WO2020138274A1 - Siの被膜を有する純銅粉を用いた積層造形物の製造方法 - Google Patents
Siの被膜を有する純銅粉を用いた積層造形物の製造方法 Download PDFInfo
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- WO2020138274A1 WO2020138274A1 PCT/JP2019/051093 JP2019051093W WO2020138274A1 WO 2020138274 A1 WO2020138274 A1 WO 2020138274A1 JP 2019051093 W JP2019051093 W JP 2019051093W WO 2020138274 A1 WO2020138274 A1 WO 2020138274A1
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- WIPO (PCT)
- Prior art keywords
- copper powder
- pure copper
- layer
- powder
- electron beam
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 49
- 238000000576 coating method Methods 0.000 title claims abstract description 28
- 239000011248 coating agent Substances 0.000 title claims abstract description 25
- 238000010894 electron beam technology Methods 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims description 43
- 239000002245 particle Substances 0.000 claims description 30
- 238000004458 analytical method Methods 0.000 claims description 8
- 230000014509 gene expression Effects 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims 3
- 238000005245 sintering Methods 0.000 abstract description 21
- 239000000654 additive Substances 0.000 abstract description 14
- 230000000996 additive effect Effects 0.000 abstract description 14
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 230000007423 decrease Effects 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 description 19
- 239000002184 metal Substances 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 18
- 230000008859 change Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004381 surface treatment Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- KSFBTBXTZDJOHO-UHFFFAOYSA-N diaminosilicon Chemical compound N[Si]N KSFBTBXTZDJOHO-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- ZPQAUEDTKNBRNG-UHFFFAOYSA-N 2-methylprop-2-enoylsilicon Chemical compound CC(=C)C([Si])=O ZPQAUEDTKNBRNG-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 epoxysilane Chemical compound 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K15/00—Electron-beam welding or cutting
- B23K15/0046—Welding
- B23K15/0086—Welding welding for purposes other than joining, e.g. built-up welding
-
- 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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- 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
-
- 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
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with 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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/34—Process control of powder characteristics, e.g. density, oxidation or flowability
-
- 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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/36—Process control of energy beam parameters
-
- 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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/10—Pre-treatment
-
- 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
- B33Y50/00—Data acquisition or data processing for additive manufacturing
- B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
-
- 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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
- B22F10/25—Direct deposition of metal particles, e.g. direct metal deposition [DMD] or laser engineered net shaping [LENS]
-
- 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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
- B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
-
- 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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/10—Copper
-
- 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
- B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
- B22F2302/45—Others, including non-metals
-
- 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
- B22F2304/00—Physical aspects of the powder
- B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
-
- 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 method for manufacturing a layered product using pure copper powder having a Si film.
- the 3D printer is also called an additive manufacturing (AM) method, in which metal powder is thinly spread on a substrate to form a metal powder layer, and the metal powder layer is scanned with an electron beam or laser light to be melted and solidified.
- AM additive manufacturing
- a new powder is thinly laid on top, melted and solidified in the same manner, and this is repeated to produce a metal-shaped object having a complicated shape.
- the metal powder when the metal powder is irradiated with the electron beam, the metal powder may have a high electric resistance and thus may be charged up. Therefore, the metal powder is preheated and the adjacent pure copper powder is necked to form a conductive path. However, at this time, there is a problem that the metal powder is partially sintered by the preheating, and if the sintering progresses, it is difficult for the powder to come out from the inside of the hole of the shaped article.
- EB electron beam
- Patent Document 1 discloses a metal powder subjected to surface treatment in order to suppress sintering and make necking as weak as possible. Specifically, an organic coating is formed on the surface of the metal powder using a silane coupling agent, etc., so that the electron beam can be directly applied to the metal powder in the deposited state without partial sintering even by preheating. Techniques that allow irradiation are described.
