
The manufacture of three-dimensional objects from these metal materials (metal particles) is performed by “powder bed fusion bonding method” (hereinafter referred to as “powder fusion bonding method”, “powder sintering lamination method”) using particles composed of metal. Or “metal powder sintered additive manufacturing method”).
この金属材料からの立体積層造形物を製造する金属粉末焼結積層造形法は、粉体の薄層を形成する工程と、造形対象物の断面形状に対応する形状にレーザー光を照射し、金属材料を結合させて、断面形状物を造形する工程とを順次繰り返すことにより、積層造形物を形成する方法である。更に詳しくは、金属粉末焼結積層法では、金属粒子を含む金属材料を平面状に敷き詰めて薄層を形成し、薄層上の造形を行う対象領域にレーザー光を照射し、上記対象領域の粒子を選択的に焼結又は溶融結合させることで、立体造形物を厚さ方向に微分割した薄層(以下、単に「造形物層」ともいう。)の1層分を形成する。こうして形成された薄層の上に、さらに粉末材料を敷き詰め、レーザーを照射して粒子を選択的に焼結又は溶融結合させることで、次の造形物層を形成する。この手順を繰り返して、造形物を積み上げていくことで、所望の形状の立体積層造形物が製造される。
The metal powder sintering additive manufacturing method for manufacturing a three-dimensional additive manufacturing object from this metal material is a process of forming a thin layer of powder and irradiating laser light to a shape corresponding to the cross-sectional shape of the object to be formed. This is a method of forming a layered object by sequentially combining a material and a step of forming a cross-sectional object. More specifically, in the metal powder sintering lamination method, a metal material containing metal particles is laid flat to form a thin layer, and a target region to be shaped on the thin layer is irradiated with a laser beam, By selectively sintering or melting and bonding the particles, one layer of a thin layer (hereinafter also simply referred to as “modeled object layer”) obtained by finely dividing the three-dimensional modeled object in the thickness direction is formed. A powder material is further spread on the thin layer thus formed, and laser irradiation is performed to selectively sinter or melt bond the particles, thereby forming the next shaped article layer. By repeating this procedure and stacking shaped objects, a three-dimensional layered object having a desired shape is manufactured.
金属粉末焼結積層造形法によって多種多様な最終製品や試作品を大量に製造する観点からは、立体積層造形物をより短時間で製造できることが強く求められている。また、立体積層造形物の用途によっては、より高精細な立体造形物を製造することに対する要求も存在する。
From the viewpoint of manufacturing a large variety of final products and prototypes by the metal powder sintering additive manufacturing method, there is a strong demand for manufacturing a three-dimensional additive manufacturing product in a shorter time. Moreover, the request | requirement with respect to manufacturing a highly detailed three-dimensional molded item also exists depending on the use of a three-dimensional laminated model.
金属粉末焼結積層法において、金属粉末にレーザー照射される時間は非常に短い。従って、レーザーのエネルギーが金属粉体に十分に伝わらない場合、金属粉末が濡れ性を持つことができない状態で粉末が結合し、積層表面が平坦にならず凹凸部位が形成されてしまう。積層表面に凹凸部が形成されると、次層の粉体薄層形成の障害となり、表面精度が落ちるといった問題も生じる。レーザー照射スピードが速くなると金属粉末にレーザーが照射される時間が短くなるためこれらの問題はより顕著となり、金属粉末焼結積層法においては、積層スピードの向上と、精細性の向上が大きな問題となっている。
In the metal powder sintering lamination method, the laser irradiation time of the metal powder is very short. Therefore, when the energy of the laser is not sufficiently transmitted to the metal powder, the powder is bonded in a state where the metal powder cannot have wettability, and the laminated surface is not flattened and uneven portions are formed. If the uneven portion is formed on the laminated surface, it becomes an obstacle to the formation of the powder thin layer of the next layer, resulting in a problem that the surface accuracy is lowered. When the laser irradiation speed is increased, the time during which the metal powder is irradiated with the laser is shortened, so these problems become more prominent.In the metal powder sintering lamination method, the improvement of the lamination speed and the improvement of the fineness are the major problems. It has become.
金属粉末にレーザー光を照射して立体積層造形物(以下、「粉末焼結積層造形物」又は「金属粉末焼結積層造形物」ともいう。)を形成する方法としては、特許文献1には、Feを主成分とし、更に合金を構成する金属として、Cr、Ni、Cu等を含む金属粉末が開示され、硬度、熱伝導性、腐食性に優れた造形物を得ることができると記載されている。
Patent Document 1 discloses a method for forming a three-dimensional layered object (hereinafter, also referred to as “powder sintered layered object” or “metal powder sintered layered object”) by irradiating a metal powder with laser light. In addition, a metal powder containing Cr, Ni, Cu or the like as a metal that contains Fe as a main component and further constitutes an alloy is disclosed, and it is described that a molded article excellent in hardness, thermal conductivity, and corrosivity can be obtained. ing.
また、特許文献2には、複数の金属粒子と、当該金属粒子を結合するバインダーとを有し、当該バインダーがレーザー光の照射により分解されて気化する特徴を有するレーザー焼結用粉末が開示されている。
Patent Document 2 discloses a laser sintering powder having a plurality of metal particles and a binder that binds the metal particles, and the binder is decomposed and vaporized by irradiation with laser light. ing.
しかしながら、上記特許文献1及び特許文献2で開示されている金属粉末の最表面は、外気と接触することから、その表面に薄い酸化被膜が形成されやすくなる。一般的に金属酸化物は融点が高く熱伝導性が低いことから、レーザー照射により立体造形物を形成する金属粉末焼結積層法においては、レーザー照射等の高温環境下で、粒子表面に薄い酸化被膜が形成されやすくなる。一般的に金属酸化物は融点が高く熱伝導性が低いことから、レーザー焼結時に、迅速に熱を伝達することを阻害する要因となる。熱が迅速に金属粒子に伝達されないと、金属粒子が溶融して、表面張力が小さくなる温度領域に到達することができず、粒子自身が濡れ拡がることができない。金属粒子を含む紛体が十分に濡れ拡がることができないと、粒子形状を維持した状態で凝固することになり、その結果、金属粒子により形成される造形物である薄層表面には凹凸構造が生じ、その上に、次の薄層を平坦に敷き詰めることが困難になるといった問題や表面の平面精度が低下する問題が生じる。これらの問題は、レーザー照射を高速にすると、より顕著となるため、積層造形の高速化の大きな障害となっている。
However, since the outermost surface of the metal powder disclosed in Patent Document 1 and Patent Document 2 is in contact with outside air, a thin oxide film is easily formed on the surface. In general, metal oxide has a high melting point and low thermal conductivity, so in the metal powder sintering lamination method that forms a three-dimensional object by laser irradiation, a thin oxidation is performed on the particle surface in a high temperature environment such as laser irradiation. A film is easily formed. In general, a metal oxide has a high melting point and a low thermal conductivity, and therefore becomes a factor that hinders rapid heat transfer during laser sintering. If the heat is not quickly transferred to the metal particles, the metal particles cannot be melted and reach a temperature region where the surface tension becomes small, and the particles themselves cannot spread. If the powder containing metal particles cannot be sufficiently wetted and spread, it will solidify while maintaining the particle shape, resulting in a concavo-convex structure on the surface of the thin layer formed by the metal particles. On top of that, there arise problems that it becomes difficult to lay the next thin layer flatly and that the planar accuracy of the surface is lowered. Since these problems become more conspicuous when laser irradiation is performed at a high speed, it is a major obstacle to increasing the speed of additive manufacturing.
一方、金属粒子の酸化防止という観点から、特許文献3には、真空雰囲気下で、1100~1400℃の高温環境下で焼結処理を行う方法が開示されており、ステンレス鋼粉末の表面に形成されている酸化被膜を除去する方法として、フラックスを粒子表面に付与することにより、粒子表面に形成されている酸化被膜の除去や酸化防止を行い、ステンレス鋼粉末の高密度焼結を可能とする方法が開示されている。
On the other hand, from the viewpoint of preventing oxidation of metal particles, Patent Document 3 discloses a method of performing a sintering treatment in a high temperature environment of 1100 to 1400 ° C. in a vacuum atmosphere, and is formed on the surface of stainless steel powder. As a method of removing the oxidized film, the flux is applied to the particle surface to remove the oxide film formed on the particle surface and prevent oxidation, thereby enabling high-density sintering of the stainless steel powder. A method is disclosed.
しかしながら、特許文献3に記載の方法は、真空雰囲気下で1100~1400℃の高温環境下により、焼結用金型に充填した金属粒子の焼結処理を行う方法であり、本発明が目的とする造形対象物の断面形状に対応する薄層にレーザー光を照射し、金属材料を結合させ、この断面形状物を造形する工程を繰り返すことにより、大気圧環境下で積層造形物を形成する金属粉末焼結積層法とは全く相違するものであり、特許文献3には、上記方法に関する言及は一切なされていない。
However, the method described in Patent Document 3 is a method in which the metal particles filled in the sintering mold are sintered under a high temperature environment of 1100 to 1400 ° C. in a vacuum atmosphere. A metal that forms a layered object under atmospheric pressure by irradiating a thin layer corresponding to the cross-sectional shape of the object to be formed with laser light, bonding the metal material, and repeating the process of forming this cross-sectional object This is completely different from the powder sintering lamination method, and Patent Document 3 makes no mention of the above method.
従って、レーザー照射時に金属粉体表面の酸化物を除去し、金属粉体に短時間でエネルギーを伝達することができ、積層体表面の平面性と、積層造形物の形成速度を高速化できる金属粉末焼結積層造形法の開発が切望されている。
Therefore, it is possible to remove the oxide on the surface of the metal powder during laser irradiation, transfer energy to the metal powder in a short time, and increase the flatness of the surface of the laminate and the speed of formation of the layered object. Development of a powder sintering additive manufacturing method is eagerly desired.
本発明は、上記問題・状況に鑑みてなされたものであり、その解決課題は、積層体の形成の高速化を達成するとともに、形状精度及び平面性に優れた立体積層造形物を形成することができる金属粉末と、それを用いた粉末焼結積層造形物及びその製造方法を提供することである。
The present invention has been made in view of the above-described problems and situations, and the problem to be solved is to achieve a high-speed formation of a laminate and to form a three-dimensional layered object having excellent shape accuracy and flatness. It is to provide a metal powder that can be manufactured, a powder sintered laminate model using the metal powder, and a method for manufacturing the same.
本発明者は、上記課題を解決すべく上記問題の原因等について検討した結果、金属粉末焼結積層造形法に用いられる金属粉末であって、個数平均粒子径が特定の範囲内にある金属粒子の表面に、特定の範囲内の厚さのフラックスが被覆されていることを特徴とする金属粉末により、積層体の形成の高速化を達成するとともに、形状精度及び平面性に優れた立体積層造形物を形成することができる金属粉末を実現することができることを見いだし、本発明に至った。
As a result of studying the cause of the above-mentioned problems in order to solve the above problems, the present inventor is a metal powder used in the metal powder sintering additive manufacturing method, and the number average particle diameter is within a specific range. The metal powder is characterized in that the surface of the coating is coated with a flux with a thickness within a specific range. The inventors have found that a metal powder capable of forming an object can be realized, and have reached the present invention.
すなわち、本発明の上記課題は、下記の手段により解決される。
That is, the above-mentioned problem of the present invention is solved by the following means.
1.金属粉末焼結積層造形法に用いられる金属粉末であって、
個数平均粒子径が5~100μmの範囲内である金属粒子の表面に、平均厚さが5~30nmの範囲内のフラックスが被覆されていることを特徴とする金属粉末。 1. Metal powder used in the metal powder sintering additive manufacturing method,
A metal powder characterized in that the surface of a metal particle having a number average particle diameter in the range of 5 to 100 μm is coated with a flux having an average thickness in the range of 5 to 30 nm.
個数平均粒子径が5~100μmの範囲内である金属粒子の表面に、平均厚さが5~30nmの範囲内のフラックスが被覆されていることを特徴とする金属粉末。 1. Metal powder used in the metal powder sintering additive manufacturing method,
A metal powder characterized in that the surface of a metal particle having a number average particle diameter in the range of 5 to 100 μm is coated with a flux having an average thickness in the range of 5 to 30 nm.
2.前記金属粒子の平均円形度が、0.90~0.98の範囲内であることを特徴とする第1項に記載の金属粉末。
2. 2. The metal powder according to item 1, wherein the average circularity of the metal particles is in the range of 0.90 to 0.98.
3.前記金属粒子の粒径分布における変動係数(CV値)が、15%以下であることを特徴とする第1項又は第2項に記載の金属粉末。
3. The coefficient of variation (CV value) in the particle size distribution of the metal particles is 15% or less.
4.前記フラックスが、ホウ酸、ホウ酸塩、ホウ砂、フッ化物及び塩化物から選ばれる少なくとも一種であることを特徴とする第1項から第3項までのいずれか一項に記載の金属粉末。
4. The metal powder according to any one of Items 1 to 3, wherein the flux is at least one selected from boric acid, borate, borax, fluoride, and chloride.
5.前記金属粒子が、鉄、鉄合金、ニッケル、ニッケル合金、コバルト、コバルト合金、銅、銅合金、アルミニウム及びアルミニウム合金から選ばれる金属材料を含有することを特徴とする第1項から第4項までのいずれか一項に記載の金属粉末。
5. The first to fourth items, wherein the metal particles contain a metal material selected from iron, iron alloy, nickel, nickel alloy, cobalt, cobalt alloy, copper, copper alloy, aluminum and aluminum alloy. Metal powder as described in any one of these.
6.第1項から第5項までのいずれか一項に記載の金属粉末を用いて立体積層造形物を製造する粉末焼結積層造形物の製造方法であって、
少なくとも、前記金属粉末を薄層に展開する薄層形成工程と、
前記薄層を構成する金属粉末に、造形対象物の断面形状に対応する形状パターンでレーザー光を照射して、前記金属粉末を結合させる断面形状形成工程を有し、
前記薄層形成工程と前記断面形状形成工程とを順次繰り返すことにより、立体積層造形物を製造することを特徴とする粉末焼結積層造形物の製造方法。 6). A method for producing a powder sintered laminate model for manufacturing a three-dimensional laminate model using the metal powder according to any one ofitems 1 to 5,
At least a thin layer forming step of developing the metal powder into a thin layer;
A cross-sectional shape forming step of irradiating the metal powder constituting the thin layer with a laser beam in a shape pattern corresponding to the cross-sectional shape of the object to be modeled to bond the metal powder,
A method for producing a powder-sintered layered object, wherein a three-dimensional layered object is manufactured by sequentially repeating the thin layer forming step and the cross-sectional shape forming step.
少なくとも、前記金属粉末を薄層に展開する薄層形成工程と、
前記薄層を構成する金属粉末に、造形対象物の断面形状に対応する形状パターンでレーザー光を照射して、前記金属粉末を結合させる断面形状形成工程を有し、
前記薄層形成工程と前記断面形状形成工程とを順次繰り返すことにより、立体積層造形物を製造することを特徴とする粉末焼結積層造形物の製造方法。 6). A method for producing a powder sintered laminate model for manufacturing a three-dimensional laminate model using the metal powder according to any one of
At least a thin layer forming step of developing the metal powder into a thin layer;
A cross-sectional shape forming step of irradiating the metal powder constituting the thin layer with a laser beam in a shape pattern corresponding to the cross-sectional shape of the object to be modeled to bond the metal powder,
A method for producing a powder-sintered layered object, wherein a three-dimensional layered object is manufactured by sequentially repeating the thin layer forming step and the cross-sectional shape forming step.
7.前記金属粉末に、造形対象物の断面形状に対応する形状パターンでレーザー光を照射する断面形状形成工程において、照射する前記レーザー光の下式(1)で表されるエネルギー密度Eが、45~150J/mm2の範囲内であることを特徴とする第6項に記載の粉末焼結積層造形物の製造方法。
7). In the cross-sectional shape forming step of irradiating the metal powder with a laser beam in a shape pattern corresponding to the cross-sectional shape of the object to be shaped, the energy density E represented by the following formula (1) of the laser beam to be irradiated Item 7. The method for producing a powder-sintered layered article according to Item 6, wherein the method is within a range of 150 J / mm 2 .
式(1)
エネルギー密度E(J/mm2)={レーザー出力/(レーザー照射スピード×焦点スポット面積)}
8.前記金属粉末に、造形対象物の断面形状に対応する形状パターンでレーザー光を照射する断面形状形成工程が、フラックスにより金属粉末表面の還元反応を促進する第1のレーザー光照射工程と、前記金属粉末を結合させる第2のレーザー光照射工程より構成されていることを特徴とする第6項又は第7項に記載の粉末焼結積層造形物の製造方法。 Formula (1)
Energy density E (J / mm 2 ) = {Laser output / (Laser irradiation speed × Focus spot area)}
8). The cross-sectional shape forming step of irradiating the metal powder with a laser beam in a shape pattern corresponding to the cross-sectional shape of the object to be shaped includes a first laser light irradiation step of accelerating a reduction reaction on the surface of the metal powder with a flux, and the metal 8. The method for producing a powder-sintered layered product according to item 6 or 7, characterized by comprising a second laser light irradiation step for bonding powder.
エネルギー密度E(J/mm2)={レーザー出力/(レーザー照射スピード×焦点スポット面積)}
8.前記金属粉末に、造形対象物の断面形状に対応する形状パターンでレーザー光を照射する断面形状形成工程が、フラックスにより金属粉末表面の還元反応を促進する第1のレーザー光照射工程と、前記金属粉末を結合させる第2のレーザー光照射工程より構成されていることを特徴とする第6項又は第7項に記載の粉末焼結積層造形物の製造方法。 Formula (1)
Energy density E (J / mm 2 ) = {Laser output / (Laser irradiation speed × Focus spot area)}
8). The cross-sectional shape forming step of irradiating the metal powder with a laser beam in a shape pattern corresponding to the cross-sectional shape of the object to be shaped includes a first laser light irradiation step of accelerating a reduction reaction on the surface of the metal powder with a flux, and the metal 8. The method for producing a powder-sintered layered product according to
9.第1項から第5項までのいずれか一項に記載の金属粉末を用いて形成されたことを特徴とする粉末焼結積層造形物。
9. A powder sintered layered product formed by using the metal powder according to any one of Items 1 to 5.
本発明の上記手段により、積層体の形成の高速化を達成するとともに、形状精度及び平面性に優れた立体積層造形物を形成することができる金属粉末と、それを用いた粉末焼結積層造形物の製造方法を提供することができる。
According to the above-mentioned means of the present invention, a metal powder capable of achieving a high-speed formation of a laminate and forming a three-dimensional laminate model having excellent shape accuracy and flatness, and a powder sintering laminate model using the metal powder A method for manufacturing a product can be provided.
本発明の効果の発現機構又は作用機構については、すべてが明確にはなっていないが、以下のように推察している。
Although the expression mechanism or action mechanism of the effect of the present invention is not completely clear, it is presumed as follows.
前述のように、金属粉末を薄層状に形成した後、当該薄層にレーザー光を所望のパターンで照射して、レーザー光により金属粉末を焼結又は溶融結合して造形物層を形成し、当該造形物層を複数層積層することにより立体積層造形物を形成する金属粉末焼結積層造形法において、金属粉末を構成している金属粒子の最表面は、環境雰囲気との界面となり、薄い酸化被膜が形成されることになる。このような金属酸化被膜は、一般的には、融点が高く熱伝導性が低くなるため、レーザー光照射による焼結時に迅速に熱を伝達することを阻害することになる。
As described above, after forming the metal powder in a thin layer, the thin layer is irradiated with laser light in a desired pattern, and the metal powder is sintered or melt-bonded with the laser light to form a modeled object layer, In the metal powder sintering additive manufacturing method for forming a three-dimensional additive structure by laminating a plurality of object layers, the outermost surface of the metal particles constituting the metal powder becomes an interface with the environmental atmosphere and is thinly oxidized. A film will be formed. Since such a metal oxide film generally has a high melting point and low thermal conductivity, it impedes rapid heat transfer during sintering by laser light irradiation.
通常、溶融金属の表面張力は、温度の上昇と共に低下する特性を有しているが、レーザー光照射による熱エネルギーが迅速に伝達されないと、金属粒子として、溶融により表面張力が低下する特性を発現する温度領域に到達することができないため、濡れ拡がる特性が不十分となる。その結果、金属粉末が薄層形成時に、十分に濡れ拡がることができないため、粒子形状を維持したまま凝固してしまうことになり、薄層表面には凹凸パターンが形成され、その上に次の薄層を積層させるときに、均一で平滑性の高い第2の薄層を敷き詰めることができなくなる。最終的には、形成する立体積層造形物の表面精度が低下することになり、所望の形成の立体積層造形物を得ることができなくなる。これの問題は、レーザー照射を高速にすると、より顕著に発現しやすくなるため、立体積層造形物の形成の高速化においては大きな障害となっていた。
Normally, the surface tension of molten metal decreases with increasing temperature, but if the thermal energy due to laser light irradiation is not transmitted quickly, the surface tension of molten metal decreases as a result of melting. Since the temperature range to be reached cannot be reached, the property of spreading and spreading becomes insufficient. As a result, since the metal powder cannot sufficiently wet and spread when forming a thin layer, it will solidify while maintaining the particle shape, and an uneven pattern is formed on the surface of the thin layer. When laminating thin layers, it becomes impossible to spread a second thin layer that is uniform and highly smooth. Eventually, the surface accuracy of the three-dimensional layered object to be formed is lowered, and a three-dimensional layered object with a desired formation cannot be obtained. This problem has become a major obstacle in speeding up the formation of a three-dimensional layered object because the laser irradiation is more likely to be manifested more remarkably.
本発明者らは、上記問題について鋭意検討を進めた結果、立体積層造形物の形成に適用する金属粉末として、個数平均粒子径が5~100μmの範囲内にある金属粒子の表面に、平均厚さが5~30nmの範囲内でフラックスを被覆した構成の金属粉末を適用することにより、金属粉末にレーザー光を照射した時に、金属粒子表面を形成している酸化物を、フラックスの還元作用等により除去することができる。その結果、金属酸化物による熱伝導低下等の阻害因子が除かれ、金属粒子に短時間でレーザー光のエネルギーを伝達することが可能となる。その結果、迅速に金属粒子を含む金属粉体の表面張力が低下する温度領域に到達させることができ、金属粉末を短時間で安定して濡れ拡がらせることができ、薄層の表面は平坦となり、その上に形成する次層の薄層の形成を阻害せず、立体積層造形物を高速かつ高精度で安定して形成することができるものである。
As a result of diligent investigations on the above problems, the present inventors have determined that the average thickness of the metal powder having a number average particle diameter in the range of 5 to 100 μm as the metal powder applied to the formation of the three-dimensional layered object is By applying a metal powder with a flux coating within a range of 5 to 30 nm, when the metal powder is irradiated with laser light, the oxide forming the metal particle surface is reduced to reduce the flux, etc. Can be removed. As a result, obstruction factors such as a decrease in heat conduction due to the metal oxide are removed, and the energy of the laser beam can be transmitted to the metal particles in a short time. As a result, it is possible to quickly reach the temperature region where the surface tension of the metal powder containing metal particles decreases, the metal powder can be stably spread in a short time, and the surface of the thin layer is flat. Therefore, the three-dimensional layered object can be stably formed at high speed and with high accuracy without hindering the formation of the next thin layer formed thereon.
上記で説明した本発明に係るフラックスの金属粒子に対する主要な作用は、上述のとおり、金属粒子表面に形成されている金属酸化物を除去することにある。
As described above, the main action of the flux according to the present invention described above on the metal particles is to remove the metal oxide formed on the surface of the metal particles.
一般的に、フラックスの作用は、金属酸化物と反応して、反応生成物(金属塩)を形成し,溶解除去する。
Generally, the action of flux reacts with a metal oxide to form a reaction product (metal salt), which is dissolved and removed.
例えば、フラックスとしてホウ砂(Na2B4O7)やホウ酸(H3BO3)を用いた場合の、酸化鉄や酸化銅の還元反応を以下に示す。
For example, the reduction reaction of iron oxide or copper oxide when borax (Na 2 B 4 O 7 ) or boric acid (H 3 BO 3 ) is used as the flux is shown below.
FeO+Na2B4O7→Fe(BO2)2+2NaBO2
CuO+2H3BO3→Cu(BO2)2+3H2O
上記反応により形成されたフラックス残渣は、立体積層造形物自身の性能に悪影響を与える場合もあるため、金属粒子に対するフラックスの被覆量としては、十分な還元反応を進行させるとともに、悪影響を最小限とする観点からは、平均厚さが5~30nmの範囲内でフラックスを被覆することが必要である。 FeO + Na 2 B 4 O 7 → Fe (BO 2 ) 2 + 2NaBO 2
CuO + 2H 3 BO 3 → Cu (BO 2 ) 2 + 3H 2 O
Since the flux residue formed by the above reaction may adversely affect the performance of the three-dimensional layered object itself, the coating amount of the flux on the metal particles is sufficiently reduced and the adverse effect is minimized. From this viewpoint, it is necessary to coat the flux within an average thickness range of 5 to 30 nm.
CuO+2H3BO3→Cu(BO2)2+3H2O
上記反応により形成されたフラックス残渣は、立体積層造形物自身の性能に悪影響を与える場合もあるため、金属粒子に対するフラックスの被覆量としては、十分な還元反応を進行させるとともに、悪影響を最小限とする観点からは、平均厚さが5~30nmの範囲内でフラックスを被覆することが必要である。 FeO + Na 2 B 4 O 7 → Fe (BO 2 ) 2 + 2NaBO 2
CuO + 2H 3 BO 3 → Cu (BO 2 ) 2 + 3H 2 O
Since the flux residue formed by the above reaction may adversely affect the performance of the three-dimensional layered object itself, the coating amount of the flux on the metal particles is sufficiently reduced and the adverse effect is minimized. From this viewpoint, it is necessary to coat the flux within an average thickness range of 5 to 30 nm.
本発明の金属粉末は、金属粉末焼結積層造形法に用いられる金属粉末であって、個数平均粒子径が5~100μmの範囲内である金属粒子の表面に、平均厚さが5~30nmの範囲内のフラックスが被覆されていることを特徴とする。この特徴は、各請求項に係る発明に共通する又は対応する技術的特徴である。
The metal powder of the present invention is a metal powder used in the metal powder sintering additive manufacturing method, and has an average thickness of 5 to 30 nm on the surface of metal particles having a number average particle diameter in the range of 5 to 100 μm. It is characterized by being coated with a flux within the range. This feature is a technical feature common to or corresponding to the claimed invention.
本発明の実施態様としては、本発明の目的とする効果をより発現できる観点から、前記金属粒子として、平均円形度が0.90~0.98の範囲内である球状粒子を適用することが、最密充填に近い条件で、表面均一性に優れた薄層を形成でき、より形状精度及び平面性に優れた立体積層造形物を形成することができる点で好ましい。
As an embodiment of the present invention, spherical metal particles having an average circularity in the range of 0.90 to 0.98 can be applied as the metal particles from the viewpoint of more manifesting the intended effect of the present invention. It is preferable in that a thin layer excellent in surface uniformity can be formed under conditions close to close-packing, and a three-dimensional layered object having better shape accuracy and flatness can be formed.
また、金属粒子の粒径分布における変動係数(CV値)が、15%以下であることが、極めて狭い粒径分布を有する金属粒子群を適用することにより、積層体の1ユニットである薄層を形成した際の凹凸を抑制し、平滑性に優れた薄層を形成することができる点で好ましい。
Further, by applying a metal particle group having an extremely narrow particle size distribution, the coefficient of variation (CV value) in the particle size distribution of the metal particles is 15% or less, so that a thin layer that is one unit of the laminate It is preferable in that it can suppress unevenness when formed and can form a thin layer with excellent smoothness.
また、適用するフラックスが、ホウ酸、ホウ酸塩、ホウ砂、フッ化物及び塩化物から選ばれる少なくとも一種の無機フラックスであることが、金属粒子表面の酸化物をレーザー照射により効率よく除去することができ、金属粒子に短時間でレーザーのエネルギーを伝達することができる観点で好ましい。
Also, the applied flux is at least one inorganic flux selected from boric acid, borate, borax, fluoride and chloride, and the oxide on the metal particle surface is efficiently removed by laser irradiation. It is preferable from the viewpoint that laser energy can be transmitted to the metal particles in a short time.
また、適用する金属粒子として、鉄、鉄合金、ニッケル、ニッケル合金、コバルト、コバルト合金、銅、銅合金、アルミニウム及びアルミニウム合金から選ばれる金属材料を含有する金属粒子であることが、良好な熱伝導率を有し、焼結適性に優れ、安定して金属粉末焼結層を形成することができる点で好ましい。
In addition, the metal particles to be applied are metal particles containing a metal material selected from iron, iron alloy, nickel, nickel alloy, cobalt, cobalt alloy, copper, copper alloy, aluminum, and aluminum alloy. It is preferable in that it has conductivity, is excellent in suitability for sintering, and can stably form a sintered metal powder layer.
また、本発明の粉末焼結積層造形物の製造方法は、本発明の金属粉末を用いて立体造形物を製造する方法で、少なくとも、前記金属粉末を薄層に展開する薄層形成工程と、前記薄層を構成する金属粉末に、造形対象物の断面形状に対応する形状パターンでレーザー光を照射して、前記金属粉末を結合させる断面形状形成工程を有し、前記薄層形成工程と前記断面形状形成工程とを順次繰り返すことにより、立体積層造形物を製造することを特徴とする。
In addition, the method for producing a powder sintered laminate model of the present invention is a method of manufacturing a three-dimensional model using the metal powder of the present invention, and at least a thin layer forming step of developing the metal powder into a thin layer, The metal powder constituting the thin layer has a cross-sectional shape forming step of irradiating a laser beam with a shape pattern corresponding to the cross-sectional shape of the object to be modeled to combine the metal powder, and the thin layer forming step and the A three-dimensional layered object is manufactured by sequentially repeating the cross-sectional shape forming step.
また、前記断面形状形成工程においては、金属粉末に照射するレーザー光のエネルギー密度Eを、45~150J/mm2の範囲内とすることが、効率よく金属粉末焼結体を形成することができる点で好ましい。
Further, in the cross-sectional shape forming step, the metal powder sintered body can be efficiently formed by setting the energy density E of the laser light applied to the metal powder within the range of 45 to 150 J / mm 2. This is preferable.
また、前記断面形状形成工程において、レーザー照射方法として、フラックスにより金属粉末表面の還元反応を促進する第1のレーザー光照射工程と、前記金属粉末を結合させる第2のレーザー光照射工程の分割した照射とすることが、更に精細な表面性を有する立体積層造形物を得ることができる点で好ましい。
Further, in the cross-sectional shape forming step, the laser irradiation method is divided into a first laser light irradiation step that promotes a reduction reaction on the surface of the metal powder by a flux and a second laser light irradiation step that combines the metal powder. Irradiation is preferable in that a three-dimensional layered object having a finer surface property can be obtained.
以下、本発明とその構成要素、及び本発明を実施するための形態・態様について詳細な説明をする。なお、本発明において示す「~」は、その前後に記載される数値を下限値及び上限値として含む意味で使用する。また、以下の各図の説明において、構成要素の末尾に括弧内で記載した数字は、各図における符号を表す。
Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In the present invention, “˜” is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value. Further, in the following description of each figure, the numbers described in parentheses at the end of the constituent elements represent the symbols in each figure.
《金属粉末》
〔金属粉末の構成〕
本発明の金属紛末では、個数平均粒子径が5~100μmの範囲内にある金属粒子の表面に、平均厚さが5~30nmの範囲内のフラックスが被覆されている構成であることを特徴とする。 《Metal powder》
[Composition of metal powder]
The metal powder of the present invention is characterized in that the surface of metal particles having a number average particle diameter in the range of 5 to 100 μm is coated with a flux having an average thickness in the range of 5 to 30 nm. And
〔金属粉末の構成〕
本発明の金属紛末では、個数平均粒子径が5~100μmの範囲内にある金属粒子の表面に、平均厚さが5~30nmの範囲内のフラックスが被覆されている構成であることを特徴とする。 《Metal powder》
[Composition of metal powder]
The metal powder of the present invention is characterized in that the surface of metal particles having a number average particle diameter in the range of 5 to 100 μm is coated with a flux having an average thickness in the range of 5 to 30 nm. And
図1は、本発明に係る金属粒子の表面にフラックスが被覆されている金属粉末の構成の一例を示す模式断面図である。
FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a metal powder in which the surface of metal particles according to the present invention is coated with a flux.
図1で示すように、本発明の金属粉末(1)は、コア部が個数平均粒子径dの金属粒子(2)により構成され、その金属粒子(2)の表面に、シェル部として、厚さhのフラックス(3)が被覆されている構成である。このとき、フラックス(3)は、金属粒子の(2)の全表面を被覆する構成であっても、あるいは、一部に未被覆部を有する不連続な構成であってもよいが、前者の構成であることが本発明の目的効果を十分に発現させることができる観点から好ましい。なお、後者の一部に未被覆部を有する不連続な構成である場合には、不連続なフラックスの全体積で、粒子表面を均一に被覆したと仮定した際の厚さをフラックスの平均厚さと定義する。
As shown in FIG. 1, in the metal powder (1) of the present invention, the core part is composed of metal particles (2) having a number average particle diameter d, and the surface of the metal particle (2) has a thickness as a shell part. This is a configuration in which a flux (3) of length h is coated. At this time, the flux (3) may be configured to cover the entire surface of the metal particles (2), or may be a discontinuous configuration having an uncoated portion in part. The configuration is preferable from the viewpoint that the objective effect of the present invention can be sufficiently exhibited. In the case of a discontinuous configuration having an uncoated part in the latter part, the average thickness of the flux is the thickness when assuming that the particle surface is uniformly coated with the total volume of the discontinuous flux. And define.
〔金属粒子〕
本発明に係る金属粒子(2)は、造形しようとする立体造形物の材料である金属を主成分として構成され、個数平均粒子径が5~100μmの範囲内の粒子である。 [Metal particles]
The metal particles (2) according to the present invention are composed mainly of a metal that is a material of a three-dimensional structure to be shaped, and have a number average particle diameter in the range of 5 to 100 μm.
本発明に係る金属粒子(2)は、造形しようとする立体造形物の材料である金属を主成分として構成され、個数平均粒子径が5~100μmの範囲内の粒子である。 [Metal particles]
The metal particles (2) according to the present invention are composed mainly of a metal that is a material of a three-dimensional structure to be shaped, and have a number average particle diameter in the range of 5 to 100 μm.
金属粒子(2)を構成する金属材料としては、特に制限はなく、例えば、アルミニウム、クロム、コバルト、銅、金、鉄、マグネシウム、シリコン、モリブデン、ニッケル、パラジウム、白金、ロジウム、銀、錫、チタン、タングステン、亜鉛等と、これらの金属元素を含む合金が含まれる。上記金属元素の中でも、特に、鉄、鉄合金、ニッケル、ニッケル合金、コバルト、コバルト合金、銅、銅合金、アルミニウム及びアルミニウム合金から選ばれる少なくとも一種の金属材料を含むことが好ましい。
There is no restriction | limiting in particular as a metal material which comprises a metal particle (2), For example, aluminum, chromium, cobalt, copper, gold, iron, magnesium, silicon, molybdenum, nickel, palladium, platinum, rhodium, silver, tin, Titanium, tungsten, zinc, and the like, and alloys containing these metal elements are included. Among the metal elements, it is particularly preferable to include at least one metal material selected from iron, iron alloy, nickel, nickel alloy, cobalt, cobalt alloy, copper, copper alloy, aluminum, and aluminum alloy.
最終的に得られる立体造形物の組成を均一にしやすくできる観点から、金属粒子(2)は、一種類の材料から構成されていることが好ましいが、上記金属粉末(1)の構成を可能とする限りにおいて、二種類以上の材料を組み合わせて用いてもよい。
The metal particles (2) are preferably composed of one kind of material from the viewpoint that the composition of the finally obtained three-dimensional structure can be easily made uniform, but the metal powder (1) can be configured. As long as it does, you may use in combination of 2 or more types of materials.
本発明に係る金属粒子では、主成分である金属元素の比率としては、75質量%以上であることが好ましく、より好ましくは85質量%以上であり、さらに好ましくは95質量%以上であり、特に好ましくは金属元素のみで構成されている金属粒子である。
In the metal particles according to the present invention, the ratio of the metal element as the main component is preferably 75% by mass or more, more preferably 85% by mass or more, further preferably 95% by mass or more, particularly Preferably, the metal particles are composed only of metal elements.
金属粒子(2)において、主成分として含まれる金属材料とは、蛍光X線分析などの公知の方法で特定した金属材料のうち、最も量が多いものとする。また、金属粉末を、界面活性剤を含有する水溶液中での超音波処理などの公知の方法で金属粒子(2)とフラックス(3)とを分離して、得られた金属粒子(2)に対して蛍光X線分析やICP発光分光分析を行って、金属粒子(2)に主成分として含まれる金属材料を特定してもよい。
In the metal particles (2), the metal material contained as a main component is the largest amount among the metal materials specified by a known method such as fluorescent X-ray analysis. Further, the metal particles (2) and the flux (3) are separated from the metal powder by a known method such as ultrasonic treatment in an aqueous solution containing a surfactant, and the resulting metal particles (2) are obtained. On the other hand, a metal material contained as a main component in the metal particles (2) may be specified by performing fluorescent X-ray analysis or ICP emission spectroscopic analysis.
(個数平均粒子径)
本発明においては、金属粒子(2)の個数平均粒子径が5~100μmの範囲内であることを特徴とし、好ましくは10~80μmの範囲内であり、更に好ましくは20~60μmの範囲内であり、特に好ましくは、30~50μmの範囲内である。 (Number average particle diameter)
In the present invention, the number average particle diameter of the metal particles (2) is in the range of 5 to 100 μm, preferably in the range of 10 to 80 μm, more preferably in the range of 20 to 60 μm. Particularly preferably in the range of 30 to 50 μm.
本発明においては、金属粒子(2)の個数平均粒子径が5~100μmの範囲内であることを特徴とし、好ましくは10~80μmの範囲内であり、更に好ましくは20~60μmの範囲内であり、特に好ましくは、30~50μmの範囲内である。 (Number average particle diameter)
In the present invention, the number average particle diameter of the metal particles (2) is in the range of 5 to 100 μm, preferably in the range of 10 to 80 μm, more preferably in the range of 20 to 60 μm. Particularly preferably in the range of 30 to 50 μm.
金属粒子(2)の個数平均粒子径が5μm未満であると、金属粒子の流動性が不足し、造形速度が遅くなり、かつ、金属粉末を形成した際に、金属粉末をより均一に敷き詰めて薄層を形成することが難しくなるため、立体造形物の形成精度が低下し、更に、金属粒子に多量のレーザー光を照射することが困難となり、金属粒子の溶融・焼結効率が低下するため、造形速度がより早くすることが難しくなる。更に、5μm未満なると金属粒子の作製の難易度が高まり、形成する金属粉末の製造コストが上昇する。
When the number average particle diameter of the metal particles (2) is less than 5 μm, the fluidity of the metal particles is insufficient, the molding speed is slow, and the metal powder is spread more uniformly when the metal powder is formed. Since it becomes difficult to form a thin layer, the formation accuracy of the three-dimensional structure is lowered, and furthermore, it becomes difficult to irradiate a large amount of laser light to the metal particles, and the melting and sintering efficiency of the metal particles is lowered. It becomes difficult to make the modeling speed faster. Furthermore, when the thickness is less than 5 μm, the difficulty of producing metal particles increases, and the production cost of the metal powder to be formed increases.
また、金属粒子(2)の個数平均粒子径が100μmを超えると、過度に凹凸パターンが強調され、高精細な立体造形物を製造することが困難となる。
Further, if the number average particle diameter of the metal particles (2) exceeds 100 μm, the uneven pattern is excessively emphasized, and it becomes difficult to produce a high-definition three-dimensional object.
金属粒子(2)の個数平均粒子径は、透過型電子顕微鏡(TEM)で撮像した金属粉末(1)の断面図において、任意に50個選択した金属粒子(2)の粒子径の平均値とすることができる。このとき、それぞれの粒子径は、各粒子の投影面積を円換算した時の直径で表し、50個の金属粒子について測定した粒子径の相加平均値を求め、これを金属粒子(2)の個数平均粒子径とする。
The number average particle diameter of the metal particles (2) is the average value of the particle diameters of 50 metal particles (2) arbitrarily selected in the cross-sectional view of the metal powder (1) imaged with a transmission electron microscope (TEM). can do. At this time, each particle diameter is expressed as a diameter when the projected area of each particle is converted into a circle, and an arithmetic average value of particle diameters measured for 50 metal particles is obtained. The number average particle size.
他の測定方法としては、金属粉末(1)を、例えば、界面活性剤を含有する水溶液中で超音波処理などの公知の分散装置を用いて分散し、金属粒子(2)表面からフラックス(3)を分離した後、得られた金属粒子(2)をレーザー回折/散乱式粒子径分布測定装置(例えば、株式会社堀場製作所製、Partica LA-960)で測定して得られた値をもとに、粒子が球形と仮定して算出した個数平均粒子径としてもよい。
As another measurement method, for example, the metal powder (1) is dispersed in an aqueous solution containing a surfactant by using a known dispersing device such as ultrasonic treatment, and the flux (3 ), And the obtained metal particles (2) were measured with a laser diffraction / scattering particle size distribution measuring apparatus (for example, Partica LA-960 manufactured by Horiba, Ltd.). Alternatively, the number average particle diameter may be calculated assuming that the particles are spherical.
(平均円形度)
本発明に係る金属粒子においては、平均円形度が0.90~0.98の範囲内であることが好ましい。 (Average circularity)
In the metal particles according to the present invention, the average circularity is preferably in the range of 0.90 to 0.98.
本発明に係る金属粒子においては、平均円形度が0.90~0.98の範囲内であることが好ましい。 (Average circularity)
In the metal particles according to the present invention, the average circularity is preferably in the range of 0.90 to 0.98.
本発明でいう円形度とは、透過型電子顕微鏡(TEM)で撮像し、下式で示すように、二次元に投影した金属粒子の粒子面積に等しい面積の円の周囲長を、撮像した金属粒子の周囲長で除した数値で表され、平均円形度とは、50個の金属粒子について上記方法に従って円形度を測定し、得られた測定値の相加平均値で表す。
The circularity referred to in the present invention is an image obtained by imaging the circumference of a circle having an area equal to the particle area of a metal particle projected two-dimensionally, as shown by the following equation, with a transmission electron microscope (TEM). The average circularity is represented by an arithmetic average value of the measured values obtained by measuring the circularity according to the above method for 50 metal particles.
円形度=(金属粒子の投影面積に等しい円の周囲長)/(金属粒子の周囲長)
金属粒子の平均円形度が0.90~0.98の範囲内であれば、金属粉末による薄層を形成した際に、均一に敷き詰めることができ、空隙率の低い薄層を効率よく形成することができ、立体積層造形物の精度をより高めることができる。 Circularity = (perimeter of circle equal to projected area of metal particle) / (perimeter of metal particle)
When the average circularity of the metal particles is in the range of 0.90 to 0.98, when a thin layer of metal powder is formed, it can be uniformly spread and a thin layer with a low porosity can be efficiently formed. It is possible to improve the accuracy of the three-dimensional layered object.