- the present invention suppresses partial sintering due to preheating of pure copper powder in additive manufacturing by an electron beam (EB) method, and suppresses a decrease in vacuum degree during modeling by carbon (C) during modeling.
- An object of the present invention is to provide a method for manufacturing a layered product using a pure copper powder having a Si coating formed thereon. Another object is to provide optimum preheating temperature and additive manufacturing conditions for the pure copper powder on which the Si coating is formed.
- the present invention provides the following embodiments. 1) Spread pure copper powder, preheat this pure copper powder, scan it with an electron beam to partially melt and solidify it, form a first layer, and spread new pure copper powder on it. After the powder is preheated, it is partially melted and solidified by scanning with an electron beam to form a second layer, and this operation is repeated to stack the layers.
- the pure copper powder is a pure copper powder on which a Si coating is formed, and the Si adhesion amount is 5 to 200 wtppm, the C adhesion amount is 15 wtppm or more, and the weight ratio C/Si is 3 or less.
- a method for producing a layered product comprising using a pure copper powder and setting the preheating temperature to 400°C or higher and lower than 800°C. 2) Spread pure copper powder, preheat this pure copper powder, scan it with an electron beam to partially melt and solidify it, form a first layer, and spread new pure copper powder on it. After the powder is preheated, it is partially melted and solidified by scanning with an electron beam to form a second layer, and this operation is repeated to stack the layers.
- the pure copper powder is a pure copper powder having a film of Si formed thereon, and when Si is analyzed by WDX analysis, a portion of 1/10 or more of the maximum signal intensity is 40% or more of the entire particles.
- a pure copper powder having a C adhesion amount of 15 wtppm or more and a weight ratio C/Si of the Si adhesion amount and the C adhesion amount of 3 or less is used, and the preheating temperature is 400° C. or higher and 800 A method for producing a layered product, wherein the temperature is lower than °C. 3)
- Spread pure copper powder preheat this pure copper powder, scan with an electron beam to partially melt and solidify it, form a first layer, and spread pure copper powder anew on it After the powder is preheated, it is partially melted and solidified by scanning with an electron beam to form a second layer, and this operation is repeated to stack the layers.
- the pure copper powder is a pure copper powder on which a Si coating is formed, and the Si coating has a film thickness of 5 nm or more and 300 nm or less, a C adhesion amount of 15 wtppm or more, and a Si adhesion amount and a C adhesion amount.
- a method for producing a laminate-molded article comprising using pure copper powder having a weight ratio C/Si of 3 or less and setting the preheating temperature to 400° C. or more and less than 800° C. 4)
- the method for producing a layered product according to any one of 1) to 3) above which is characterized by the following.
- the unit of each parameter is as follows. Voltage (kV) Current (mA) Scan speed (mm/sec) Beam diameter (diameter) (mm) 5)
- the unit of each parameter is as follows.
- ADVANTAGE OF THE INVENTION in the additive manufacturing by an electron beam (EB) system, partial sintering by preheating can be suppressed and the fall of the vacuum degree at the time of modeling by carbon (C) at the time of modeling is suppressed. It becomes possible. Further, according to the present invention, preheating at a high temperature is possible and heat diffusion due to heat conduction can be suppressed, so that subsequent melting with an electron beam can be efficiently performed. Further, according to the present invention, it becomes possible to manufacture a pure copper laminated model having a good surface condition.
- ⁇ Metallic powder used in additive manufacturing by electron beam (EB) method is usually preheated for the purpose of suppressing charge-up. Preheating is performed at a relatively low temperature, but the metal powder partially sinters and necks, making it difficult to remove the metal powder remaining in the modeled object. There was a problem that it could not be used.
- Patent Document 1 discloses a technique for forming a coating film of Si or Ti on the surface of the metal powder by performing a surface treatment with an organic substance such as diaminosilane or aminotitanate on the surface treatment means of the metal powder. The formation of such a coating is effective in suppressing partial sintering due to preheating.