金属粒子の平均円形度が0.90~0.98の範囲内であれば、金属粉末による薄層を形成した際に、均一に敷き詰めることができ、空隙率の低い薄層を効率よく形成することができ、立体積層造形物の精度をより高めることができる。 Circularity = (perimeter of circle equal to projected area of metal particle) / (perimeter of metal particle)
When the average circularity of the metal particles is in the range of 0.90 to 0.98, when a thin layer of metal powder is formed, it can be uniformly spread and a thin layer with a low porosity can be efficiently formed. It is possible to improve the accuracy of the three-dimensional layered object.
(変動係数:CV値)
本発明に係る金属粒子においては、粒度分布における変動係数(CV値)が、15%以下であることが好ましい。下限値は特に制限はないが、現実的には、0.1%以上であり、より現実的には、1.0%以上である。 (Coefficient of variation: CV value)
In the metal particles according to the present invention, the coefficient of variation (CV value) in the particle size distribution is preferably 15% or less. The lower limit is not particularly limited, but is practically 0.1% or more, and more practically 1.0% or more.
本発明に係る金属粒子においては、粒度分布における変動係数(CV値)が、15%以下であることが好ましい。下限値は特に制限はないが、現実的には、0.1%以上であり、より現実的には、1.0%以上である。 (Coefficient of variation: CV value)
In the metal particles according to the present invention, the coefficient of variation (CV value) in the particle size distribution is preferably 15% or less. The lower limit is not particularly limited, but is practically 0.1% or more, and more practically 1.0% or more.
金属粒子のCV値が15%以下であれば、薄層を形成したときに金属粒子を含む金属粉末がより均一に敷き詰められやすくなり、製造される立体積層造形物の精度をより高めることができる。
If the CV value of the metal particles is 15% or less, the metal powder containing the metal particles can be more uniformly spread when the thin layer is formed, and the accuracy of the three-dimensional layered object to be manufactured can be further increased. .
本発明においては、金属粒子のCV値は10%以下であることが、造形速度をさらに速くし、かつ、製造される立体積層造形物の形成精度をさらに高める観点から好ましく、8%以下であることがさらに好ましい。
In the present invention, the CV value of the metal particles is preferably 10% or less from the viewpoint of further increasing the modeling speed and further improving the formation accuracy of the three-dimensional layered object to be manufactured, and is 8% or less. More preferably.
ここでいうCV値は、透過型電子顕微鏡(TEM)で撮像した金属粉末の断面写真において、任意に50個選択した金属粒子の粒子径(長径と短径との平均値)から、これら粒子径の標準偏差σ及び平均粒子径Dを算出して、(σ/D)×100として求められる値である。
The CV value here is determined from the particle diameter (average value of major axis and minor axis) of arbitrarily selected 50 metal particles in a cross-sectional photograph of the metal powder imaged with a transmission electron microscope (TEM). The standard deviation σ and the average particle diameter D are calculated as (σ / D) × 100.
また、他の方法としては、金属粒子の標準偏差σ及び平均粒子径Dは、界面活性剤を含有する水溶液中での超音波処理などの公知の方法で金属粉末を構成する金属粒子とフラックスとを分離して、得られた金属粒子をレーザー回折/散乱式粒子径分布測定装置(例えば、株式会社堀場製作所製、Partica LA-960)で測定して得られた値をもとに、粒子が球形と仮定して算出した値としてもよい。CV値は、粒度分布にどの程度の広がりがあるかを示す値であり、CV値が小さいほど粒度分布が狭いことを示す。
Further, as another method, the standard deviation σ and the average particle diameter D of the metal particles are determined according to a known method such as ultrasonic treatment in an aqueous solution containing a surfactant. Based on the value obtained by measuring the obtained metal particles with a laser diffraction / scattering particle size distribution measuring device (for example, Partica LA-960, manufactured by Horiba, Ltd.), A value calculated assuming a spherical shape may be used. The CV value is a value indicating how wide the particle size distribution is, and the smaller the CV value, the narrower the particle size distribution.
(金属粒子の製造方法)
本発明に係る金属粒子は、例えば、ガスアトマイズ法、水アトマイズ法、プラズマアトマイズ法及び遠心力アトマイズ法を含む、公知のアトマイズ法で作製することができる。また、具体的な方法としては、例えば、特開2001-181703号公報、特開2007-113107号公報、特開2010-090421号公報、特開2010-144197号公報、特開2015-059253号公報、特開2015-096646号公報等に記載されている方法を、適宜選択及び適用することにより、当該金属粒子を作製することができる。 (Method for producing metal particles)
The metal particles according to the present invention can be produced by known atomization methods including, for example, a gas atomization method, a water atomization method, a plasma atomization method, and a centrifugal atomization method. As specific methods, for example, JP 2001-181703 A, JP 2007-113107 A, JP 2010-090421 A, JP 2010-144197 A, JP 2015-059253 A, and the like. The metal particles can be produced by appropriately selecting and applying the methods described in JP-A-2015-096646.
本発明に係る金属粒子は、例えば、ガスアトマイズ法、水アトマイズ法、プラズマアトマイズ法及び遠心力アトマイズ法を含む、公知のアトマイズ法で作製することができる。また、具体的な方法としては、例えば、特開2001-181703号公報、特開2007-113107号公報、特開2010-090421号公報、特開2010-144197号公報、特開2015-059253号公報、特開2015-096646号公報等に記載されている方法を、適宜選択及び適用することにより、当該金属粒子を作製することができる。 (Method for producing metal particles)
The metal particles according to the present invention can be produced by known atomization methods including, for example, a gas atomization method, a water atomization method, a plasma atomization method, and a centrifugal atomization method. As specific methods, for example, JP 2001-181703 A, JP 2007-113107 A, JP 2010-090421 A, JP 2010-144197 A, JP 2015-059253 A, and the like. The metal particles can be produced by appropriately selecting and applying the methods described in JP-A-2015-096646.
〔フラックス〕
本発明の金属粉末においては、上記説明した金属粒子の表面が、平均厚さが5~30nmの範囲内のフラックスにより被覆されている構成であることを特徴とする。 〔flux〕
The metal powder of the present invention is characterized in that the surface of the metal particles described above is coated with a flux having an average thickness in the range of 5 to 30 nm.
本発明の金属粉末においては、上記説明した金属粒子の表面が、平均厚さが5~30nmの範囲内のフラックスにより被覆されている構成であることを特徴とする。 〔flux〕
The metal powder of the present invention is characterized in that the surface of the metal particles described above is coated with a flux having an average thickness in the range of 5 to 30 nm.
金属表面にフラックスを付与することにより、金属粒子表面に形成されている酸化膜等を、フラックスの還元作用等により除去(清浄化作用ともいう。)する、レーザー照射時の再酸化防止機能を発現する、金属粒子の表面張力を低減する等の効果を発現し、金属酸化物による熱伝導低下等の阻害因子が除かれ、金属粒子に短時間でレーザー光のエネルギーを伝達することが可能となり、高品位の立体積層構造体を形成することができる。
By applying flux to the metal surface, the oxide film formed on the surface of the metal particles is removed (also referred to as cleaning action) by the flux reducing action, etc., and the anti-oxidation function at the time of laser irradiation is expressed. The effect of reducing the surface tension of the metal particles is expressed, and the obstruction factors such as the decrease in heat conduction due to the metal oxide are removed, and the energy of the laser beam can be transmitted to the metal particles in a short time. A high-quality three-dimensional laminated structure can be formed.
金属粒子の表面におけるフラックスの平均厚さは5~30nmの範囲内であることを特徴とするが、好ましくは10~20nmの範囲内である。
The average thickness of the flux on the surface of the metal particles is characterized by being in the range of 5 to 30 nm, but is preferably in the range of 10 to 20 nm.
フラックスの平均厚さが5nm未満になると、金属粒子表面の酸化膜の除去効果及び再酸化防止効果を発現させることが難しくなる。また、30nmを超えると、粒子表面に過剰にフラックスが残留することとなり、後処理等の観点から好ましくない。
If the average thickness of the flux is less than 5 nm, it becomes difficult to exhibit the effect of removing the oxide film on the surface of the metal particles and the effect of preventing reoxidation. On the other hand, if it exceeds 30 nm, the flux remains excessively on the particle surface, which is not preferable from the viewpoint of post-treatment and the like.
本発明に係るフラックスの平均厚さは下記の方法により求めることができる。
The average thickness of the flux according to the present invention can be obtained by the following method.
金属粉末の中心部を、集束イオンビーム加工装置(株式会社日立ハイテクサイエンス社製、SMI2050)を用いて切断して、粒子薄片を作製した。透過型電子顕微鏡(日本電子株式会社製、JEM-2010F)を用いて倍率10000倍で撮像した上記粒子の中心線断面画像について、被覆しているフラックスの厚さを10か所で測定し、その平均値1を求めた。次いで、この測定を50個の金属粉末について行い、得られた平均値1の全平均を求め、これをフラックスの平均厚さとして求め、これをフラックスの平均厚さとした。
The center part of the metal powder was cut using a focused ion beam processing apparatus (manufactured by Hitachi High-Tech Science Co., Ltd., SMI2050) to produce particle flakes. Using a transmission electron microscope (manufactured by JEOL Ltd., JEM-2010F), the thickness of the coated flux was measured at 10 locations on the center line cross-sectional image of the particles imaged at a magnification of 10,000 times. An average value of 1 was determined. Next, this measurement was performed on 50 metal powders, the total average of the obtained average values 1 was determined, and this was determined as the average thickness of the flux, which was defined as the average thickness of the flux.
本発明に適用が可能なフラックスとしては、金属粒子表面に形成されている酸化膜等に対する清浄化作用や、レーザー照射時の再酸化防止機能を発現する材料であれば、特に制限はないが、以下に示す各フラックスを適宜選択して適用することができる。
The flux applicable to the present invention is not particularly limited as long as it is a material that exhibits a cleaning action on an oxide film or the like formed on the surface of metal particles and a reoxidation preventing function during laser irradiation, Each flux shown below can be appropriately selected and applied.
本発明に係るフラックスとしては、大別して、1)樹脂系フラックス、2)水溶性有機フラックス、3)無機系フラックス等を挙げることができる。
The flux according to the present invention can be broadly classified into 1) resin flux, 2) water-soluble organic flux, 3) inorganic flux, and the like.
(1)樹脂系フラックス
樹脂系フラックスとしては、ロジン(松脂)やその変性樹脂又は合成樹脂などが挙げられる。 (1) Resin-based flux Examples of the resin-based flux include rosin (pine resin) and its modified resin or synthetic resin.
樹脂系フラックスとしては、ロジン(松脂)やその変性樹脂又は合成樹脂などが挙げられる。 (1) Resin-based flux Examples of the resin-based flux include rosin (pine resin) and its modified resin or synthetic resin.
天然樹脂であるロジン(松脂)は、アビエチン酸、パラストリン酸、デヒドロアビエチン酸、ネオアビエチン酸、イソピマール酸、ピマール酸等の有機酸を主成分とするものである。また、天然ロジンは軟化点が低く(70~80℃)、脆い性質であるため、ロジン誘導体が用いられており、例えば、水添ロジン(荒川化学社製 商品名:ハイペールCH)、重合ロジン(荒川化学社製 商品名:アラダイムR-140、軟化点:140℃)、酸変性ロジン(荒川化学社製 商品名:マルキードNo.33、軟化点:150℃)、超淡色ロジン(荒川化学社製 商品名:バインクリスタルKR-85、軟化点:85℃)等が挙げられる。
Rosin (pine resin), which is a natural resin, is composed mainly of organic acids such as abietic acid, parastrinic acid, dehydroabietic acid, neoabietic acid, isopimaric acid, and pimaric acid. Further, natural rosin has a low softening point (70 to 80 ° C.) and is brittle, so rosin derivatives are used. For example, hydrogenated rosin (trade name: Hyper CH manufactured by Arakawa Chemical Co., Ltd.), polymerized rosin ( Arakawa Chemical Co., Ltd. (trade name: Aradim R-140, softening point: 140 ° C.), acid-modified rosin (Arakawa Chemical Co., Ltd., trade name: Marquide No. 33, softening point: 150 ° C.), ultra light rosin (Arakawa Chemical Co. Trade name: Vine Crystal KR-85, softening point: 85 ° C.).
樹脂系フラックスは、そのまま金属粒子表面に付与したのち溶融して被膜を形成する方法であっても、あるいは、活性剤やその他の添加剤を加えたのち、アルコールやグリコールエーテル類などの溶媒に溶解したのち、スプレーコート法や転動流動層(マルチプレックス)などの公知の湿式塗布方法を適用して、シェル部としてフラックス被膜を形成する方法を適用することができ、その形成方法には、特段の制約はない。
Resin flux can be applied to the surface of metal particles and then melted to form a coating, or after adding an activator or other additive, it can be dissolved in a solvent such as alcohol or glycol ethers. Then, a known wet coating method such as a spray coating method or a rolling fluidized bed (multiplex) can be applied to apply a method for forming a flux film as the shell portion. There are no restrictions.
(2)水溶性有機フラックス
水溶性を有する有機フラックスとしては、例えば、有機酸、有機アミン・ハロゲン化水素酸塩、有機酸・アミン塩等を挙げることができるが、有機酸であることが好ましく、更には、金属粒子表面の酸化膜等の清浄化作用及び再酸化防止機能に優れる観点から、モノカルボン酸、又はジカルボン酸、トリカルボン酸、テトラカルボン酸等の多価カルボン酸を含んでいることが好ましい。本発明においては、金属粒子表面への活性作用が強まる点から、多価カルボン酸を含むことが好ましい。ジカルボン酸としては、例えば、シュウ酸、グルタル酸、アジピン酸、コハク酸、セバシン酸、マロン酸、マレイン酸、フマル酸、フタル酸、ピメリン酸、スベリン酸、アゼライン酸、シトラコン酸、α-ケトグルタル酸、ジグリコール酸、チオジグリコール酸、ジチオジグリコール酸、4-シクロヘキセン-1,2-ジカルボン酸等が挙げられ、トリカルボン酸としては、例えば、トリメリット酸、クエン酸、イソクエン酸、シクロヘキサン-1,2,4-トリカルボン酸、1,2,3-プロパントリカルボン酸等が挙げられ、そしてテトラカルボン酸としては、例えば、エチレンテトラカルボン酸、1,2,3,4-ブタンテトラカルボン酸等が挙げられる。 (2) Water-soluble organic flux Examples of the water-soluble organic flux include organic acids, organic amines / hydrohalides, and organic acids / amine salts. Organic acids are preferred. Furthermore, from the viewpoint of excellent cleaning action of the oxide film etc. on the metal particle surface and re-oxidation preventing function, it should contain monocarboxylic acid or polycarboxylic acid such as dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid, etc. Is preferred. In the present invention, it is preferable that a polyvalent carboxylic acid is contained from the viewpoint of enhancing the active action on the surface of the metal particles. Examples of the dicarboxylic acid include oxalic acid, glutaric acid, adipic acid, succinic acid, sebacic acid, malonic acid, maleic acid, fumaric acid, phthalic acid, pimelic acid, suberic acid, azelaic acid, citraconic acid, α-ketoglutaric acid , Diglycolic acid, thiodiglycolic acid, dithiodiglycolic acid, 4-cyclohexene-1,2-dicarboxylic acid and the like. Examples of the tricarboxylic acid include trimellitic acid, citric acid, isocitric acid, cyclohexane-1 1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid and the like, and examples of the tetracarboxylic acid include ethylenetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid and the like. Can be mentioned.
水溶性を有する有機フラックスとしては、例えば、有機酸、有機アミン・ハロゲン化水素酸塩、有機酸・アミン塩等を挙げることができるが、有機酸であることが好ましく、更には、金属粒子表面の酸化膜等の清浄化作用及び再酸化防止機能に優れる観点から、モノカルボン酸、又はジカルボン酸、トリカルボン酸、テトラカルボン酸等の多価カルボン酸を含んでいることが好ましい。本発明においては、金属粒子表面への活性作用が強まる点から、多価カルボン酸を含むことが好ましい。ジカルボン酸としては、例えば、シュウ酸、グルタル酸、アジピン酸、コハク酸、セバシン酸、マロン酸、マレイン酸、フマル酸、フタル酸、ピメリン酸、スベリン酸、アゼライン酸、シトラコン酸、α-ケトグルタル酸、ジグリコール酸、チオジグリコール酸、ジチオジグリコール酸、4-シクロヘキセン-1,2-ジカルボン酸等が挙げられ、トリカルボン酸としては、例えば、トリメリット酸、クエン酸、イソクエン酸、シクロヘキサン-1,2,4-トリカルボン酸、1,2,3-プロパントリカルボン酸等が挙げられ、そしてテトラカルボン酸としては、例えば、エチレンテトラカルボン酸、1,2,3,4-ブタンテトラカルボン酸等が挙げられる。 (2) Water-soluble organic flux Examples of the water-soluble organic flux include organic acids, organic amines / hydrohalides, and organic acids / amine salts. Organic acids are preferred. Furthermore, from the viewpoint of excellent cleaning action of the oxide film etc. on the metal particle surface and re-oxidation preventing function, it should contain monocarboxylic acid or polycarboxylic acid such as dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid, etc. Is preferred. In the present invention, it is preferable that a polyvalent carboxylic acid is contained from the viewpoint of enhancing the active action on the surface of the metal particles. Examples of the dicarboxylic acid include oxalic acid, glutaric acid, adipic acid, succinic acid, sebacic acid, malonic acid, maleic acid, fumaric acid, phthalic acid, pimelic acid, suberic acid, azelaic acid, citraconic acid, α-ketoglutaric acid , Diglycolic acid, thiodiglycolic acid, dithiodiglycolic acid, 4-cyclohexene-1,2-dicarboxylic acid and the like. Examples of the tricarboxylic acid include trimellitic acid, citric acid, isocitric acid, cyclohexane-1 1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid and the like, and examples of the tetracarboxylic acid include ethylenetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid and the like. Can be mentioned.
(3)無機フラックス
無機フラックスとしては、例えば、無機酸、ホウ化物、ハロゲン化物を挙げることができる。 (3) Inorganic flux Examples of the inorganic flux include inorganic acids, borides, and halides.
無機フラックスとしては、例えば、無機酸、ホウ化物、ハロゲン化物を挙げることができる。 (3) Inorganic flux Examples of the inorganic flux include inorganic acids, borides, and halides.
ホウ化物は、ホウ素とそれより電気陰性度が小さい元素との間の電解質(化合物)の総称である。例えば、ホウ酸(H3BO3)、ホウ砂(Na2B4O7)、酸化ホウ素(B2OB)、ホウ酸カリウム(K2B4O7)、などが挙げられる。
A boride is a general term for an electrolyte (compound) between boron and an element having a lower electronegativity. For example, boric acid (H 3 BO 3 ), borax (Na 2 B 4 O 7 ), boron oxide (B 2 OB), potassium borate (K 2 B 4 O 7 ), and the like can be given.
また、ホウ酸塩としては、オルトホウ酸塩、二ホウ酸塩、メタホウ酸塩、四ホウ酸塩、五ホウ酸塩及び八ホウ酸塩などがあり、それらの塩としては、リチウム、ナトリウム、カリウム、マグネシウム、カルシウム、バリウム、クロム、鉄、コバルト、ニッケル、マンガン、珪素、鉛、銅、チタン及びアルミニウムなどの金属のホウ酸塩類が挙げられる。
In addition, as borate, there are orthoborate, diborate, metaborate, tetraborate, pentaborate and octaborate, and as salts thereof, lithium, sodium, potassium And borate salts of metals such as magnesium, calcium, barium, chromium, iron, cobalt, nickel, manganese, silicon, lead, copper, titanium and aluminum.
また、フッ素、塩素、臭素、ヨウ素などのハロゲン元素を含むハロゲン化物としては、例えば、フッ化物としては、フッ化カリウム(KF)、フッ化ナトリウム(NaF)、酸性フッ化ナトリウム(NaHF2)、ホウフッ化カリウム(KBF4)、ホウフッ化ナトリウム(NaBF4)、ホウフッ化アンモニウム(NH4BF4)、ケイフッ化カリウム(K2SiF6)、フッ化アルミナトリウム(液晶石、Na3ALF6)、酸性フッ化カリウム(HBF4)、フッ化アルミカリウム(カリ永晶石、K3ALF6)、ケイフッ化ナトリウム(NaHF6)などが挙げられる。
Examples of halides containing halogen elements such as fluorine, chlorine, bromine and iodine include, for example, fluorides such as potassium fluoride (KF), sodium fluoride (NaF), acidic sodium fluoride (NaHF 2 ), Potassium borofluoride (KBF 4 ), sodium borofluoride (NaBF 4 ), ammonium borofluoride (NH 4 BF 4 ), potassium silicofluoride (K 2 SiF 6 ), sodium aluminum fluoride (liquid crystal stone, Na 3 ALF 6 ), Examples thereof include acidic potassium fluoride (HBF 4 ), potassium aluminum fluoride (potassium peridotite, K 3 ALF 6 ), sodium silicofluoride (NaHF 6 ), and the like.
また、塩化物としては、塩化カリウム(KCl)、塩化亜鉛(ZnCl)、塩化アンモニウム(NH4Cl)などがある。臭化物としては臭化水素酸(HBr)、臭化カリウム(KBr)、ヨウ化物としてはヨウ化アンモニウム(NH4I)などが挙げられる。
Examples of the chloride include potassium chloride (KCl), zinc chloride (ZnCl), and ammonium chloride (NH 4 Cl). Examples of bromide include hydrobromic acid (HBr) and potassium bromide (KBr), and examples of iodide include ammonium iodide (NH 4 I).
本発明においては、特に、フラックスとしては、無機フラックスを適用することが好ましく、更には、ホウ酸、ホウ酸塩、ホウ砂、フッ化物及び塩化物から選ばれる少なくとも一種であることが好ましい。
In the present invention, in particular, an inorganic flux is preferably used as the flux, and at least one selected from boric acid, borate, borax, fluoride, and chloride is preferable.
無機系フラックスについても、そのまま金属粒子表面に付与したのち溶融して被膜を形成する方法であっても、あるいは、活性剤やその他の添加剤を加えたのち、アルコールやグリコールエーテル類などの溶媒に溶解したのち、スプレーコート法や転動流動層(マルチプレックス)などの公知の湿式塗布方法を適用して、シェル部としてフラックス被膜を形成する方法を適用することができ、その形成方法には、特段の制約はない。
As for inorganic flux, it can be applied to the surface of the metal particles as it is and then melted to form a film, or after adding an activator or other additive, it is added to a solvent such as alcohol or glycol ethers. After dissolution, a known wet coating method such as spray coating or rolling fluidized bed (multiplex) can be applied, and a method of forming a flux film as a shell part can be applied. There are no particular restrictions.
〔金属粉末の製造方法〕
金属粉末は、金属粒子の表面に、厚さ5~30nmの範囲内の薄層のフラックスを被覆させることにより製造する。 [Production method of metal powder]
The metal powder is produced by coating the surface of the metal particles with a thin layer of flux having a thickness in the range of 5 to 30 nm.
金属粉末は、金属粒子の表面に、厚さ5~30nmの範囲内の薄層のフラックスを被覆させることにより製造する。 [Production method of metal powder]
The metal powder is produced by coating the surface of the metal particles with a thin layer of flux having a thickness in the range of 5 to 30 nm.
具体的には、金属粉末は、1)金属粒子及び被覆させるフラックスを準備する工程と、2)金属粒子の表面にフラックスを固着させる工程と、によって製造することができる。
Specifically, the metal powder can be manufactured by 1) a step of preparing metal particles and a flux to be coated, and 2) a step of fixing the flux to the surface of the metal particles.
1)金属粒子及びフラックスを準備する工程
この工程では、個数平均粒子径が5~100μmの範囲内である金属粒子と、フラックスを準備する。 1) Step of preparing metal particles and flux In this step, metal particles having a number average particle diameter in the range of 5 to 100 μm and a flux are prepared.
この工程では、個数平均粒子径が5~100μmの範囲内である金属粒子と、フラックスを準備する。 1) Step of preparing metal particles and flux In this step, metal particles having a number average particle diameter in the range of 5 to 100 μm and a flux are prepared.
金属粒子としては、更には、平均円形度が0.90~0.98の範囲内であること、あるいは粒度分布における変動係数(CV値)が、15%以下であることが好ましい形態である。
Further, the metal particles preferably have an average circularity in the range of 0.90 to 0.98 or a variation coefficient (CV value) in the particle size distribution of 15% or less.
また、金属粒子としては、鉄、鉄合金、ニッケル、ニッケル合金、コバルト、コバルト合金、銅、銅合金、アルミニウム及びアルミニウム合金から選ばれる少なくとも一種の金属材料を含むこと形態であることが好ましく、また、フラックスとしては、ホウ酸、ホウ化物、フッ化物及び塩化物から選ばれる少なくとも一種であることが好ましい。
The metal particles preferably include at least one metal material selected from iron, iron alloy, nickel, nickel alloy, cobalt, cobalt alloy, copper, copper alloy, aluminum, and aluminum alloy. The flux is preferably at least one selected from boric acid, boride, fluoride and chloride.
上記条件が満たされる限りにおいて、金属粒子及びフラックスは、市販のものを購入してもよいし、例えば、アトマイズ法などの公知の方法で作製してもよい。また、メンブレンフィルターなどの公知の篩によって造粒後の粒子を分級したものを用いてもよい。
As long as the above conditions are satisfied, commercially available metal particles and flux may be purchased, or may be produced by a known method such as an atomizing method. Moreover, you may use what classified the particle | grains after granulation by well-known sieves, such as a membrane filter.
金属粒子に対するフラックスの比率は、特に制限はなく、上記で規定する厚さが5~30nmの範囲内となるように、金属粒子に対するフラックスの準備量を設定する。
The ratio of the flux with respect to the metal particles is not particularly limited, and the amount of flux to be prepared with respect to the metal particles is set so that the thickness specified above is in the range of 5 to 30 nm.
上記条件が満たされる限りにおいて、金属粒子及び低熱伝導粒子は、市販のものを購入してもよいし、たとえばアトマイズ法などの公知の方法で作製してもよい。また、メンブレンフィルターなどの公知の篩によって造粒後の粒子を分級したものを用いてもよい。
As long as the above conditions are satisfied, the metal particles and the low thermal conductive particles may be purchased commercially or may be produced by a known method such as an atomizing method. Moreover, you may use what classified the particle | grains after granulation by well-known sieves, such as a membrane filter.
2)金属粒子表面にフラックスを被覆させる工程
当該工程は、金属粒子の表面にフラックスを固着させる工程である。当工程においては、金属粒子の表面に他の粒子を固着させるために用いられる公知の方法を適宜選択して行うことができる。 2) Step of coating flux on metal particle surface This step is a step of fixing flux on the surface of metal particles. In this step, a known method used for fixing other particles to the surface of the metal particles can be selected as appropriate.
当該工程は、金属粒子の表面にフラックスを固着させる工程である。当工程においては、金属粒子の表面に他の粒子を固着させるために用いられる公知の方法を適宜選択して行うことができる。 2) Step of coating flux on metal particle surface This step is a step of fixing flux on the surface of metal particles. In this step, a known method used for fixing other particles to the surface of the metal particles can be selected as appropriate.
例えば、フラックスを溶媒等で溶解した塗布液を用いる湿式コート法(例えば、スプレーコート法、転動流動層方式等)、金属粒子とフラックスとを撹拌して機械的衝撃により結合させる乾式コート法、あるいはこれらの方法の組み合わせなどによって行うことができる。
For example, a wet coating method using a coating solution in which a flux is dissolved with a solvent (for example, a spray coating method, a rolling fluidized bed method, etc.), a dry coating method in which metal particles and a flux are stirred and bonded by mechanical impact, Or it can carry out by the combination of these methods.
湿式コート法を採用する場合、金属粒子の表面に、フラックスを含む塗布液をスプレー塗布してもよいし、金属粒子を上記塗布液中に浸漬してもよい。
When the wet coating method is employed, a coating solution containing a flux may be spray-coated on the surface of the metal particles, or the metal particles may be immersed in the coating solution.
上記乾式コート法は、例えば、金属粒子及びフラックスを通常の混合撹拌装置で撹拌して均一に混合し、得られた混合物を通常の回転翼型混合撹拌装置で5~40分程度撹拌及び混合する方法とすることができる。
In the dry coating method, for example, the metal particles and the flux are stirred and mixed uniformly with a normal mixing and stirring device, and the resulting mixture is stirred and mixed for about 5 to 40 minutes with a normal rotary blade type mixing and stirring device. It can be a method.
〔その他の添加剤〕
また、金属粉末には、本発明の目的効果を損なわない範囲で、金属粒子及びフラックスの他に、各種添加剤を適用することができる。 [Other additives]
In addition to the metal particles and the flux, various additives can be applied to the metal powder as long as the object effects of the present invention are not impaired.
また、金属粉末には、本発明の目的効果を損なわない範囲で、金属粒子及びフラックスの他に、各種添加剤を適用することができる。 [Other additives]
In addition to the metal particles and the flux, various additives can be applied to the metal powder as long as the object effects of the present invention are not impaired.
(レーザー光吸収剤)
金属粉末に構成されている薄層に照射するレーザー光の光エネルギーをより効率的に熱エネルギーに変換する観点から、金属粉末には、レーザー光吸収剤を更に含んでもよい。レーザー光吸収剤は、使用する波長のレーザー光を吸収して、発熱する材料であればよい。このようなレーザー光吸収剤としては、例えば、カーボン粉末、ナイロン樹脂粉末、顔料及び染料等を挙げることができる。これらのレーザー光吸収剤は、一種類のみ用いても、二種類を組み合わせて用いてもよい。 (Laser light absorber)
From the viewpoint of more efficiently converting the light energy of the laser light applied to the thin layer formed of the metal powder into thermal energy, the metal powder may further include a laser light absorber. The laser light absorber may be a material that absorbs laser light having a wavelength to be used and generates heat. Examples of such laser light absorbers include carbon powder, nylon resin powder, pigments and dyes. These laser light absorbers may be used alone or in combination of two kinds.
金属粉末に構成されている薄層に照射するレーザー光の光エネルギーをより効率的に熱エネルギーに変換する観点から、金属粉末には、レーザー光吸収剤を更に含んでもよい。レーザー光吸収剤は、使用する波長のレーザー光を吸収して、発熱する材料であればよい。このようなレーザー光吸収剤としては、例えば、カーボン粉末、ナイロン樹脂粉末、顔料及び染料等を挙げることができる。これらのレーザー光吸収剤は、一種類のみ用いても、二種類を組み合わせて用いてもよい。 (Laser light absorber)
From the viewpoint of more efficiently converting the light energy of the laser light applied to the thin layer formed of the metal powder into thermal energy, the metal powder may further include a laser light absorber. The laser light absorber may be a material that absorbs laser light having a wavelength to be used and generates heat. Examples of such laser light absorbers include carbon powder, nylon resin powder, pigments and dyes. These laser light absorbers may be used alone or in combination of two kinds.
レーザー光吸収剤の量は、金属粉末の溶融及び結合が容易になる範囲で適宜設定することができ、例えば、金属粉末の全質量に対して、0質量%より多く3質量%未満の範囲内で設定することができる。
The amount of the laser light absorber can be appropriately set within a range in which the metal powder can be easily melted and bonded. Can be set.
(流動助剤)
薄層形成時の金属粉末の流動性をより向上させ、立体積層造形物の製造時における金属粉末の取り扱いを容易にする観点から、金属粉末は流動助剤を含んでもよい。流動助剤は、摩擦係数が小さく、自己潤滑性を有する材料であり、このような流動助剤の例には、二酸化ケイ素や窒化ホウ素が含まれる。これらの流動助剤は、一種類のみ用いても、二種類以上を組み合わせて用いてもよい。上記金属粉末は、流動助剤によって流動性が高まっても、金属粉末が帯電しにくく、薄層を形成するときに金属粉末をさらに密に充填させることができる。 (Flow aid)
From the viewpoint of further improving the fluidity of the metal powder during the formation of the thin layer and facilitating the handling of the metal powder during the production of the three-dimensional layered object, the metal powder may contain a flow aid. The flow aid is a material having a small coefficient of friction and a self-lubricating property, and examples of such flow aid include silicon dioxide and boron nitride. These flow aids may be used alone or in combination of two or more. Even if the fluidity of the metal powder is increased by the flow aid, the metal powder is difficult to be charged, and the metal powder can be filled more densely when forming a thin layer.
薄層形成時の金属粉末の流動性をより向上させ、立体積層造形物の製造時における金属粉末の取り扱いを容易にする観点から、金属粉末は流動助剤を含んでもよい。流動助剤は、摩擦係数が小さく、自己潤滑性を有する材料であり、このような流動助剤の例には、二酸化ケイ素や窒化ホウ素が含まれる。これらの流動助剤は、一種類のみ用いても、二種類以上を組み合わせて用いてもよい。上記金属粉末は、流動助剤によって流動性が高まっても、金属粉末が帯電しにくく、薄層を形成するときに金属粉末をさらに密に充填させることができる。 (Flow aid)
From the viewpoint of further improving the fluidity of the metal powder during the formation of the thin layer and facilitating the handling of the metal powder during the production of the three-dimensional layered object, the metal powder may contain a flow aid. The flow aid is a material having a small coefficient of friction and a self-lubricating property, and examples of such flow aid include silicon dioxide and boron nitride. These flow aids may be used alone or in combination of two or more. Even if the fluidity of the metal powder is increased by the flow aid, the metal powder is difficult to be charged, and the metal powder can be filled more densely when forming a thin layer.
流動助剤の量は、金属粉末の流動性がより向上し、かつ、金属粉末の溶融結合が十分に生じる範囲で適宜設定することができ、例えば、金属粉末の全質量に対して、0.1質量%より多く2.0質量%未満とすることができる。
The amount of the flow aid can be appropriately set within the range in which the fluidity of the metal powder is further improved and the melt bonding of the metal powder is sufficiently generated. It can be more than 1% by mass and less than 2.0% by mass.
《粉末焼結積層造形物の製造方法》
本発明の粉末焼結積層造形物の製造方法は、上記説明した本発明の金属粉末を用いて立体積層造形物を製造する粉末焼結積層造形物の製造方法であり、具体的には、少なくとも、前記金属粉末を薄層に展開する薄層形成工程と、前記薄層を構成する金属粉末に、造形対象物の断面形状に対応する形状パターンでレーザー光を照射して、前記金属粉末を結合させる断面形状形成工程を有し、前記薄層形成工程と前記断面形状形成工程とを順次繰り返すことにより、立体積層造形物を製造することを特徴とする方法である。 << Production Method of Powder Sintered Laminate Model >>
The method for producing a powder sintered laminate model of the present invention is a method for producing a powder sintered model by using the metal powder of the present invention described above, and specifically, at least, A thin layer forming step of developing the metal powder into a thin layer, and irradiating the metal powder constituting the thin layer with a laser beam in a shape pattern corresponding to a cross-sectional shape of the object to be modeled to combine the metal powder A method of manufacturing a three-dimensional layered object by sequentially repeating the thin layer forming step and the cross sectional shape forming step.
本発明の粉末焼結積層造形物の製造方法は、上記説明した本発明の金属粉末を用いて立体積層造形物を製造する粉末焼結積層造形物の製造方法であり、具体的には、少なくとも、前記金属粉末を薄層に展開する薄層形成工程と、前記薄層を構成する金属粉末に、造形対象物の断面形状に対応する形状パターンでレーザー光を照射して、前記金属粉末を結合させる断面形状形成工程を有し、前記薄層形成工程と前記断面形状形成工程とを順次繰り返すことにより、立体積層造形物を製造することを特徴とする方法である。 << Production Method of Powder Sintered Laminate Model >>
The method for producing a powder sintered laminate model of the present invention is a method for producing a powder sintered model by using the metal powder of the present invention described above, and specifically, at least, A thin layer forming step of developing the metal powder into a thin layer, and irradiating the metal powder constituting the thin layer with a laser beam in a shape pattern corresponding to a cross-sectional shape of the object to be modeled to combine the metal powder A method of manufacturing a three-dimensional layered object by sequentially repeating the thin layer forming step and the cross sectional shape forming step.
〔金属粉末による粉末焼結積層造形物の製造方法〕
(粉末焼結積層造形物の製造フロー)
はじめに、本発明の金属粉末を用いて立体積層造形物を製造する本発明の粉末焼結積層造形物の製造方法の技術的特徴について、図を交えて説明する。 [Production Method of Powder Sintered Laminate Model with Metallic Powder]
(Production flow of powder-sintered layered product)
First, the technical features of the method for producing a powder sintered laminated shaped article of the present invention for producing a three-dimensional laminated shaped article using the metal powder of the present invention will be described with reference to the drawings.
(粉末焼結積層造形物の製造フロー)
はじめに、本発明の金属粉末を用いて立体積層造形物を製造する本発明の粉末焼結積層造形物の製造方法の技術的特徴について、図を交えて説明する。 [Production Method of Powder Sintered Laminate Model with Metallic Powder]
(Production flow of powder-sintered layered product)
First, the technical features of the method for producing a powder sintered laminated shaped article of the present invention for producing a three-dimensional laminated shaped article using the metal powder of the present invention will be described with reference to the drawings.
本発明の粉末焼結積層造形物の製造方法は、金属粒子を含む金属粉末を薄層に展開する薄層形成工程1と、形成された薄層に、造形対象物の断面形状に対応する形状にレーザー光を照射して、該金属粉末を結合させる断面形状形成工程とを順次繰り返すことを特徴としている。
The method for producing a powder sintered laminate model of the present invention includes a thin layer forming step 1 in which a metal powder containing metal particles is developed into a thin layer, and a shape corresponding to the cross-sectional shape of the modeling target in the formed thin layer. And a step of forming a cross-sectional shape in which the metal powder is bonded by sequentially irradiating with laser light.
図2A及び図2Bは、従来法と本発明における金属粉末を用いた粉末焼結積層造形物の製造方法の特徴を説明するための製造フロー図である。
FIG. 2A and FIG. 2B are production flow diagrams for explaining the features of the conventional method and the method for producing a powder sintered laminate model using metal powder in the present invention.
図2Aは、従来の立体積層造形物の形成方法の一例を示す図である。
FIG. 2A is a diagram illustrating an example of a conventional method for forming a three-dimensional layered object.
第1ステップ(a)である「第1の薄層形成工程」では、造形ステージ(6)上に、粉末リコーター(7)を用いて、粉末供給部(不図示)から供給された金属粒子(2)とその表面に金属酸化被膜(4)を有する複数の金属粉末(1B)を平らに敷き詰めて、第1の薄層(5B)を形成する。
In the “first thin layer forming step” that is the first step (a), metal particles (not shown) supplied from a powder supply unit (not shown) using a powder recoater (7) on the modeling stage (6). 2) and a plurality of metal powders (1B) having a metal oxide film (4) on the surface thereof are laid flat to form a first thin layer (5B).
次いで、第2ステップ(b)である「レーザー光照射・焼結工程」では、形成した第1の薄層(5B)に対し、レーザー光(L)を照射して、金属粉末を焼結して、焼結金属粉末(1C)による造形物層(5C)を形成する。この時、大気圧環境下で金属粉末(1B)にレーザー光(L)を照射するため、金属粉末(1B)を構成している金属粒子(2)の最表面は、大気と接することとなるため、その粒子表面には薄い金属酸化被膜(4)が形成されている。この金属酸化被膜(4)は、金属粒子(2)より融点が高く、熱伝導性が低くなるため、レーザー光(L)の照射による焼結時に迅速に熱を伝達することができなくなる。溶融金属の表面張力は、温度の上昇と共に低下する特性を有しているが、レーザー光(L)の照射による熱エネルギーが迅速に伝達されないと、金属粒子(2)として、溶融により表面張力が低下する特性を発現する温度領域に到達することができないため、濡れ拡がる特性が不十分となる。その結果、金属粉末は、第2ステップで示すように粒子が凝集して2次粒子塊を形成するため、薄層表面には凹凸パターンが形成され、平面性に乏しい造形物層(5C)となる。
Next, in the “laser light irradiation / sintering process” as the second step (b), the formed first thin layer (5B) is irradiated with laser light (L) to sinter the metal powder. Then, a shaped article layer (5C) is formed from the sintered metal powder (1C). At this time, since the metal powder (1B) is irradiated with laser light (L) under an atmospheric pressure environment, the outermost surface of the metal particles (2) constituting the metal powder (1B) comes into contact with the atmosphere. Therefore, a thin metal oxide film (4) is formed on the particle surface. Since the metal oxide film (4) has a higher melting point than the metal particles (2) and has a low thermal conductivity, heat cannot be transferred quickly during sintering by irradiation with the laser beam (L). The surface tension of the molten metal has a characteristic that it decreases as the temperature rises. However, if the thermal energy due to the irradiation with the laser beam (L) is not rapidly transmitted, the surface tension of the molten metal as a metal particle (2) is reduced by melting. Since it is not possible to reach the temperature range in which the deteriorating characteristic is expressed, the characteristic of spreading and spreading becomes insufficient. As a result, as shown in the second step, the metal powder aggregates particles to form a secondary particle lump, so that a concavo-convex pattern is formed on the surface of the thin layer, and the shaped object layer (5C) having poor planarity Become.
そのため、次工程の第3ステップ(c)である「第2の薄層の形成工程」では、表面に凹凸構造を有する造形物層(5C)上に、金属粉末(1B)により第2の薄層(8B)を形成するため、その表面にも、同様の凹凸パターンが反映されるため、最終的に形成する立体積層造形物の表面精度が低下することになり、所望の形成の立体積層造形物を得ることができなくなる。これら凹凸パターンの形成は、レーザー光(L)の照射を高速にすると、より顕著に発現しやすくなるため、立体積層造形物の形成を高速化する上では、問題となっていた。
Therefore, in the “second thin layer forming step”, which is the third step (c) of the next step, the second thin layer is formed by the metal powder (1B) on the shaped article layer (5C) having a concavo-convex structure on the surface. Since the same uneven pattern is also reflected on the surface of the layer (8B), the surface accuracy of the three-dimensional layered object to be finally formed is lowered, and the three-dimensional layered object having a desired formation is formed. You can't get things. The formation of these concavo-convex patterns has become a problem in speeding up the formation of a three-dimensional layered object, since it becomes more prominent when the laser beam (L) is irradiated at high speed.
これに対し、図2Bは、本発明の金属粉末を適用した立体積層造形物の形成方法を示してある。
In contrast, FIG. 2B shows a method for forming a three-dimensional layered object to which the metal powder of the present invention is applied.
図2Bで示す第1ステップ(a)である第1の薄層形成工程では、造形ステージ(6)上に、粉末リコーター(7)を用いて、平均円形度が0.90~0.98の範囲内で、かつ変動係数(CV値)が15%以下である球状の金属粒子(2)と、その表面にフラックス(3)を被覆している金属粉末(1)を適用することにより、最密充填に近い条件で、表面均一性に優れた第1の薄層(5)を形成する。
In the first thin layer forming process, which is the first step (a) shown in FIG. 2B, the average circularity is 0.90 to 0.98 using the powder recoater (7) on the modeling stage (6). By applying spherical metal particles (2) within a range and having a coefficient of variation (CV value) of 15% or less, and metal powder (1) covering the surface with flux (3), A first thin layer (5) excellent in surface uniformity is formed under conditions close to close packing.