- the organic substance (C) is also attached at the same time, but when pure copper powder to which such an organic substance is attached is used, the degree of vacuum is lowered during the layered manufacturing. , The molding conditions become unstable. Further, during molding, a part of the organic matter may be decomposed by heat and turned into a gas to generate an offensive odor.
- the inventors of the present invention have made intensive studies on such a problem and found that the degree of vacuum is lowered during modeling when the ratio of C to Si exceeds a predetermined range. Further, it was found that by heating the surface-treated pure copper powder under a certain condition, the ratio of C adhering to the pure copper powder can be suppressed within a certain range, and the decrease in the degree of vacuum can be suppressed. In view of such circumstances, the present inventors provide a method for manufacturing a layered product using a pure copper powder on which a Si film is formed as a raw material, and a method for manufacturing a layered product optimal for this pure copper powder. Is provided.
- the pure copper powder according to the embodiment of the present invention is a pure copper powder on which a Si coating is formed, the Si adhesion amount is 5 wtppm or more and 200 wtppm or less, the C adhesion amount is 15 wtppm or more, and the weight ratio C/Si is 3 or less.
- the Si adhesion amount is 5 wtppm or more and 200 wtppm or less
- the C adhesion amount is 15 wtppm or more
- the weight ratio C/Si is 3 or less.
- the adhered amount of Si exceeds 200 wtppm, the conductivity and density of the shaped article may be reduced, so Si is preferably set to 200 wtppm or less. Further, it is considered that the same effect can be obtained not only when the Si film is formed on the pure copper powder but also when the Ti film is formed.
- the amount of C attached is 15 wtppm or more and the weight ratio C/Si is 3 or less. While the organic matter (film) containing C has the effect of suppressing oxidation, if the weight ratio C/Si exceeds 3 and adheres, the degree of vacuum decreases due to the desorption of C from the pure copper powder, and the molding conditions May not be stable, and the density and strength of the modeled object may be reduced. Also, an offensive odor may occur during modeling. Therefore, the C adhesion amount and the weight ratio C/Si are within the above ranges.
- a pure copper powder having a Si film formed thereon is 1/10 or more of a maximum signal intensity when Si is analyzed by WDX analysis.
- the part is 40% or more of the particles
- the C adhesion amount is 15 wtppm or more
- the weight ratio C/Si of the Si adhesion amount and the C adhesion amount is 3 or less. Since WDX (wavelength dispersive X-ray) analysis can specify where and to what extent Si element exists in the pure copper powder, it can be used as an index of the coverage of Si that coats the pure copper powder.
- the portion of 1/10 or more of the maximum signal intensity means an area excluding a portion of less than 1/10 of the maximum signal intensity detected by the detector when the pure copper powder is analyzed by WDX.
- the corresponding portion is a portion having a signal intensity of 40 to 400. If the coverage of Si is less than 40%, the necking portion due to partial sintering becomes large during preheating, and during EB spraying, heat escapes to the surrounding pure copper powder through necking, making it difficult to melt the pure copper powder. May be.
- the present invention is a pure copper powder having a Si coating formed thereon, the thickness of the Si coating is 5 nm or more and 300 nm or less, the C adhesion amount is 15 wtppm or more, and the Si adhesion amount and C It is characterized in that the weight ratio C/Si of the attached amount is 3 or less.
- the film thickness of the film is determined from the time taken until Auger electrons are detected by Auger electron spectroscopy (AES) and Si is no longer detected while digging the powder surface at a constant sputter rate and the sputter rate. It is the calculated value. Two points were randomly selected from one particle to be detected, and the values in the examples show the average values.
- the film thickness of the film is preferably 5 nm or more and 300 nm or less.
- the pure copper powder has an average particle diameter D50 (median diameter) of 10 ⁇ m or more and 150 ⁇ m or less.
- D50 average particle diameter
- the average particle diameter D50 means the average particle diameter at an integrated value of 50% in the particle size distribution measured by image analysis.
- the pure copper powder preferably has a purity of 99.9% or more. Since pure copper has high conductivity, it is possible to manufacture a molded article having excellent thermal conductivity by manufacturing a complicated shape that could not be manufactured conventionally by additive manufacturing. Further, when the density of the shaped article is low, the thermal conductivity also becomes low because a substance having poor thermal conductivity (such as air) enters the shaped article, but when the pure copper powder according to the embodiment of the present invention is used, It is possible to produce a layered product having a relative density of 95% or more.
- a method for producing pure copper powder according to the embodiment of the present invention will be described.
- a required amount of pure copper powder is prepared. It is preferable to use the pure copper powder having an average particle diameter D50 (median diameter) of 10 to 150 ⁇ m.
- the target particle size can be obtained by sieving the average particle size.
- the pure copper powder can be produced by using the atomizing method, but the pure copper powder according to the embodiment of the present invention may be produced by another method and is not limited thereto.
- pure copper powder is pretreated. Since a natural oxide film is usually formed on pure copper powder, it may be difficult to form a desired bond. Therefore, it is preferable to remove (pickle) the oxide film in advance.
- the natural oxide film can be removed by immersing the copper powder in a dilute sulfuric acid aqueous solution.
- this pretreatment is a treatment performed when a natural oxide film is formed on the pure copper powder, and it is not necessary to perform this pretreatment on all the pure copper powder. After pickling, if desired, you may wash with pure water.
- the pure copper powder is immersed in a solution containing a silane coupling agent to form a Si film on the surface of the pure copper powder.
- the solution temperature is preferably 5 to 40° C., and the longer the immersion time is, the larger the amount of Si adhered is. Therefore, it is preferable to adjust the immersion time by adjusting the target amount of Si adhered.
- silane coupling agent a commercially available silane coupling agent can be used, and aminosilane, vinylsilane, epoxysilane, mercaptosilane, methacrylsilane, ureidosilane, alkylsilane, or the like can be used.
- a 0.1 to 30% aqueous solution obtained by diluting this solution with pure water can be used. However, since the higher the concentration of the solution, the greater the amount of Si deposited, the concentration can be adjusted according to the target amount of Si deposited. Is preferably adjusted. Moreover, you may perform the said surface treatment, stirring desired.
- a coupling reaction is caused by heating in vacuum or in the air, and then dried to form a Si film.
- the heating temperature varies depending on the coupling agent used and can be, for example, 70 to 120°C.
- the heating temperature can be set to a temperature that gives a desired weight ratio C/Si.
- the temperature may be 400° C. or higher and 1000° C. or lower. If the heating temperature is lower than 400° C., the organic substances cannot be sufficiently removed, which causes deterioration of the degree of vacuum at the time of modeling and contamination. If it exceeds 1000° C., the sintering progresses quickly and the powder state cannot be maintained.
- the heating can be performed in vacuum (about 10 ⁇ 3 Pa). Furthermore, the heating time can be adjusted together with the temperature so that the desired weight ratio C/Si can be obtained, and for example, it is preferably 2 to 12 hours.
- the pure copper powder having the Si coating film As described above, it is possible to obtain the pure copper powder having the Si coating film, the pure copper powder having the desired amount of Si and C attached and the weight ratio C/Si.
- the layered product according to the present embodiment can be manufactured by an electron beam (EB) system layered manufacturing method.
- EB electron beam
- a three-dimensional metal-molded article can be manufactured.
- the electron beam irradiation can be performed based on the three-dimensional data (design drawing) regarding the shape of the layered product.
- preheating is preferably performed at 400° C. or higher and lower than 800° C. If the temperature is less than 400° C., when the resistance of the pure copper powder spread in the above process is high, the pure copper powder is negatively charged by the electron beam, and the electrostatic force causes the powder to scatter, causing so-called smoke formation. On the other hand, if the temperature is 800° C. or higher, pre-sintering proceeds excessively and a desired shaped article cannot be obtained. Normally, when pure copper powder not subjected to surface treatment is used, it is necessary to perform preheating at about 300 to 400° C. in order to prevent charge-up, but by using the pure copper powder according to the present embodiment, it is possible to obtain a temperature of 400° C. or higher.