本発明の粉末焼結積層造形物の製造工程のうち、薄層形成工程1では、一回の薄層の厚さは0.01~0.3mmの範囲内であることが好ましく、より精密な造形物を得るためには、0.01~0.1mmの範囲内であることが好ましい。
Of the manufacturing steps of the powder sintered laminate model of the present invention, in the thin layer forming step 1, the thickness of one thin layer is preferably in the range of 0.01 to 0.3 mm, and more precise. In order to obtain a shaped article, it is preferably within a range of 0.01 to 0.1 mm.
薄層状に展開する方法は、特に制限はないが、例えば、金属粉末焼結材料を上方より散布する方法がある。また、供給した金属粉末焼結材料をローラーでならして均一な厚さの薄層状とする方法もある。ローラーでならす方法は、均一な厚みで空隙率の低い薄層を再現性良く形成することができるので、好適に用いることができる。
There is no particular limitation on the method of developing the thin layer, but for example, there is a method of spraying a metal powder sintered material from above. There is also a method in which the supplied metal powder sintered material is leveled with a roller to form a thin layer with a uniform thickness. The method of leveling with a roller can be preferably used because a thin layer with a uniform thickness and a low porosity can be formed with good reproducibility.
次いで、第2ステップ(b)であるレーザー光照射・焼結工程で、形成した第1の薄層(5)に対し、レーザー光(L)を照射して、金属粉末(1)を焼結して、焼結金属粉末(1A)による造形物層(5A)を形成する。この時、金属粉末(1)を構成する金属粒子(2)にレーザー光(L)を照射した時に、金属粒子(2)表面に存在している金属酸化物膜を、フラックス(3)の還元作用等により除去することにより、上記説明したような金属酸化物による熱伝導低下等の阻害因子が除かれ、金属粒子(2)に短時間でレーザー光(L)のエネルギーを伝達することができ、その結果、迅速に金属粒子(2)を含む金属粉体(1)の表面張力が低下する温度領域に到達させ、金属粉末(1)が短時間で安定して濡れ拡がることができ、凹凸がなく、表面平滑性に優れた造形物層(5A)を形成することができる。
Next, in the laser light irradiation / sintering process, which is the second step (b), the first thin layer (5) formed is irradiated with laser light (L) to sinter the metal powder (1). Then, a model layer (5A) is formed from the sintered metal powder (1A). At this time, when the metal particles (2) constituting the metal powder (1) are irradiated with laser light (L), the metal oxide film existing on the surface of the metal particles (2) is reduced to the flux (3). By removing by action, etc., the obstruction factors such as the decrease in heat conduction due to the metal oxide as described above are removed, and the energy of the laser beam (L) can be transmitted to the metal particles (2) in a short time. As a result, the metal powder (1) containing the metal particles (2) can quickly reach the temperature range where the surface tension is lowered, and the metal powder (1) can be stably spread in a short time. There is not, and a modeling thing layer (5A) excellent in surface smoothness can be formed.
その結果、第3ステップ(c)である第2の薄層の形成工程でも、平面性に優れた造形物層(5A)上に、金属粉末(1)により第2の薄層(8A)を形成した場合でも、下層である造形物層(5A)の優れた平面性が反映されるため、最終的に立体積層造形物を高速かつ高精度で形成することができる。
As a result, the second thin layer (8A) is formed by the metal powder (1) on the model layer (5A) excellent in flatness even in the second thin layer forming step which is the third step (c). Even when formed, since the excellent planarity of the modeled object layer (5A) as the lower layer is reflected, it is possible to finally form a three-dimensional layered modeled object at high speed and with high accuracy.
(立体積層造形物の製造条件)
〈形成する薄層の厚さ〉
図2Bに示す本発明の粉末焼結積層造形物の製造方法において、形成する薄層の厚さは、立体積層造形物を構成する造形物層の1層分の厚さと同じとする。薄層の厚さは、製造しようとする立体積層造形物の形状などに応じて任意に設定することができるが、通常、0.01~0.30mmの範囲内であることが好ましく、より精密な造形物を得るためには、0.05~0.10mmの範囲内であることが好ましい。薄層の厚さを0.01mm以上とすることで、次の薄層を形成するためのレーザー光照射によって下の薄層の金属粒子が再度、焼結又は溶融結合されることを防ぐことができる。薄層の厚さを0.3mm以下とすることで、レーザー光を対象とする薄層の下部まで伝導させて、薄層を構成する金属粉末に含まれる金属粒子を、厚さ方向の全体にわたって十分に焼結又は溶融結合させることができる。 (Conditions for manufacturing three-dimensional layered objects)
<Thickness of thin layer to be formed>
In the manufacturing method of the powder sintered laminate model of the present invention shown in FIG. 2B, the thickness of the thin layer to be formed is the same as the thickness of one layer of the model layer constituting the three-dimensional laminate model. The thickness of the thin layer can be arbitrarily set according to the shape of the three-dimensional layered object to be manufactured, but it is usually preferably in the range of 0.01 to 0.30 mm, and more precise. In order to obtain a simple shaped article, it is preferably in the range of 0.05 to 0.10 mm. By making the thickness of the thin layer 0.01 mm or more, it is possible to prevent the metal particles of the lower thin layer from being sintered or melt-bonded again by laser light irradiation for forming the next thin layer. it can. By setting the thickness of the thin layer to 0.3 mm or less, the laser light is conducted to the lower part of the thin layer, and the metal particles included in the metal powder constituting the thin layer are spread over the entire thickness direction. It can be fully sintered or melt bonded.
〈形成する薄層の厚さ〉
図2Bに示す本発明の粉末焼結積層造形物の製造方法において、形成する薄層の厚さは、立体積層造形物を構成する造形物層の1層分の厚さと同じとする。薄層の厚さは、製造しようとする立体積層造形物の形状などに応じて任意に設定することができるが、通常、0.01~0.30mmの範囲内であることが好ましく、より精密な造形物を得るためには、0.05~0.10mmの範囲内であることが好ましい。薄層の厚さを0.01mm以上とすることで、次の薄層を形成するためのレーザー光照射によって下の薄層の金属粒子が再度、焼結又は溶融結合されることを防ぐことができる。薄層の厚さを0.3mm以下とすることで、レーザー光を対象とする薄層の下部まで伝導させて、薄層を構成する金属粉末に含まれる金属粒子を、厚さ方向の全体にわたって十分に焼結又は溶融結合させることができる。 (Conditions for manufacturing three-dimensional layered objects)
<Thickness of thin layer to be formed>
In the manufacturing method of the powder sintered laminate model of the present invention shown in FIG. 2B, the thickness of the thin layer to be formed is the same as the thickness of one layer of the model layer constituting the three-dimensional laminate model. The thickness of the thin layer can be arbitrarily set according to the shape of the three-dimensional layered object to be manufactured, but it is usually preferably in the range of 0.01 to 0.30 mm, and more precise. In order to obtain a simple shaped article, it is preferably in the range of 0.05 to 0.10 mm. By making the thickness of the thin layer 0.01 mm or more, it is possible to prevent the metal particles of the lower thin layer from being sintered or melt-bonded again by laser light irradiation for forming the next thin layer. it can. By setting the thickness of the thin layer to 0.3 mm or less, the laser light is conducted to the lower part of the thin layer, and the metal particles included in the metal powder constituting the thin layer are spread over the entire thickness direction. It can be fully sintered or melt bonded.
上記観点からは、薄層の厚さは0.02~0.30mmの範囲内であることがより好ましく、0.03~0.20mmの範囲内であることが更に好ましく、0.05~0.10mmの範囲内であることが特に好ましい。また、薄層の厚さ方向の全体にわたってより十分に金属粒子を焼結又は溶融結合させ、積層間の割れをより生じにくくする観点からは、薄層の厚さは、後述するレーザーのビームスポット径との差が0.10mm以内になるよう設定することが好ましい。
From the above viewpoint, the thickness of the thin layer is more preferably in the range of 0.02 to 0.30 mm, further preferably in the range of 0.03 to 0.20 mm, and 0.05 to 0. It is particularly preferable that it is within the range of 10 mm. In addition, from the viewpoint of sintering or melting and bonding metal particles more fully throughout the thickness direction of the thin layer and making cracks between the layers less likely to occur, the thickness of the thin layer is determined by the laser beam spot described later. It is preferable to set so that the difference from the diameter is within 0.10 mm.
〈レーザー光〉
レーザー光の波長は、金属粒子に主成分として含まれる金属材料が効率的にレーザー光を吸収することができる範囲内で設定すればよい。 <Laser light>
The wavelength of the laser beam may be set within a range in which the metal material contained as a main component in the metal particles can efficiently absorb the laser beam.
レーザー光の波長は、金属粒子に主成分として含まれる金属材料が効率的にレーザー光を吸収することができる範囲内で設定すればよい。 <Laser light>
The wavelength of the laser beam may be set within a range in which the metal material contained as a main component in the metal particles can efficiently absorb the laser beam.
本発明において、照射するレーザー光の下式(1)で表されるエネルギー密度Eが、45~150J/mm2の範囲内であることが好ましい。
In the present invention, the energy density E represented by the following formula (1) of the laser beam to be irradiated is preferably within a range of 45 to 150 J / mm 2 .
式(1)
エネルギー密度E(J/mm2)={レーザー出力/(レーザー照射スピード×焦点スポット面積)}
また、レーザー光の出力時のパワーは、レーザー光の走査速度において、金属粉末を構成する金属粒子が十分に焼結又は溶融結合する範囲内で設定すればよい。具体的には、5.0~1000Wの範囲内であることが好ましい。金属粉末は、金属材料の種類によらず、低エネルギーのレーザー光でも金属粒子の焼結又は溶融結合が容易になり、立体積層造形物の製造が可能となる。レーザー光のエネルギーを低くして、製造コストを低くし、かつ、製造装置の構成を簡易なものにする観点からは、レーザー光の出力時のパワーは500W以下であることがより好ましく、300W以下であることが更に好ましい。 Formula (1)
Energy density E (J / mm 2 ) = {Laser output / (Laser irradiation speed × Focus spot area)}
The power at the time of laser beam output may be set within a range where the metal particles constituting the metal powder are sufficiently sintered or melt bonded at the scanning speed of the laser beam. Specifically, it is preferably in the range of 5.0 to 1000 W. Regardless of the type of metal material, the metal powder can easily sinter or melt bond the metal particles even with low-energy laser light, and can produce a three-dimensional layered object. From the viewpoint of reducing the energy of the laser beam, reducing the manufacturing cost, and simplifying the configuration of the manufacturing apparatus, the power at the time of laser beam output is more preferably 500 W or less, and 300 W or less. More preferably.
エネルギー密度E(J/mm2)={レーザー出力/(レーザー照射スピード×焦点スポット面積)}
また、レーザー光の出力時のパワーは、レーザー光の走査速度において、金属粉末を構成する金属粒子が十分に焼結又は溶融結合する範囲内で設定すればよい。具体的には、5.0~1000Wの範囲内であることが好ましい。金属粉末は、金属材料の種類によらず、低エネルギーのレーザー光でも金属粒子の焼結又は溶融結合が容易になり、立体積層造形物の製造が可能となる。レーザー光のエネルギーを低くして、製造コストを低くし、かつ、製造装置の構成を簡易なものにする観点からは、レーザー光の出力時のパワーは500W以下であることがより好ましく、300W以下であることが更に好ましい。 Formula (1)
Energy density E (J / mm 2 ) = {Laser output / (Laser irradiation speed × Focus spot area)}
The power at the time of laser beam output may be set within a range where the metal particles constituting the metal powder are sufficiently sintered or melt bonded at the scanning speed of the laser beam. Specifically, it is preferably in the range of 5.0 to 1000 W. Regardless of the type of metal material, the metal powder can easily sinter or melt bond the metal particles even with low-energy laser light, and can produce a three-dimensional layered object. From the viewpoint of reducing the energy of the laser beam, reducing the manufacturing cost, and simplifying the configuration of the manufacturing apparatus, the power at the time of laser beam output is more preferably 500 W or less, and 300 W or less. More preferably.
レーザー光の走査速度は、製造コストを高めることなく、かつ装置構成を過剰に複雑にしない範囲内で設定すればよい。具体的には、5~10000mm/秒の範囲内で設定することが好ましく、100~8000mm/秒の範囲内とすることがより好ましく、2000~7000mm/秒の範囲内とすることが更に好ましい。
The scanning speed of the laser beam may be set within a range that does not increase the manufacturing cost and does not excessively complicate the apparatus configuration. Specifically, it is preferably set within the range of 5 to 10000 mm / sec, more preferably within the range of 100 to 8000 mm / sec, and even more preferably within the range of 2000 to 7000 mm / sec.
レーザー光のビーム径は、製造しようとする立体積層造形物の形状などに応じて適宜設定することができる。
The beam diameter of the laser beam can be appropriately set according to the shape of the three-dimensional layered object to be manufactured.
本発明の粉末焼結積層造形物の製造に適用可能なレーザー光としては、特に制限はなく、例えば、炭酸ガスレーザー、YAGレーザー、エキシマレーザー、He-Cdレーザー、半導体励起固体レーザー、ファイバーレーザーなどが挙げられる。
The laser beam applicable to the production of the powder-sintered layered product of the present invention is not particularly limited, and examples thereof include a carbon dioxide laser, a YAG laser, an excimer laser, a He—Cd laser, a semiconductor excitation solid laser, and a fiber laser. Is mentioned.
これらのレーザーは一種を単独で用いることができ、又は2種以上を組み合わせて使用することもできる。
These lasers can be used alone or in combination of two or more.
〈立体積層物の形成環境〉
図2Bで示した各ステップにおいて、焼結又は溶融結合中に金属粒子に主成分として含まれる金属材料が酸化又は窒化することによる、立体積層造形物の強度の低下を防ぐ観点からは、少なくとも第2ステップ(レーザー光照射・焼結工程)は減圧下又は不活性ガス雰囲気中で行うことが好ましい。減圧するときの圧力は1×10-2Pa以下であることが好ましく、1×10-3Pa以下であることがより好ましい。本発明に適用可能な不活性ガスとしては、例えば、窒素ガス、希ガス等が挙げられる。これらの不活性ガスのうち、入手の容易さの観点からは、窒素(N2)ガス、ヘリウム(He)ガス又はアルゴン(Ar)ガスが好ましい。製造工程を簡略化する観点からは、図2Bで示すすべてのステップを減圧下又は不活性ガス雰囲気中で行うことが好ましい。また、特別なケースにおいては、大気中でレーザー光の照射を行うこともできる。 <Formation environment of three-dimensional laminate>
In each step shown in FIG. 2B, at least from the viewpoint of preventing the strength of the three-dimensional layered object from being reduced due to oxidation or nitridation of the metal material contained as a main component in the metal particles during sintering or fusion bonding. The two steps (laser light irradiation / sintering step) are preferably performed under reduced pressure or in an inert gas atmosphere. The pressure when the pressure is reduced is preferably 1 × 10 −2 Pa or less, and more preferably 1 × 10 −3 Pa or less. Examples of the inert gas applicable to the present invention include nitrogen gas and rare gas. Among these inert gases, nitrogen (N 2 ) gas, helium (He) gas, or argon (Ar) gas is preferable from the viewpoint of availability. From the viewpoint of simplifying the manufacturing process, it is preferable to perform all the steps shown in FIG. 2B under reduced pressure or in an inert gas atmosphere. In a special case, the laser beam can be irradiated in the atmosphere.
図2Bで示した各ステップにおいて、焼結又は溶融結合中に金属粒子に主成分として含まれる金属材料が酸化又は窒化することによる、立体積層造形物の強度の低下を防ぐ観点からは、少なくとも第2ステップ(レーザー光照射・焼結工程)は減圧下又は不活性ガス雰囲気中で行うことが好ましい。減圧するときの圧力は1×10-2Pa以下であることが好ましく、1×10-3Pa以下であることがより好ましい。本発明に適用可能な不活性ガスとしては、例えば、窒素ガス、希ガス等が挙げられる。これらの不活性ガスのうち、入手の容易さの観点からは、窒素(N2)ガス、ヘリウム(He)ガス又はアルゴン(Ar)ガスが好ましい。製造工程を簡略化する観点からは、図2Bで示すすべてのステップを減圧下又は不活性ガス雰囲気中で行うことが好ましい。また、特別なケースにおいては、大気中でレーザー光の照射を行うこともできる。 <Formation environment of three-dimensional laminate>
In each step shown in FIG. 2B, at least from the viewpoint of preventing the strength of the three-dimensional layered object from being reduced due to oxidation or nitridation of the metal material contained as a main component in the metal particles during sintering or fusion bonding. The two steps (laser light irradiation / sintering step) are preferably performed under reduced pressure or in an inert gas atmosphere. The pressure when the pressure is reduced is preferably 1 × 10 −2 Pa or less, and more preferably 1 × 10 −3 Pa or less. Examples of the inert gas applicable to the present invention include nitrogen gas and rare gas. Among these inert gases, nitrogen (N 2 ) gas, helium (He) gas, or argon (Ar) gas is preferable from the viewpoint of availability. From the viewpoint of simplifying the manufacturing process, it is preferable to perform all the steps shown in FIG. 2B under reduced pressure or in an inert gas atmosphere. In a special case, the laser beam can be irradiated in the atmosphere.
照射する際の温度は、特に限定されず、冷却下、室温又は加熱下で行うことができる。金属粉末焼結材料の薄層の形成及びレーザー光照射による焼結は、必要な回数順次繰り返した後、未焼結の微小球体を分離することにより、所望の造形物を得ることができる。
The temperature at the time of irradiation is not particularly limited, and can be performed under cooling, at room temperature or under heating. Formation of a thin layer of metal powder sintered material and sintering by laser light irradiation are sequentially repeated as many times as necessary, and then a desired shaped object can be obtained by separating unsintered microspheres.
〔立体積層造形物の製造方法〕
次いで、本発明の粉末焼結積層造形物の製造方法を適用した立体積層造形物の製造フローについて、図を交えて説明する。 [Method for producing three-dimensional layered object]
Next, a manufacturing flow of a three-dimensional layered object to which the method for manufacturing a powder sintered layered object of the present invention is applied will be described with reference to the drawings.
次いで、本発明の粉末焼結積層造形物の製造方法を適用した立体積層造形物の製造フローについて、図を交えて説明する。 [Method for producing three-dimensional layered object]
Next, a manufacturing flow of a three-dimensional layered object to which the method for manufacturing a powder sintered layered object of the present invention is applied will be described with reference to the drawings.
図3は、本発明に適用可能な立体積層造形物の形成装置の一例の全体構成を示す概略図である。
FIG. 3 is a schematic diagram showing an overall configuration of an example of a three-dimensional layered object forming apparatus applicable to the present invention.
図3で示すように、立体積層造形物の形成装置(400)は、開口内に位置する造形ステージ(6)、フラックスが被覆されている金属粒子を含む金属粉末(1)の薄層(5)を造形ステージ(6)に形成する薄層形成部(420)、前記造形ステージ(6)上に形成される薄層(5)の表面又は装置内を加熱又は冷却する温度調整部(430)、薄層(5)にレーザー光(L)を照射して、前記金属粒子が溶融結合してなる造形物層(5A)を形成するレーザー光照射部(440)、鉛直方向の位置を可変に造形ステージ(6)を支持するステージ支持部(450)、及び上記各部を支持する支持基盤(490)を備えている。
As shown in FIG. 3, a three-dimensional layered object forming apparatus (400) includes a modeling stage (6) located in an opening, and a thin layer (5) of metal powder (1) containing metal particles coated with flux. ) On the modeling stage (6), and a temperature adjusting unit (430) for heating or cooling the surface of the thin layer (5) formed on the modeling stage (6) or the inside of the apparatus. The laser beam irradiation part (440) for irradiating the thin layer (5) with the laser beam (L) to form the shaped article layer (5A) formed by fusion bonding of the metal particles, the position in the vertical direction being variable A stage support part (450) for supporting the modeling stage (6) and a support base (490) for supporting the above parts are provided.
ステージ支持部(450)は、造形ステージ(6)を、その鉛直方向の位置を可変に支持する。すなわち、造形ステージ(6)は、ステージ支持部(450)によって鉛直方向に精密に移動可能に構成されている。ステージ支持部(450)としては、種々の構成を採用できるが、例えば、造形ステージ(6)を保持する保持部材と、この保持部材(6)を鉛直方向に案内するガイド部材と、ガイド部材に設けられたねじ孔に係合するボールねじ等で構成することができる。
The stage support section (450) supports the modeling stage (6) variably in the vertical position. That is, the modeling stage (6) is configured to be precisely movable in the vertical direction by the stage support portion (450). Various configurations can be adopted as the stage support portion (450). For example, a holding member that holds the modeling stage (6), a guide member that guides the holding member (6) in the vertical direction, and a guide member It can be configured by a ball screw or the like that engages with the provided screw hole.
造形ステージ(6)には、薄層形成部(420)による薄層(5)の形成、温度調整部(430)による温度の調整及びレーザー光照射部(440)によるレーザー光(L)の照射によって造形物層(5A)が形成され、この造形物層(5A)が積層されることにより、立体積層造形物(3DM)が造形される。
On the modeling stage (6), the thin layer (5) is formed by the thin layer forming part (420), the temperature is adjusted by the temperature adjusting part (430), and the laser light irradiation part (440) is irradiated with the laser light (L). A three-dimensional layered object (3DM) is formed by forming a three-dimensional object layer (5A) and laminating this three-dimensional object layer (5A).
薄層形成部(420)は、例えば、造形ステージ(6)が昇降する開口の縁部と、水平方向にほぼ同一平面上にその縁部がある開口、開口から鉛直方向下方に延在する金属粉末供給部(421)、及び金属粉末供給部(421)の底部に設けられ開口内を昇降する供給ピストンを備える昇降用リフト(451)、及び供給された金属粉末(1)を造形ステージ(6)上に平らに敷き詰めて、金属材料の薄層(5)を形成する粉末リコーター(7)を備えた構成とすることができる。
The thin layer forming part (420) includes, for example, an edge part of the opening on which the modeling stage (6) moves up and down, an opening having the edge part substantially on the same plane in the horizontal direction, and a metal extending vertically downward from the opening. The powder supply unit (421), the lift for lift (451) provided with the supply piston provided at the bottom of the metal powder supply unit (421) to move up and down in the opening, and the supplied metal powder (1) to the modeling stage (6 ) And a powder recoater (7) that is laid flat on top of each other to form a thin layer (5) of metal material.
なお、金属粉末供給部(421)は、造形ステージ(6)に対して鉛直方向上方に設けられた金属粉末収納部、及びノズルを備えて、前記造形ステージと水平方向に同一の平面上に、金属粉末を吐出する構成としてもよい。
The metal powder supply unit (421) includes a metal powder storage unit and a nozzle provided vertically above the modeling stage (6), and on the same plane in the horizontal direction as the modeling stage. It is good also as a structure which discharges metal powder.
温度調整部(430)は、薄層(5)の表面のうち造形物層(5A)を形成すべき領域を加熱するか、形成された造形物層(5A)の表面を冷却し、その温度を維持できるものであればよい。たとえば、温度調整部(430)は、造形ステージ(6)上に形成された薄層(5)の表面を加熱又は冷却可能な第1の温度調整装置(431)を備えた構成としてもよいし、造形ステージ(6)上に供給される前の金属粉末(1)を加熱する第2の温度調整装置(432)をさらに備えた構成としてもよい。また、温度調整部(430)は、上記造形物層(5A)を形成すべき領域を選択的に加熱する構成であってもよいし、装置内の全体を予め加熱しておいて、上記形成された薄層(5)の表面を所定の温度に調温する構成であってもよい。
A temperature adjustment part (430) heats the area | region which should form a modeling object layer (5A) among the surfaces of a thin layer (5), or cools the surface of the formed modeling object layer (5A), and is the temperature. What is necessary is just to be able to maintain. For example, the temperature adjustment unit (430) may include a first temperature adjustment device (431) that can heat or cool the surface of the thin layer (5) formed on the modeling stage (6). It is good also as a structure further provided with the 2nd temperature control apparatus (432) which heats the metal powder (1) before being supplied on the modeling stage (6). Moreover, the structure which selectively heats the area | region which should form the said molded article layer (5A) may be sufficient as the temperature adjustment part (430), or the whole inside of an apparatus is heated beforehand, and the said formation The structure which adjusts the temperature of the surface of the made thin layer (5) to predetermined temperature may be sufficient.
温度測定器(不図示)は、上記造形物層(5A)を形成すべき領域の表面温度を非接触で測定できるものであればよく、例えば、赤外線センサーや光高温計等を適用することができる。
Any temperature measuring device (not shown) may be used as long as it can measure the surface temperature of the region where the shaped article layer (5A) is to be formed in a non-contact manner. For example, an infrared sensor or an optical pyrometer can be applied. it can.
レーザー光照射部(440)は、主にレーザー光源(441)及びガルバノミラー(442)を具備している。レーザー光照射部(440)には、更に、レーザー光(L)を透過させるレーザー光窓(443)及びレーザー光(L)の焦点距離を薄層(5)の表面にあわせるためのレンズ(不図示)を備えていてもよい。 レーザー光源(441)は、所望の波長のレーザー光(L)を、例えば、エネルギー密度Eとして45~150J/mm2の範囲内で出射する光源であればよい。レーザー光源(441)の例には、前述のとおり、炭酸ガスレーザー、YAGレーザー、エキシマレーザー、He-Cdレーザー、半導体励起固体レーザー、ファイバーレーザー等を挙げることができる。
The laser beam irradiation unit (440) mainly includes a laser light source (441) and a galvanometer mirror (442). The laser beam irradiator (440) further includes a laser beam window (443) that transmits the laser beam (L) and a lens for adjusting the focal length of the laser beam (L) to the surface of the thin layer (5). (Shown) may be provided. The laser light source (441) may be a light source that emits laser light (L) having a desired wavelength, for example, in the range of 45 to 150 J / mm 2 as the energy density E. Examples of the laser light source (441) include a carbon dioxide gas laser, a YAG laser, an excimer laser, a He—Cd laser, a semiconductor excitation solid laser, and a fiber laser as described above.
ガルバノミラー(442)は、レーザー光源(441)から出射したレーザー光(L)を反射して、レーザー光(L)をX方向に走査するXミラー及びY方向に走査するYミラーから構成されてもよい。レーザー光窓(443)は、レーザー光(L)を透過させる材料からなるものであればよい。
The galvanometer mirror (442) includes an X mirror that reflects the laser light (L) emitted from the laser light source (441) and scans the laser light (L) in the X direction and a Y mirror that scans in the Y direction. Also good. The laser beam window (443) may be made of a material that transmits the laser beam (L).
〔立体積層造形物の形成フロー〕
次いで、上記説明した立体積層造形物の形成装置を用い、立体積層造形物を形成するフローについて説明する。 [Formation flow of three-dimensional layered object]
Next, a flow for forming a three-dimensional layered object using the above-described three-dimensional layered object forming device will be described.
次いで、上記説明した立体積層造形物の形成装置を用い、立体積層造形物を形成するフローについて説明する。 [Formation flow of three-dimensional layered object]
Next, a flow for forming a three-dimensional layered object using the above-described three-dimensional layered object forming device will be described.
図4は、本発明に適用可能な立体積層造形物の形成装置における制御方法の一例を示すブロック図
図4で示すように、立体積層造形物の形成装置(400)の制御系は、主に金属粉末供給部(421)、粉末リコーター(7)、薄層形成部(420)より構成されている立体積層造形物の形成部(401)、温度調整部(430)、レーザー光照射部(440)、及びステージ支持部(450)の下降速度を制御して、造形物層(5A)を繰り返し形成して立体積層造形物(3DM)の形成を制御するための制御部(460)、各種情報を表示するための表示部(470)、ユーザーからの指示を受け付けるためのポインティングデバイス等を含む操作部(475)、制御部(460)で実行する制御プログラムを含む各種の情報を記憶する記憶部(480)、並びに外部機器との間で立体積層造形物(3DM)の造形データ等の各種情報を送受信するためのインターフェース等を含むデータ入力部(485)を備えてもよい。また、立体積層造形物の形成装置(400)は、造形ステージ(6)上に形成された薄層(5)の表面のうち、造形物層(5A)を形成すべき領域の温度を測定する温度測定器(不図示)を備えてもよい。立体積層造形物の形成装置(400)には、立体造形用のデータを作成するためのコンピューター装置(500)が接続されてもよい。 FIG. 4 is a block diagram showing an example of a control method in the three-dimensional layered object forming apparatus applicable to the present invention. As shown in FIG. 4, the control system of the three-dimensional layered object forming apparatus (400) is mainly used. A three-dimensional layered object forming part (401), a temperature adjusting part (430), a laser light irradiation part (440) composed of a metal powder supply part (421), a powder recoater (7), and a thin layer forming part (420). ), And a control unit (460) for controlling the lowering speed of the stage support unit (450) to repeatedly form the modeled object layer (5A) to control the formation of the three-dimensional layered object (3DM), various information A display unit (470) for displaying an image, an operation unit (475) including a pointing device for receiving an instruction from a user, and various types of information including a control program executed by the control unit (460) are stored. You may provide the data input part (485) containing the interface etc. for transmitting / receiving various information, such as modeling data of a three-dimensional laminate modeling thing (3DM), between a memory | storage part (480) and an external device. Moreover, the formation apparatus (400) of a three-dimensional laminate modeling thing measures the temperature of the area | region which should form a modeling thing layer (5A) among the surfaces of the thin layer (5) formed on the modeling stage (6). A temperature measuring device (not shown) may be provided. A computer apparatus (500) for creating data for three-dimensional modeling may be connected to the three-dimensional modeled object forming apparatus (400).
図4で示すように、立体積層造形物の形成装置(400)の制御系は、主に金属粉末供給部(421)、粉末リコーター(7)、薄層形成部(420)より構成されている立体積層造形物の形成部(401)、温度調整部(430)、レーザー光照射部(440)、及びステージ支持部(450)の下降速度を制御して、造形物層(5A)を繰り返し形成して立体積層造形物(3DM)の形成を制御するための制御部(460)、各種情報を表示するための表示部(470)、ユーザーからの指示を受け付けるためのポインティングデバイス等を含む操作部(475)、制御部(460)で実行する制御プログラムを含む各種の情報を記憶する記憶部(480)、並びに外部機器との間で立体積層造形物(3DM)の造形データ等の各種情報を送受信するためのインターフェース等を含むデータ入力部(485)を備えてもよい。また、立体積層造形物の形成装置(400)は、造形ステージ(6)上に形成された薄層(5)の表面のうち、造形物層(5A)を形成すべき領域の温度を測定する温度測定器(不図示)を備えてもよい。立体積層造形物の形成装置(400)には、立体造形用のデータを作成するためのコンピューター装置(500)が接続されてもよい。 FIG. 4 is a block diagram showing an example of a control method in the three-dimensional layered object forming apparatus applicable to the present invention. As shown in FIG. 4, the control system of the three-dimensional layered object forming apparatus (400) is mainly used. A three-dimensional layered object forming part (401), a temperature adjusting part (430), a laser light irradiation part (440) composed of a metal powder supply part (421), a powder recoater (7), and a thin layer forming part (420). ), And a control unit (460) for controlling the lowering speed of the stage support unit (450) to repeatedly form the modeled object layer (5A) to control the formation of the three-dimensional layered object (3DM), various information A display unit (470) for displaying an image, an operation unit (475) including a pointing device for receiving an instruction from a user, and various types of information including a control program executed by the control unit (460) are stored. You may provide the data input part (485) containing the interface etc. for transmitting / receiving various information, such as modeling data of a three-dimensional laminate modeling thing (3DM), between a memory | storage part (480) and an external device. Moreover, the formation apparatus (400) of a three-dimensional laminate modeling thing measures the temperature of the area | region which should form a modeling thing layer (5A) among the surfaces of the thin layer (5) formed on the modeling stage (6). A temperature measuring device (not shown) may be provided. A computer apparatus (500) for creating data for three-dimensional modeling may be connected to the three-dimensional modeled object forming apparatus (400).
制御部(460)は、中央処理装置等のハードウェアプロセッサを含んでおり、立体積層造形物(3DM)の造形動作中、立体造形装置(400)全体の動作を制御する。
The control unit (460) includes a hardware processor such as a central processing unit, and controls the operation of the entire three-dimensional modeling apparatus (400) during the modeling operation of the three-dimensional layered object (3DM).
また、制御部(460)は、例えば、データ入力部(485)がコンピューター装置(500)から取得した立体造形データを、造形物層(5A)の積層方向について薄く切った複数のスライスデータに変換するよう構成されてもよい。スライスデータは、立体積層造形物(3DM)を造形するための各造形物層(5A)の造形データである。スライスデータの厚さ、すなわち造形物層(5A)の厚さは、造形物層(5A)の一層分の厚さに応じた距離(積層ピッチ)と一致する。
In addition, the control unit (460) converts, for example, the three-dimensional modeling data acquired from the computer device (500) by the data input unit (485) into a plurality of slice data sliced in the stacking direction of the modeling object layer (5A). It may be configured to do. Slice data is modeling data of each modeling object layer (5A) for modeling a three-dimensional laminate modeling object (3DM). The thickness of the slice data, that is, the thickness of the modeled object layer (5A) matches the distance (lamination pitch) corresponding to the thickness of one layer of the modeled object layer (5A).
表示部(470)は、例えば、液晶ディスプレイ、有機エレクトロルミネッセンスディスプレイ等で構成することができる。
The display unit (470) can be composed of, for example, a liquid crystal display, an organic electroluminescence display, or the like.
操作部(475)は、例えば、キーボードやマウスなどのポインティングデバイスを含むものとすることができ、テンキー、実行キー、スタートキー等の各種操作キーを備えてもよい。
The operation unit (475) can include, for example, a pointing device such as a keyboard and a mouse, and may include various operation keys such as a numeric keypad, an execution key, and a start key.
記憶部(480)は、例えば、ROM、RAM、磁気ディスク、HDD、SSD等の各種の記憶媒体を含むものとすることができる。
The storage unit (480) may include various storage media such as a ROM, a RAM, a magnetic disk, an HDD, and an SSD.
立体積層造形物の形成装置(400)は、制御部(460)の制御を受けて、装置内を減圧する、減圧ポンプなどの減圧部(不図示)、又は、制御部(460)の制御を受けて、不活性ガスを装置内に供給する、不活性ガス供給部(不図示)を備えていてもよい。
The three-dimensional layered object formation apparatus (400) receives the control of the control unit (460), and depressurizes the inside of the apparatus, such as a decompression unit (not shown) such as a decompression pump, or controls the control unit (460). An inert gas supply unit (not shown) that receives and supplies the inert gas into the apparatus may be provided.
次いで、立体積層造形物の形成装置(400)を用いた立体積層造形物(3DM)の具体的な形成方法について説明する。
Next, a specific method for forming a three-dimensional layered object (3DM) using the three-dimensional layered object forming device (400) will be described.
制御部(460)は、データ入力部(485)がコンピューター装置(500)から取得した立体造形データを、造形物層(5A)の積層方向について薄く切った複数のスライスデータに変換する。その後、制御部(460)は、立体積層造形物の形成装置(400)における以下の動作の制御を行う。
The control unit (460) converts the three-dimensional modeling data acquired from the computer device (500) by the data input unit (485) into a plurality of slice data sliced in the stacking direction of the modeled object layer (5A). Then, a control part (460) controls the following operation | movement in the formation apparatus (400) of a three-dimensional laminated structure.
金属粉末供給部(421)は、制御部(460)から出力された供給情報に従って、モーター及び駆動機構(いずれも不図示)を駆動し、昇降用リフト(451)を鉛直方向上方(図中矢印方向)に移動させ、前記造形ステージ(6)と水平方向同一平面上に、金属粉末(1)を押し出す。
The metal powder supply unit (421) drives the motor and the drive mechanism (both not shown) according to the supply information output from the control unit (460), and moves the lifting lift (451) vertically upward (arrow in the figure). The metal powder (1) is extruded on the same horizontal plane as the modeling stage (6).
その後、粉末リコーター(7)の駆動部は、制御部(460)から出力された薄層形成情報に従って、水平方向(図中矢印方向)に粉末リコーター(7)を、ポジション1(P1)から図面の右側のポジション2(P2)まで移動して、金属粉末(1)を、薄膜形成部(420)に運搬し、かつ、薄層(5)の厚さが造形物層(5A)の1層分の厚さとなるように金属粉末(1)を敷き詰める。
Thereafter, the drive unit of the powder recoater (7) draws the powder recoater (7) from the position 1 (P1) in the horizontal direction (arrow direction in the figure) according to the thin layer formation information output from the control unit (460). The metal powder (1) is transported to the thin film forming part (420), and the thickness of the thin layer (5) is one layer of the shaped article layer (5A). Spread metal powder (1) to a thickness of 1 minute.
温度調整部(430)は、制御部(460)から出力された温度情報に従って形成された薄層(5)の表面又は装置内の全体を加熱する。上記温度情報は、たとえば、データ入力部(485)から入力された金属粒子を構成する材料が溶融する温度(Tmc)のデータに基づいて制御部(460)が記憶部(480)から引き出した、上記温度との差が5~50℃の範囲内となる温度に薄層(5)の表面を加熱するための情報とすることができる。温度調整部(430)は、薄層(5)が形成された後に加熱を開始してもよいし、薄層(5)が形成される前から、形成されるべき薄層(5)の表面に該当する箇所又は装置内の加熱を行っていてもよい。
The temperature adjustment unit (430) heats the surface of the thin layer (5) formed in accordance with the temperature information output from the control unit (460) or the entire apparatus. The temperature information is extracted from the storage unit (480) by the control unit (460) based on, for example, data on the temperature (Tmc) at which the material constituting the metal particles is input from the data input unit (485). It can be information for heating the surface of the thin layer (5) to a temperature at which the difference from the above temperature is in the range of 5 to 50 ° C. The temperature adjustment unit (430) may start heating after the thin layer (5) is formed, or the surface of the thin layer (5) to be formed before the thin layer (5) is formed. Heating may be performed at a location corresponding to or in the apparatus.
その後、レーザー光照射部(440)は、制御部(460)から出力されたレーザー光照射情報に従って、薄層(5)上の、各スライスデータにおける立体積層造形物(3DM)を構成する領域に適合して、レーザー光源(441)からレーザー光(L)を出射し、ガルバノミラー駆動部(442)によりガルバノミラーを駆動してレーザー光(L)を走査する。レーザー光(L)の照射によって金属粉末に含まれる金属粒子が溶融結合し、造形物層(5A)が形成される。この時、金属粉末に、造形対象物の断面形状に対応する形状パターンでレーザー光を照射する断面形状形成工程として、フラックスにより金属粉末表面の還元反応を促進する第1のレーザー光照射と、金属粉末を結合させる第2のレーザー光照射を行う方法がより好ましい。
Thereafter, the laser beam irradiation unit (440) is arranged on the thin layer (5) according to the laser beam irradiation information output from the control unit (460) in a region constituting the three-dimensional layered object (3DM) in each slice data. In conformity, laser light (L) is emitted from the laser light source (441), and the galvano mirror is driven by the galvano mirror driving unit (442) to scan the laser light (L). The metal particles contained in the metal powder are melt-bonded by the irradiation of the laser beam (L), and the shaped article layer (5A) is formed. At this time, as a cross-sectional shape forming step of irradiating the metal powder with a laser beam in a shape pattern corresponding to the cross-sectional shape of the object to be shaped, a first laser light irradiation that promotes a reduction reaction on the surface of the metal powder with a flux, and a metal A method of performing second laser light irradiation for bonding powder is more preferable.
上記方法でレーザー照射を行う場合、第1のレーザー光照射工程におけるレーザー光の照射条件としては、出力として50~100Wの範囲内であることが好ましく、第2のレーザー光照射工程におけるレーザー光の照射条件としては、100~400Wの範囲内であることが好ましい。
When laser irradiation is performed by the above method, the laser light irradiation conditions in the first laser light irradiation step are preferably in the range of 50 to 100 W as output, and the laser light irradiation in the second laser light irradiation step The irradiation conditions are preferably in the range of 100 to 400W.
その後、ステージ支持部(450)は、制御部(460)から出力された位置制御情報に従って、モーター及び駆動機構(いずれも不図示)を駆動し、造形ステージ(6)を、積層ピッチだけ鉛直方向下方(図中矢印方向)に移動する。
Thereafter, the stage support unit (450) drives the motor and the drive mechanism (both not shown) according to the position control information output from the control unit (460), and moves the modeling stage (6) in the vertical direction by the stacking pitch. Move downward (arrow direction in the figure).
表示部(470)は、必要に応じて、制御部(460)の制御を受けて、ユーザーに認識させるべき各種の情報やメッセージを表示する。操作部(475)は、ユーザーによる各種入力操作を受け付けて、その入力操作に応じた操作信号を制御部(460)に出力する。例えば、形成される仮想の立体造形物を表示部(470)に表示して、所望の形状が形成されるか否かを確認し、所望の形状が形成されない場合は、操作部(475)から修正を加えてもよい。
The display unit (470) displays various information and messages to be recognized by the user under the control of the control unit (460) as necessary. The operation unit (475) receives various input operations by the user and outputs an operation signal corresponding to the input operation to the control unit (460). For example, a virtual three-dimensional object to be formed is displayed on the display unit (470) to check whether a desired shape is formed. If the desired shape is not formed, the operation unit (475) is used. Modifications may be made.
制御部(460)は、必要に応じて、記憶部(480)へのデータの格納又は記憶部(480)からのデータの引き出しを行う。
The control unit (460) stores data in the storage unit (480) or extracts data from the storage unit (480) as necessary.
また、制御部(460)は、薄層(5)の表面のうち、造形物層(5A)を形成すべき領域の温度の情報を温度測定器から受け取り、前記造形物層を形成すべき領域の温度が、前記コ金属粒子の構成材料が溶融する温度(Tmc)よりも5~50℃の範囲内、好ましくは5~25℃の範囲内になるように、温度調整部(430)による加熱を制御してもよい。
Moreover, a control part (460) receives the information of the temperature of the area | region which should form a modeling object layer (5A) among the surfaces of a thin layer (5) from a temperature measuring device, and the area | region which should form the said modeling object layer Is heated by the temperature adjusting unit (430) so that the temperature is within the range of 5 to 50 ° C., preferably within the range of 5 to 25 ° C., than the temperature (Tmc) at which the constituent material of the metal particles melts. May be controlled.
これらの動作を繰り返すことで、造形物層(5A)が積層され、立体積層造形物(3DM)が製造される。
By repeating these operations, the model object layer (5A) is stacked, and a three-dimensional model object (3DM) is manufactured.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお、実施例において「部」又は「%」の表示を用いるが、特に断りがない限り「質量部」又は「質量%」を表す。
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.
《金属粉末の作製》
以下の方法に従って、金属粉末1~30を作製した。 <Production of metal powder>
Metal powders 1 to 30 were produced according to the following method.
以下の方法に従って、金属粉末1~30を作製した。 <Production of metal powder>
Metal powders 1 to 30 were produced according to the following method.