- Preheating is possible. Since copper is a material having a high thermal conductivity, the temperature of the modeled object is lowered due to thermal diffusion, which complicates the modeling conditions, but such preheating at a high temperature makes it possible The temperature decrease can be suppressed.
- the unit of each parameter is It is as follows. Voltage (kV) Current (mA) Scan speed (mm/sec) Beam diameter (diameter) (mm) Thickness of one layer of powder (mm)
- modeling can be performed by adjusting the area of the powder irradiated when the electron beam is scanned in a unit time and the output of the electron beam. For example, when the scan speed is increased, the output can be adjusted by increasing the output of the electron beam or decreasing the beam diameter accordingly.
- the pure copper powder according to the present embodiment can be molded.
- the beam diameter can be adjusted by an offset function that adjusts the focus position. Further, the thickness of the powder can be adjusted by the width of the stage lowered.
- the evaluation method and the like according to the embodiment of the present invention including the examples and the comparative examples are as follows.
- the average particle diameter D50 (volume basis) was measured by the following device and conditions. Manufacturer: Spectris Co., Ltd. (Malvern Division) Device name: Dry particle image analyzer Morphologi G3 Measurement condition: Particle introduction amount: 11 mm 3 Injection pressure: 0.8 bar Measurement particle size range: 3.5-210 ⁇ m Number of particles measured: 20000
- SII device name SPS3500DD
- Analytical method ICP-OES (high frequency inductively coupled plasma optical emission spectrometry) Measurement sample amount: 1g Number of measurements: Two times, and the average value is taken as the amount of adhesion.
- the amount of change in oxygen concentration after heating 150° C., 24 hours
- the pure copper powder on which the Si coating was formed was examined, and the amount of change in oxygen concentration (after heating/before heating) was 5 or less. It was judged that the thing was circle (o), and the thing exceeding 5 was x (x).
- Si coverage When Si is analyzed by WDX analysis, the ratio of 1/10 or more of the maximum signal intensity to the entire particle is called “Si coverage”.
- One particle is analyzed as a sample, and the coverage of Si is measured using the image processing function in WDX. Specifically, one screen of one particle on the screen by WDX is scanned, and the signal intensity of Si is measured. However, since the back side of the particle cannot be scanned, accurately speaking, when the area of the image viewed from one direction is 100%, Si occupies the image (portion of 1/10 or more of the maximum signal intensity). The area ratio of is the coverage.
- Si film thickness is a value calculated from the time taken until Auger electrons are detected by Auger electron spectroscopy (AES) and Si is no longer detected while digging the powder surface at a constant sputter rate, and the sputter rate. Is. Two points were randomly selected from one particle to be detected, and the values in the examples show the average values.
- Manufacturer JEOL Ltd.
- Example 1 Heat treatment temperature after surface treatment
- pure copper powder prepared was pure copper powder having an average particle size (D50) of 72 ⁇ m and a specific surface area of 0.0024 m 2 /g, which was prepared by an atomizing method. The film was removed. Next, pure copper powder was immersed in an aqueous coupling agent solution (5%) diluted with pure water for 60 minutes, and then dried at 70 to 120° C. in vacuum or in the air. After drying, this pure copper powder was heat-treated in vacuum at 550 to 800° C. (Examples 1-1 and 1-2). On the other hand, Comparative Examples 1-1 and 1-2 are not heat-treated. Table 1 shows a summary of the amount of Si deposited, the Si coverage, the Si film thickness, the amount of C deposited, and the weight ratio C/Si of the pure copper powder on which the film has been formed by the above processing.