〔金属粉末1の作製〕
転動流動層乾燥機(パウレック社製:マルチプレックスMP-01)を用い、金属粒子として100質量部の銅粒子(ヒカリ素材工業株式会社製、商品名 銅粉末、個数平均粒子径:40μm、CV値:10%、円形度:0.93)に、フラックスとして0.24質量部のホウ砂(Na2B4O7)に水を加えたコーティング液を噴霧した後、風量:45m3/hr、設定温度:60℃下で流動化させて乾燥させた後、風量:45m3/hr、で冷却して、フラックスの被覆層の平均厚さが15nmである金属粉末1を作製した。 [Preparation of metal powder 1]
Using a rolling fluidized bed dryer (manufactured by POWREC: Multiplex MP-01), 100 parts by mass of copper particles (manufactured by Hikari Material Industries Co., Ltd., trade name: copper powder, number average particle size: 40 μm, CV) After spraying a coating solution obtained by adding water to 0.24 parts by mass of borax (Na 2 B 4 O 7 ) as a flux to a value: 10%, circularity: 0.93), an air volume: 45 m 3 / hr Then, after fluidizing and drying at a set temperature of 60 ° C., cooling was performed with an air volume of 45 m 3 / hr to prepare ametal powder 1 having an average thickness of a flux coating layer of 15 nm.
転動流動層乾燥機(パウレック社製:マルチプレックスMP-01)を用い、金属粒子として100質量部の銅粒子(ヒカリ素材工業株式会社製、商品名 銅粉末、個数平均粒子径:40μm、CV値:10%、円形度:0.93)に、フラックスとして0.24質量部のホウ砂(Na2B4O7)に水を加えたコーティング液を噴霧した後、風量:45m3/hr、設定温度:60℃下で流動化させて乾燥させた後、風量:45m3/hr、で冷却して、フラックスの被覆層の平均厚さが15nmである金属粉末1を作製した。 [Preparation of metal powder 1]
Using a rolling fluidized bed dryer (manufactured by POWREC: Multiplex MP-01), 100 parts by mass of copper particles (manufactured by Hikari Material Industries Co., Ltd., trade name: copper powder, number average particle size: 40 μm, CV) After spraying a coating solution obtained by adding water to 0.24 parts by mass of borax (Na 2 B 4 O 7 ) as a flux to a value: 10%, circularity: 0.93), an air volume: 45 m 3 / hr Then, after fluidizing and drying at a set temperature of 60 ° C., cooling was performed with an air volume of 45 m 3 / hr to prepare a
〔金属粉末2~8の作製〕
上記金属粉末1の作製において、銅粒子(ヒカリ素材工業株式会社製、商品名 銅粉末、個数平均粒子径:40μm、CV値:10%、円形度:0.93)を、それぞれ表Iに記載の各金属粒子に変更した以外は同様にして、金属粉末2~8を作製した。 [Production ofmetal powders 2 to 8]
In the production of themetal powder 1, copper particles (manufactured by Hikari Material Kogyo Co., Ltd., trade name: copper powder, number average particle diameter: 40 μm, CV value: 10%, circularity: 0.93) are described in Table I, respectively. Metal powders 2 to 8 were produced in the same manner except that the metal particles were changed to the above metal particles.
上記金属粉末1の作製において、銅粒子(ヒカリ素材工業株式会社製、商品名 銅粉末、個数平均粒子径:40μm、CV値:10%、円形度:0.93)を、それぞれ表Iに記載の各金属粒子に変更した以外は同様にして、金属粉末2~8を作製した。 [Production of
In the production of the
なお、使用した各金属粒子は、ヒカリ素材工業(株)、安達新産業(株)、関東化学(株)、コアフロント(株)の各社より販売されている金属粒子を適宜選択し、かつ複数種のメンブレンフィルターによる分級操作を行って、表Iに記載の個数平均粒子径、CV値となるように調整した。
For each metal particle used, the metal particles sold by Hikari Material Industry Co., Ltd., Adachi Shin Sangyo Co., Ltd., Kanto Chemical Co., Ltd., and Core Front Co., Ltd. are appropriately selected, and a plurality of metal particles are used. Classification operation using a seed membrane filter was performed, and the number average particle size and the CV value described in Table I were adjusted.
〔金属粉末9~17の作製〕
上記金属粉末1の作製において、銅粒子(ヒカリ素材工業株式会社製、商品名 銅粉末、個数平均粒子径:40μm、CV値:10%、円形度:0.93)を、それぞれ表Iに記載の個数平均粒子径、CV値及び円形度を有する銅粒子に変更した以外は同様にして、金属粉末9~17を作製した。 [Production of metal powders 9 to 17]
In the production of themetal powder 1, copper particles (manufactured by Hikari Material Kogyo Co., Ltd., trade name: copper powder, number average particle diameter: 40 μm, CV value: 10%, circularity: 0.93) are described in Table I, respectively. Metal powders 9 to 17 were produced in the same manner except that the number average particle diameter, CV value, and circularity of the copper particles were changed to copper particles.
上記金属粉末1の作製において、銅粒子(ヒカリ素材工業株式会社製、商品名 銅粉末、個数平均粒子径:40μm、CV値:10%、円形度:0.93)を、それぞれ表Iに記載の個数平均粒子径、CV値及び円形度を有する銅粒子に変更した以外は同様にして、金属粉末9~17を作製した。 [Production of metal powders 9 to 17]
In the production of the
各銅粒子は、ヒカリ素材工業(株)、関東化学(株)、コアフロント(株)の各社より販売されている銅粒子より選択した。
Each copper particle was selected from copper particles sold by Hikari Material Industry Co., Ltd., Kanto Chemical Co., Ltd., and Core Front Co., Ltd.
〔金属粉末18の作製〕
上記金属粉末1の作製において、フラックスとして、ホウ砂(Na2B4O7)に代えて、同量のロジン(重合ロジン、荒川化学社製 商品名:アラダイムR-140、軟化点:140℃)を用いた以外は同様にして、金属粉末18を作製した。 [Preparation of metal powder 18]
In the production of themetal powder 1, instead of borax (Na 2 B 4 O 7 ), the same amount of rosin (polymerized rosin, manufactured by Arakawa Chemical Co., Ltd., trade name: Aradim R-140, softening point: 140 ° C. The metal powder 18 was produced in the same manner except that (1) was used.
上記金属粉末1の作製において、フラックスとして、ホウ砂(Na2B4O7)に代えて、同量のロジン(重合ロジン、荒川化学社製 商品名:アラダイムR-140、軟化点:140℃)を用いた以外は同様にして、金属粉末18を作製した。 [Preparation of metal powder 18]
In the production of the
〔金属粉末19~21の作製〕
上記金属粉末1の作製において、フラックスとして、ホウ砂(Na2B4O7)を、それぞれホウ酸、フッ化カリウム(KF)、塩化亜鉛(ZnCl)に変更した以外は同様にして、金属粉末19~21を作製した。 [Production of metal powders 19 to 21]
In the production of themetal powder 1, the metal powder was similarly obtained except that borax (Na 2 B 4 O 7 ) was changed to boric acid, potassium fluoride (KF), and zinc chloride (ZnCl), respectively. 19 to 21 were produced.
上記金属粉末1の作製において、フラックスとして、ホウ砂(Na2B4O7)を、それぞれホウ酸、フッ化カリウム(KF)、塩化亜鉛(ZnCl)に変更した以外は同様にして、金属粉末19~21を作製した。 [Production of metal powders 19 to 21]
In the production of the
〔金属粉末22の作製〕
上記金属粉末1の作製において、フラックスの添加は行わず、銅粒子(ヒカリ素材工業株式会社製、商品名 銅粉末、個数平均粒子径:40μm、CV値:10%、円形度:0.93)単独で使用した以外は同様にして、金属粉末22を作製した。 [Production of Metal Powder 22]
In the production of themetal powder 1, the addition of flux was not performed, and copper particles (trade name: copper powder, number average particle diameter: 40 μm, CV value: 10%, circularity: 0.93, manufactured by Hikari Material Industries Co., Ltd.) A metal powder 22 was produced in the same manner except that it was used alone.
上記金属粉末1の作製において、フラックスの添加は行わず、銅粒子(ヒカリ素材工業株式会社製、商品名 銅粉末、個数平均粒子径:40μm、CV値:10%、円形度:0.93)単独で使用した以外は同様にして、金属粉末22を作製した。 [Production of Metal Powder 22]
In the production of the
〔金属粉末23~26の作製〕
上記金属粉末1の作製において、金属粒子である銅粒子(ヒカリ素材工業株式会社製、商品名 銅粉末、個数平均粒子径:40μm、CV値:10%、円形度:0.93)に対する、フラックスであるホウ砂の混合比率を適宜変更して、フラックスの被覆層の平均厚さを、それぞれ2nm、5nm、30nm、45nmに変更した以外は同様にして、金属粉末23~26を作製した。 [Production of metal powders 23 to 26]
In the production of themetal powder 1, a flux with respect to copper particles that are metal particles (trade name: copper powder, number average particle diameter: 40 μm, CV value: 10%, circularity: 0.93, manufactured by Hikari Kogyo Kogyo Co., Ltd.) The metal powders 23 to 26 were produced in the same manner except that the mixing ratio of borax was changed to change the average thickness of the flux coating layer to 2 nm, 5 nm, 30 nm, and 45 nm, respectively.
上記金属粉末1の作製において、金属粒子である銅粒子(ヒカリ素材工業株式会社製、商品名 銅粉末、個数平均粒子径:40μm、CV値:10%、円形度:0.93)に対する、フラックスであるホウ砂の混合比率を適宜変更して、フラックスの被覆層の平均厚さを、それぞれ2nm、5nm、30nm、45nmに変更した以外は同様にして、金属粉末23~26を作製した。 [Production of metal powders 23 to 26]
In the production of the
〔各特性値の測定〕
上記金属粉末1~26を構成している金属粒子及びフラックス被覆層の特性値を、下記の方法に従って測定し、得られた結果を表1に示す。 [Measurement of each characteristic value]
The characteristic values of the metal particles constituting themetal powders 1 to 26 and the flux coating layer were measured according to the following method, and the results obtained are shown in Table 1.
上記金属粉末1~26を構成している金属粒子及びフラックス被覆層の特性値を、下記の方法に従って測定し、得られた結果を表1に示す。 [Measurement of each characteristic value]
The characteristic values of the metal particles constituting the
(金属粒子)
〈個数平均粒子径〉
上記金属粉末の作製に用いた金属粒子の個数平均粒子径は、透過型電子顕微鏡(TEM)を用いて、金属粒子の投影画像を撮影し、任意に50個選択した金属粒子の粒子径の平均値として求めた。なお、それぞれの金属粒子の粒子径は、各粒子の投影面積を円換算した時の直径で表し、50個の各金属粒子について測定した粒子径の相加平均値を求め、これを金属粒子(2)の個数平均粒子径とした。 (Metal particles)
<Number average particle diameter>
The number average particle diameter of the metal particles used for the production of the metal powder is an average of the particle diameters of 50 metal particles selected by photographing a projected image of the metal particles using a transmission electron microscope (TEM). Obtained as a value. In addition, the particle diameter of each metal particle is represented by the diameter when the projected area of each particle is converted into a circle, and the arithmetic average value of the particle diameters measured for each of the 50 metal particles is obtained. The number average particle diameter of 2) was used.
〈個数平均粒子径〉
上記金属粉末の作製に用いた金属粒子の個数平均粒子径は、透過型電子顕微鏡(TEM)を用いて、金属粒子の投影画像を撮影し、任意に50個選択した金属粒子の粒子径の平均値として求めた。なお、それぞれの金属粒子の粒子径は、各粒子の投影面積を円換算した時の直径で表し、50個の各金属粒子について測定した粒子径の相加平均値を求め、これを金属粒子(2)の個数平均粒子径とした。 (Metal particles)
<Number average particle diameter>
The number average particle diameter of the metal particles used for the production of the metal powder is an average of the particle diameters of 50 metal particles selected by photographing a projected image of the metal particles using a transmission electron microscope (TEM). Obtained as a value. In addition, the particle diameter of each metal particle is represented by the diameter when the projected area of each particle is converted into a circle, and the arithmetic average value of the particle diameters measured for each of the 50 metal particles is obtained. The number average particle diameter of 2) was used.
〈CV値:変動係数〉
各金属粒子のCV値は、レーザー回折/散乱式粒子径分布測定装置(株式会社堀場製作所製、Partica LA-960)を用いて測定して求めた。 <CV value: coefficient of variation>
The CV value of each metal particle was determined by measurement using a laser diffraction / scattering particle size distribution measuring device (Horiba, Ltd., Partica LA-960).
各金属粒子のCV値は、レーザー回折/散乱式粒子径分布測定装置(株式会社堀場製作所製、Partica LA-960)を用いて測定して求めた。 <CV value: coefficient of variation>
The CV value of each metal particle was determined by measurement using a laser diffraction / scattering particle size distribution measuring device (Horiba, Ltd., Partica LA-960).
〈平均円形度〉
上記金属粉末の作製に用いた金属粒子の円形度は、透過型電子顕微鏡(TEM)を用いて、金属粒子の投影画像を撮影し、下式に従って、二次元に投影した金属粒子の粒子面積と等しい面積の円の周囲長を、撮像した金属粒子の周囲長で除した数値で表し、50個の金属粒子について上記方法に従って円形度を測定した。次いで、得られた測定値の相加平均値で求め、これを平均円形度とした。 <Average circularity>
The circularity of the metal particles used for the production of the metal powder is obtained by taking a projected image of the metal particles using a transmission electron microscope (TEM), and according to the following formula, the particle area of the metal particles projected in two dimensions The circumference of a circle with the same area was expressed by a numerical value obtained by dividing the circumference of the imaged metal particles, and the circularity of 50 metal particles was measured according to the above method. Subsequently, it calculated | required by the arithmetic mean value of the obtained measured value, and made this into the average circularity.
上記金属粉末の作製に用いた金属粒子の円形度は、透過型電子顕微鏡(TEM)を用いて、金属粒子の投影画像を撮影し、下式に従って、二次元に投影した金属粒子の粒子面積と等しい面積の円の周囲長を、撮像した金属粒子の周囲長で除した数値で表し、50個の金属粒子について上記方法に従って円形度を測定した。次いで、得られた測定値の相加平均値で求め、これを平均円形度とした。 <Average circularity>
The circularity of the metal particles used for the production of the metal powder is obtained by taking a projected image of the metal particles using a transmission electron microscope (TEM), and according to the following formula, the particle area of the metal particles projected in two dimensions The circumference of a circle with the same area was expressed by a numerical value obtained by dividing the circumference of the imaged metal particles, and the circularity of 50 metal particles was measured according to the above method. Subsequently, it calculated | required by the arithmetic mean value of the obtained measured value, and made this into the average circularity.
円形度=(金属粒子の投影面積に等しい円の周囲長)/(金属粒子の周囲長)
(フラックスの平均厚さの測定)
上記作製した金属粉末の中心部を、集束イオンビーム加工装置(株式会社日立ハイテクサイエンス社製、SMI2050)を用いて切断して、粒子薄片を作製した。透過型電子顕微鏡(日本電子株式会社製、JEM-2010F)を用いて倍率10000倍で撮像した上記粒子の中心線断面画像について、被覆しているフラックスの厚さを10か所で測定し、その平均値1を求めた。次いで、この測定を50個の金属粉末について行い、得られた平均値1の全平均を求め、これをフラックスの平均厚さとして求めた。 Circularity = (perimeter of circle equal to projected area of metal particle) / (perimeter of metal particle)
(Measurement of average thickness of flux)
The center part of the produced metal powder was cut using a focused ion beam processing apparatus (manufactured by Hitachi High-Tech Science Co., Ltd., SMI2050) to produce particle flakes. Using a transmission electron microscope (manufactured by JEOL Ltd., JEM-2010F), the thickness of the coated flux was measured at 10 locations on the center line cross-sectional image of the particles imaged at a magnification of 10,000 times. An average value of 1 was determined. Subsequently, this measurement was performed for 50 metal powders, and the total average of the obtainedaverage values 1 was determined, and this was determined as the average thickness of the flux.
(フラックスの平均厚さの測定)
上記作製した金属粉末の中心部を、集束イオンビーム加工装置(株式会社日立ハイテクサイエンス社製、SMI2050)を用いて切断して、粒子薄片を作製した。透過型電子顕微鏡(日本電子株式会社製、JEM-2010F)を用いて倍率10000倍で撮像した上記粒子の中心線断面画像について、被覆しているフラックスの厚さを10か所で測定し、その平均値1を求めた。次いで、この測定を50個の金属粉末について行い、得られた平均値1の全平均を求め、これをフラックスの平均厚さとして求めた。 Circularity = (perimeter of circle equal to projected area of metal particle) / (perimeter of metal particle)
(Measurement of average thickness of flux)
The center part of the produced metal powder was cut using a focused ion beam processing apparatus (manufactured by Hitachi High-Tech Science Co., Ltd., SMI2050) to produce particle flakes. Using a transmission electron microscope (manufactured by JEOL Ltd., JEM-2010F), the thickness of the coated flux was measured at 10 locations on the center line cross-sectional image of the particles imaged at a magnification of 10,000 times. An average value of 1 was determined. Subsequently, this measurement was performed for 50 metal powders, and the total average of the obtained
《積層造形物の作製》
〔積層造形物1の作製〕
下記の方法に従って、図2の(b)で示したフローに従って、図3に記載の立体積層造形物の形成装置を用いて、アルゴンガス雰囲気下で10mm×10mm×10mmの立方体の積層造形物1を作製した。 << Preparation of Laminated Model >>
[Preparation of Laminated Model 1]
According to the following method, according to the flow shown in FIG. 2 (b), using the three-dimensional layered object forming apparatus shown in FIG. 3, a cubiclayered object 1 of 10 mm × 10 mm × 10 mm in an argon gas atmosphere 1 Was made.
〔積層造形物1の作製〕
下記の方法に従って、図2の(b)で示したフローに従って、図3に記載の立体積層造形物の形成装置を用いて、アルゴンガス雰囲気下で10mm×10mm×10mmの立方体の積層造形物1を作製した。 << Preparation of Laminated Model >>
[Preparation of Laminated Model 1]
According to the following method, according to the flow shown in FIG. 2 (b), using the three-dimensional layered object forming apparatus shown in FIG. 3, a cubic
図3に示すように、金属粉末供給部(421)に上記作製した金属粉末1(1)を充填し、昇降用リフト(451)を上昇させ、当該金属粉末(1)を上方に押し出した。次いで、粉末リコーター(7)を用いて、厚さ規制を行いながら、薄層形成部(420)で、造形ステージ(6)上に、厚さ0.2mmとなる条件で金属粉末を水平に敷き詰め、薄層(5)を形成した。
As shown in FIG. 3, the metal powder supply part (421) was filled with the produced metal powder 1 (1), the lifting lift (451) was raised, and the metal powder (1) was pushed upward. Next, using the powder recoater (7), the metal powder is horizontally spread on the modeling stage (6) on the modeling stage (6) at the thin layer forming part (420) while controlling the thickness. A thin layer (5) was formed.
レーザー光照射部(440)は、レーザー光源(441)としてファイバーレーザー(波長:1.07μm、100%出力時:300W、エネルギー密度:120J/mm2))と、3Dガルバノスキャンヘッド(ARGES社製)、単焦点レンズ(f100)により構成し、金属粉末の薄層(5)表面での焦点スポットが30μmとなる条件で、走査速度を2000mm/sec、走査ピッチを40μmとし、レーザー光照射を2段階に分けて、10mm×10mmの面積に照射して焼結処理を行い、構造物層(5A)を形成した。第1の照射工程は、レーザー光源の出力を100Wで行い、次いで、第2の照射工程として、出力条件を300Wに変更して行った。
The laser beam irradiation unit (440) includes a fiber laser (wavelength: 1.07 μm, 100% output: 300 W, energy density: 120 J / mm 2 ) as a laser light source (441), and a 3D galvano scan head (manufactured by ARGES). ), Composed of a single focus lens (f100), under the condition that the focal spot on the surface of the thin layer (5) of the metal powder is 30 μm, the scanning speed is 2000 mm / sec, the scanning pitch is 40 μm, and laser beam irradiation is 2 By dividing into stages, an area of 10 mm × 10 mm was irradiated and sintered to form a structure layer (5A). In the first irradiation step, the output of the laser light source was performed at 100 W, and then as the second irradiation step, the output condition was changed to 300 W.
次いで、形成した第1の構造物層(5A)上に、上記と同様の方法で、厚さ0.2mmの第2の薄層を積層及びレーザー照射による焼結処理を計50回繰り返して行い、厚さ10mmの積層造形物1を作製した。
Next, a second thin layer having a thickness of 0.2 mm is laminated on the formed first structural layer (5A) in the same manner as described above, and the sintering treatment by laser irradiation is repeated 50 times in total. A layered object 1 having a thickness of 10 mm was produced.
〔積層造形物2~26の作製〕
上記積層造形物1の作製において、金属粉末1に代えて、それぞれ金属粉末2~26を用いた以外は同様にして、積層造形物2~26を作製した。 [Preparation of layered objects 2-26]
In the production of thelayered product 1, the layered products 2 to 26 were produced in the same manner except that the metal powders 2 to 26 were used in place of the metal powder 1, respectively.
上記積層造形物1の作製において、金属粉末1に代えて、それぞれ金属粉末2~26を用いた以外は同様にして、積層造形物2~26を作製した。 [Preparation of layered objects 2-26]
In the production of the
〔積層造形物27の作製〕
上記積層造形物1の作製において、金属粉末1により形成した薄層へのレーザー光照射を、第2ステップ(出力:300W)の1回照射に変更した以外は同様にして、積層造形物27を作製した。 [Preparation of Laminated Model 27]
In the production of thelayered object 1, the layered object 27 is formed in the same manner except that the laser beam irradiation to the thin layer formed of the metal powder 1 is changed to the single irradiation of the second step (output: 300 W). Produced.
上記積層造形物1の作製において、金属粉末1により形成した薄層へのレーザー光照射を、第2ステップ(出力:300W)の1回照射に変更した以外は同様にして、積層造形物27を作製した。 [Preparation of Laminated Model 27]
In the production of the
〔積層造形物28~30の作製〕
上記積層造形物1の作製において、金属粉末1により形成した薄層へのレーザー光照射として、使用するレーザー光のエネルギー密度を、それぞれ30J/mm2、45J/mm2、150J/mm2に変更した以外は同様にして、積層造形物28~30を作製した。 [Preparation of Laminated Model 28-30]
In the production of thelayered object 1, the energy density of the laser beam used for the laser beam irradiation to the thin layer formed of the metal powder 1 is changed to 30 J / mm 2 , 45 J / mm 2 and 150 J / mm 2 , respectively. Laminated shaped products 28 to 30 were produced in the same manner except that.
上記積層造形物1の作製において、金属粉末1により形成した薄層へのレーザー光照射として、使用するレーザー光のエネルギー密度を、それぞれ30J/mm2、45J/mm2、150J/mm2に変更した以外は同様にして、積層造形物28~30を作製した。 [Preparation of Laminated Model 28-30]
In the production of the
《積層造形物の評価》
〔表面粗さの評価〕
上記作製した各積層造形物の最表面を、キーエンス社製のデジタルマイクロスコープ VHX-5000を用いて三次元での形状表示を行い、その表示画像における凹凸状態を観察し、下記の基準に従って、積層造形物の表面粗さを評価した。 << Evaluation of Laminated Model >>
[Evaluation of surface roughness]
The outermost surface of each of the layered objects produced above is displayed in three dimensions using a digital microscope VHX-5000 manufactured by Keyence, and the uneven state in the displayed image is observed. The surface roughness of the shaped object was evaluated.
〔表面粗さの評価〕
上記作製した各積層造形物の最表面を、キーエンス社製のデジタルマイクロスコープ VHX-5000を用いて三次元での形状表示を行い、その表示画像における凹凸状態を観察し、下記の基準に従って、積層造形物の表面粗さを評価した。 << Evaluation of Laminated Model >>
[Evaluation of surface roughness]
The outermost surface of each of the layered objects produced above is displayed in three dimensions using a digital microscope VHX-5000 manufactured by Keyence, and the uneven state in the displayed image is observed. The surface roughness of the shaped object was evaluated.
◎:積層造形物の最表面は、金属粒子の粒子径起因の凹凸のみで、極めて平滑である
○:積層造形物の最表面は、ほぼ金属粒子の粒子径起因の凹凸のみで、平滑である
△:わずかに、焼結時の金属粒子の凝集に起因する凹凸は認められるが、実用上は許容される品質である
×:明らかに焼結時の金属粒子の凝集による凹凸が発生しており、実用上問題となる品質である
××:焼結時に、金属粒子の凝集による強い凹凸が発生しており、実用に耐えない品質である
〔造形速度の評価〕
上記積層造形物の作製において、レーザー光照射時の走査速度を、500mm/sec、1000mm/sec、2000mm/sec(上記実施条件)、3000mm/sec、4000mm/secに変更して、各評価用サンプルを作製した。 A: The outermost surface of the layered object is extremely smooth due to only the irregularities due to the particle size of the metal particles. ○: The outermost surface of the layered object is smooth only due to the irregularities due to the particle size of the metal particles. Δ: Slight irregularities due to aggregation of metal particles during sintering are observed, but acceptable in practical use. X: Clear irregularities due to aggregation of metal particles during sintering have occurred. , Which is a quality that is a problem in practical use XX: Strong unevenness due to aggregation of metal particles is generated during sintering, and it is a quality that cannot withstand practical use [Evaluation of modeling speed]
In the production of the layered object, the scanning speed at the time of laser light irradiation is changed to 500 mm / sec, 1000 mm / sec, 2000 mm / sec (the above implementation conditions), 3000 mm / sec, 4000 mm / sec, and each evaluation sample. Was made.
○:積層造形物の最表面は、ほぼ金属粒子の粒子径起因の凹凸のみで、平滑である
△:わずかに、焼結時の金属粒子の凝集に起因する凹凸は認められるが、実用上は許容される品質である
×:明らかに焼結時の金属粒子の凝集による凹凸が発生しており、実用上問題となる品質である
××:焼結時に、金属粒子の凝集による強い凹凸が発生しており、実用に耐えない品質である
〔造形速度の評価〕
上記積層造形物の作製において、レーザー光照射時の走査速度を、500mm/sec、1000mm/sec、2000mm/sec(上記実施条件)、3000mm/sec、4000mm/secに変更して、各評価用サンプルを作製した。 A: The outermost surface of the layered object is extremely smooth due to only the irregularities due to the particle size of the metal particles. ○: The outermost surface of the layered object is smooth only due to the irregularities due to the particle size of the metal particles. Δ: Slight irregularities due to aggregation of metal particles during sintering are observed, but acceptable in practical use. X: Clear irregularities due to aggregation of metal particles during sintering have occurred. , Which is a quality that is a problem in practical use XX: Strong unevenness due to aggregation of metal particles is generated during sintering, and it is a quality that cannot withstand practical use [Evaluation of modeling speed]
In the production of the layered object, the scanning speed at the time of laser light irradiation is changed to 500 mm / sec, 1000 mm / sec, 2000 mm / sec (the above implementation conditions), 3000 mm / sec, 4000 mm / sec, and each evaluation sample. Was made.
上記作製した各評価用サンプルの表面を、キーエンス社製のデジタルマイクロスコープ VHX-5000を用いて観察し、それぞれの積層造形物の作製に用いた金属粒子の大きさより大きい欠損(レーザー光による焼結が不十分で、構造物が形成されず、空隙となった部分)の発生の有無を確認し、欠損の発生が生じないレーザー光の走査速度を求め、下記の基準に従って、造形速度を判定した。
The surface of each sample for evaluation prepared above was observed using a digital microscope VHX-5000 manufactured by Keyence Corporation, and a defect larger than the size of the metal particles used for the production of each layered object (sintering by laser light) Is not sufficient, the structure is not formed, and the void portion is confirmed to be generated), the scanning speed of the laser beam that does not generate defects is obtained, and the modeling speed is determined according to the following criteria .
◎:欠損が生じない最も速い走査速度が、4000mm/secである
○:欠損が生じない最も速い走査速度が、3000mm/secである
△:欠損が生じない最も速い走査速度が、2000mm/secである
×:欠損が生じない最も速い走査速度が、1000mm/secである
××:欠損が生じない最も速い走査速度が500mm/secである、又は500mm/secでも欠損が生じている
〔形成精度の評価〕
上記作製した10mm×10mm×10mmの各積層造形物の最表面部において、縦方向で10か所、横方向で10か所の寸法を、デジタルノギス(株式会社ミツトヨ製、スーパキャリパCD67-S PS/PM、「スーパキャリパ」は同社の登録商標)で測定した。次いで、測定した20か所の寸法の平均値を求め、積層造形物の設計値である「10.0mm」に対する寸法差の絶対値を求め、下記の基準に従って形成精度の評価を行った。 A: The fastest scanning speed at which no defect occurs is 4000 mm / sec. O: The fastest scanning speed at which no defect occurs is 3000 mm / sec. Δ: The fastest scanning speed at which no defect occurs is 2000 mm / sec. A: The fastest scanning speed at which no defect occurs is 1000 mm / sec. Xx: The fastest scanning speed at which no defect occurs is 500 mm / sec, or a defect occurs even at 500 mm / sec. Evaluation)
On the outermost surface portion of each of the 10 mm × 10 mm × 10 mm layered objects produced as described above, the dimensions of 10 places in the vertical direction and 10 places in the horizontal direction are digital calipers (Super Caliper CD67-S PS manufactured by Mitutoyo Corporation). / PM, “Super Caliper” is a registered trademark of the same company). Subsequently, the average value of the measured 20 dimensions was obtained, the absolute value of the dimensional difference with respect to “10.0 mm” which is the design value of the layered object was obtained, and the formation accuracy was evaluated according to the following criteria.
○:欠損が生じない最も速い走査速度が、3000mm/secである
△:欠損が生じない最も速い走査速度が、2000mm/secである
×:欠損が生じない最も速い走査速度が、1000mm/secである
××:欠損が生じない最も速い走査速度が500mm/secである、又は500mm/secでも欠損が生じている
〔形成精度の評価〕
上記作製した10mm×10mm×10mmの各積層造形物の最表面部において、縦方向で10か所、横方向で10か所の寸法を、デジタルノギス(株式会社ミツトヨ製、スーパキャリパCD67-S PS/PM、「スーパキャリパ」は同社の登録商標)で測定した。次いで、測定した20か所の寸法の平均値を求め、積層造形物の設計値である「10.0mm」に対する寸法差の絶対値を求め、下記の基準に従って形成精度の評価を行った。 A: The fastest scanning speed at which no defect occurs is 4000 mm / sec. O: The fastest scanning speed at which no defect occurs is 3000 mm / sec. Δ: The fastest scanning speed at which no defect occurs is 2000 mm / sec. A: The fastest scanning speed at which no defect occurs is 1000 mm / sec. Xx: The fastest scanning speed at which no defect occurs is 500 mm / sec, or a defect occurs even at 500 mm / sec. Evaluation)
On the outermost surface portion of each of the 10 mm × 10 mm × 10 mm layered objects produced as described above, the dimensions of 10 places in the vertical direction and 10 places in the horizontal direction are digital calipers (Super Caliper CD67-S PS manufactured by Mitutoyo Corporation). / PM, “Super Caliper” is a registered trademark of the same company). Subsequently, the average value of the measured 20 dimensions was obtained, the absolute value of the dimensional difference with respect to “10.0 mm” which is the design value of the layered object was obtained, and the formation accuracy was evaluated according to the following criteria.
◎:設計値との差(絶対値)は、0.2mm未満である
○:設計値との差(絶対値)は、0.2mm以上、0.5mm未満である
△:設計値との差(絶対値)は、0.5mm以上、1.0mm未満である
×:設計値との差(絶対値)は、1.0mm以上、1.5mm未満である
××:設計値との差(絶対値)は、1.5mm以上である
以上により得られた各評価結果を、表Iに示す。 ◎: Difference from design value (absolute value) is less than 0.2 mm ○: Difference from design value (absolute value) is 0.2 mm or more and less than 0.5 mm △: Difference from design value (Absolute value) is 0.5 mm or more and less than 1.0 mm ×: Difference from design value (absolute value) is 1.0 mm or more and less than 1.5 mm XX: Difference from design value ( (Absolute value) is 1.5 mm or more Table I shows the evaluation results obtained as described above.
○:設計値との差(絶対値)は、0.2mm以上、0.5mm未満である
△:設計値との差(絶対値)は、0.5mm以上、1.0mm未満である
×:設計値との差(絶対値)は、1.0mm以上、1.5mm未満である
××:設計値との差(絶対値)は、1.5mm以上である
以上により得られた各評価結果を、表Iに示す。 ◎: Difference from design value (absolute value) is less than 0.2 mm ○: Difference from design value (absolute value) is 0.2 mm or more and less than 0.5 mm △: Difference from design value (Absolute value) is 0.5 mm or more and less than 1.0 mm ×: Difference from design value (absolute value) is 1.0 mm or more and less than 1.5 mm XX: Difference from design value ( (Absolute value) is 1.5 mm or more Table I shows the evaluation results obtained as described above.
表Iに記載の結果より明らかなように、個数平均粒子径が5~100μmの範囲内である金属粒子の表面に、平均厚さが5~30nmの範囲内のフラックスが被覆されている本発明の金属粉末を用いて形成した立体積層造形物は、比較例に対し、優れた表面粗さと形成精度を有し、かつ造形速度が速いことがわかる。
As is clear from the results shown in Table I, the present invention is such that the surface of metal particles having a number average particle diameter in the range of 5 to 100 μm is coated with a flux having an average thickness in the range of 5 to 30 nm. It can be seen that the three-dimensional layered object formed using this metal powder has excellent surface roughness and forming accuracy and has a high forming speed as compared with the comparative example.
更には、金属紛末を構成する金属粒子として、平均円形度が、0.90~0.98の範囲内である金属粒子を適用すること、粒度分布における変動係数(CV値)が15%以下の金属粒子を適用すること、金属粒子として、鉄、鉄合金、ニッケル、ニッケル合金、コバルト、コバルト合金、銅、銅合金、アルミニウム及びアルミニウム合金から選ばれる少なくとも一種の金属材料を適用すること、あるいはフラックスとして、ホウ酸、ホウ砂、ロジン、フッ化物及び塩化物から選ばれる少なくとも一種を適用すること、あるいは、粉末焼結積層造形物の製造方法として、適用するレーザー光として、エネルギー密度Eが45~150J/mm2の範囲内であるレーザー光を使用すること、金属粉末により形成している薄層にレーザー光を照射する際に、フラックスにより金属粉末表面の還元反応を促進する第1のレーザー光照射工程と、金属粉末を結合させる第2のレーザー光照射工程に分割して照射する方法とすることが、本発明の目的効果をより発揮させることができる点で好ましいことがわかる。
Further, as the metal particles constituting the metal powder, metal particles having an average circularity in the range of 0.90 to 0.98 are applied, and the coefficient of variation (CV value) in the particle size distribution is 15% or less. Applying at least one metal material selected from iron, iron alloy, nickel, nickel alloy, cobalt, cobalt alloy, copper, copper alloy, aluminum and aluminum alloy, or as metal particles, or As the flux, at least one selected from boric acid, borax, rosin, fluoride and chloride is applied, or as a method for producing a powder sintered laminate model, the energy density E is 45 as laser light to be applied. Use laser light in the range of up to 150 J / mm 2 and irradiate a thin layer made of metal powder with laser light In this case, the present invention can be divided into a first laser light irradiation step for promoting the reduction reaction on the surface of the metal powder by flux and a second laser light irradiation step for bonding the metal powder. It can be seen that this is preferable in that the objective effect can be exhibited more.
本発明の金属粉末は、積層体の形成の高速化を達成するとともに、形状精度及び平面性に優れた立体積層造形物を形成することができ、多種多様な最終製品や試作品を大量に製造する分野において、立体積層造形物をより短時間で製造することができる。
The metal powder of the present invention can achieve a high-speed formation of a laminate and can form a three-dimensional layered product excellent in shape accuracy and flatness, and manufacture a large variety of final products and prototypes. In the field to do, a three-dimensional laminate modeling thing can be manufactured in a shorter time.
1、1B 金属粉末
1A、1C 焼結金属粉末
2 金属粒子
3 フラックス
4 金属酸化被膜
5、5B 薄層(第1の薄層)
5A、5C 造形物層
6 造形ステージ
7 粉末リコーター
8A、8B 第2の薄層
400 立体積層造形物の形成装置
401 立体積層造形物の形成部
420 薄層形成部
421 金属粉末供給部
430 温度調整部
431 第1の温度調整装置
432 第2の温度調整装置
440 レーザー照射部
441 レーザー光源
442 ガルバノミラー駆動部
443 レーザー光窓
450 ステージ支持部
451 昇降用リフト
460 制御部
470 表示部
475 操作部
480 記憶部
485 データ入力部
490 支持基盤
500 コンピューター装置
3DM 立体積層造形物
d 金属粒子の粒子径
h フラックスの厚さ
L レーザー光
P1 ポジション1
P2 ポジション2 1,1B metal powder 1A, 1C sintered metal powder 2 metal particles 3 flux 4 metal oxide film 5, 5B thin layer (first thin layer)
5A, 5C Modeledobject layer 6 Modeling stage 7 Powder recoater 8A, 8B Second thin layer 400 Three-dimensional modeled object forming device 401 Three-dimensional modeled object forming part 420 Thin layer forming part 421 Metal powder supply part 430 Temperature adjusting part 431 First temperature adjustment device 432 Second temperature adjustment device 440 Laser irradiation unit 441 Laser light source 442 Galvano mirror driving unit 443 Laser light window 450 Stage support unit 451 Lift for lifting 460 Control unit 470 Display unit 475 Operation unit 480 Storage unit 485 Data input part 490 Support base 500 Computer device 3DM Three-dimensional layered object d Particle diameter of metal particle h Thickness of flux L Laser light P1 Position 1
P2 Position 2
1A、1C 焼結金属粉末
2 金属粒子
3 フラックス
4 金属酸化被膜
5、5B 薄層(第1の薄層)
5A、5C 造形物層
6 造形ステージ
7 粉末リコーター
8A、8B 第2の薄層
400 立体積層造形物の形成装置
401 立体積層造形物の形成部
420 薄層形成部
421 金属粉末供給部
430 温度調整部
431 第1の温度調整装置
432 第2の温度調整装置
440 レーザー照射部
441 レーザー光源
442 ガルバノミラー駆動部
443 レーザー光窓
450 ステージ支持部
451 昇降用リフト
460 制御部
470 表示部
475 操作部
480 記憶部
485 データ入力部
490 支持基盤
500 コンピューター装置
3DM 立体積層造形物
d 金属粒子の粒子径
h フラックスの厚さ
L レーザー光
P1 ポジション1
P2 ポジション2 1,
5A, 5C Modeled
Claims (9)
- 金属粉末焼結積層造形法に用いられる金属粉末であって、
個数平均粒子径が5~100μmの範囲内である金属粒子の表面に、平均厚さが5~30nmの範囲内のフラックスが被覆されていることを特徴とする金属粉末。 Metal powder used in the metal powder sintering additive manufacturing method,
A metal powder characterized in that the surface of a metal particle having a number average particle diameter in the range of 5 to 100 μm is coated with a flux having an average thickness in the range of 5 to 30 nm. - 前記金属粒子の平均円形度が、0.90~0.98の範囲内であることを特徴とする請求項1に記載の金属粉末。 2. The metal powder according to claim 1, wherein an average circularity of the metal particles is in a range of 0.90 to 0.98.
- 前記金属粒子の粒径分布における変動係数(CV値)が、15%以下であることを特徴とする請求項1又は請求項2に記載の金属粉末。 The metal powder according to claim 1 or 2, wherein a coefficient of variation (CV value) in a particle size distribution of the metal particles is 15% or less.
- 前記フラックスが、ホウ酸、ホウ酸塩、ホウ砂、フッ化物及び塩化物から選ばれる少なくとも一種であることを特徴とする請求項1から請求項3までのいずれか一項に記載の金属粉末。 The metal powder according to any one of claims 1 to 3, wherein the flux is at least one selected from boric acid, borate, borax, fluoride, and chloride.
- 前記金属粒子が、鉄、鉄合金、ニッケル、ニッケル合金、コバルト、コバルト合金、銅、銅合金、アルミニウム及びアルミニウム合金から選ばれる金属材料を含有することを特徴とする請求項1から請求項4までのいずれか一項に記載の金属粉末。 The metal particles contain a metal material selected from iron, iron alloy, nickel, nickel alloy, cobalt, cobalt alloy, copper, copper alloy, aluminum, and aluminum alloy. Metal powder as described in any one of these.
- 請求項1から請求項5までのいずれか一項に記載の金属粉末を用いて立体積層造形物を製造する焼結積層造形物の製造方法であって、
少なくとも、前記金属粉末を薄層に展開する薄層形成工程と、
前記薄層を構成する金属粉末に、造形対象物の断面形状に対応する形状パターンでレーザー光を照射して、前記金属粉末を結合させる断面形状形成工程を有し、
前記薄層形成工程と前記断面形状形成工程とを順次繰り返すことにより、立体積層造形物を製造することを特徴とする粉末焼結積層造形物の製造方法。 A method for producing a sintered layered product that produces a three-dimensional layered product using the metal powder according to any one of claims 1 to 5,
At least a thin layer forming step of developing the metal powder into a thin layer;
A cross-sectional shape forming step of irradiating the metal powder constituting the thin layer with a laser beam in a shape pattern corresponding to the cross-sectional shape of the object to be modeled to bond the metal powder,
A method for producing a powder-sintered layered object, wherein a three-dimensional layered object is manufactured by sequentially repeating the thin layer forming step and the cross-sectional shape forming step. - 前記金属粉末に、造形対象物の断面形状に対応する形状パターンでレーザー光を照射する断面形状形成工程において、照射する前記レーザー光の下式(1)で表されるエネルギー密度Eが、45~150J/mm2の範囲内であることを特徴とする請求項6に記載の粉末焼結積層造形物の製造方法。
式(1)
エネルギー密度E(J/mm2)={レーザー出力/(レーザー照射スピード×焦点スポット面積)} In the cross-sectional shape forming step of irradiating the metal powder with a laser beam in a shape pattern corresponding to the cross-sectional shape of the object to be shaped, the energy density E represented by the following formula (1) of the laser beam to be irradiated It is in the range of 150 J / mm < 2 >, The manufacturing method of the powder sintered laminated molded article of Claim 6 characterized by the above-mentioned.
Formula (1)
Energy density E (J / mm 2 ) = {Laser output / (Laser irradiation speed × Focus spot area)} - 前記金属粉末に、造形対象物の断面形状に対応する形状パターンでレーザー光を照射する断面形状形成工程が、フラックスにより金属粉末表面の還元反応を促進する第1のレーザー光照射工程と、前記金属粉末を結合させる第2のレーザー光照射工程より構成されていることを特徴とする請求項6又は請求項7に記載の粉末焼結積層造形物の製造方法。 The cross-sectional shape forming step of irradiating the metal powder with a laser beam in a shape pattern corresponding to the cross-sectional shape of the object to be shaped includes a first laser light irradiation step of accelerating a reduction reaction on the surface of the metal powder by flux, The method for producing a powder-sintered layered article according to claim 6 or 7, comprising a second laser light irradiation step for bonding powder.
- 請求項1から請求項5までのいずれか一項に記載の金属粉末を用いて形成されたことを特徴とする粉末焼結積層造形物。 A powder sintered layered product formed using the metal powder according to any one of claims 1 to 5.
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