- Example 2 Types of surface treatment agents
- pure copper powder prepared is pure copper powder having an average particle size (D50) of 72 ⁇ m and a specific surface area of 0.0028 m 2 /g, which is prepared by an atomizing method. The film was removed. Next, pure copper powder was diluted with pure water and immersed in an epoxysilane aqueous solution (5%) for 60 minutes, and then dried at 70 to 120° C. in vacuum or in the air. After drying, this pure copper powder was heat-treated in vacuum at 800° C. (Example 2-1). Table 2 shows a summary of the amount of Si attached, the amount of C attached, and the weight ratio C/Si of the pure copper powder having the Si film formed by the above treatment. As for the pure copper powder on which these Si coatings were formed, the “state of the powder after the preliminary sintering test” was verified, and as a result, a good result was shown. The above results are shown in Table 2.
- Example 3 Particle diameter of pure copper powder
- a pure copper powder having an average particle diameter (D50) of 38 ⁇ m prepared by an atomizing method was prepared, and the pure copper powder was immersed in a dilute sulfuric acid aqueous solution to remove the natural oxide film on the surface.
- pure copper powder was diluted with pure water and immersed in a diaminosilane aqueous solution (5%) for 60 minutes, and then dried at 70 to 120° C. in vacuum or in the air. After being dried, this pure copper powder was heat-treated in vacuum at 550° C.
- Example 3-1 Through the above treatments, the pure copper powder on which the Si coating was formed had an Si adhesion amount, a C adhesion amount, and a weight. Table 3 summarizes the ratio C/Si. As for the pure copper powder on which these Si coatings were formed, the “state of the powder after the preliminary sintering test” was verified, and as a result, a good result was shown. The above results are shown in Table 3.
- Example 4 Manufacturing method of layered product
- a metal additive manufacturing apparatus A2X manufactured by Arcam a 35 mm square, 35 mm thick modeled object was produced.
- the pure copper powder of Example 1-2 (pure copper powder having a Si film formed thereon) was used as a raw material, and a 200 mm square and 20 mm thick copper plate was used as a substrate.
- a thermocouple was placed in the center of the back side of the substrate to monitor the preheating temperature.
- the preheating temperature was 650° C.
- the EB acceleration voltage, the beam current, and the scanning speed. was changed to perform modeling.
- the additive manufacturing by the electron beam (EB) method it is possible to suppress the partial sintering due to preheating or the like, and at the same time, the contamination of the modeling machine or the occurrence of the contamination due to the carbon (C) occurs. It becomes possible to suppress.
- This makes it possible to manufacture a laminate-molded article having a complicated shape, and further, although a pure copper powder layer is formed, it can be reused even if it remains without being irradiated with an electron beam. Have an effect.
- the pure copper powder according to the embodiment of the present invention can be used also in the additive manufacturing by the laser method, although it is particularly useful in the additive manufacturing by the EB method.
- the pure copper powder according to the embodiment of the present invention is particularly useful as a pure copper powder for a metal 3D printer.
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Abstract
Description
1)純銅粉を敷き詰め、この純銅粉を予備加熱後、電子ビームを走査させて部分的に溶融、凝固させて、第一の層を形成し、その上に新たに純銅粉を敷き詰め、この純銅粉を予備加熱後、電子ビームを走査させて部分的に溶融、凝固させて、第二の層を形成し、この作業を繰り返して積層していく、EB方式の積層造形法による積層造形物の製造方法であって、前記純銅粉として、Siの被膜が形成された純銅粉であって、Si付着量が5~200wtppm、C付着量が15wtppm以上であり、重量比率C/Siが3以下である純銅粉を使用し、前記予備加熱温度を400℃以上800℃未満とすることを特徴とする積層造形物の製造方法。
2)純銅粉を敷き詰め、この純銅粉を予備加熱後、電子ビームを走査させて部分的に溶融、凝固させて、第一の層を形成し、その上に新たに純銅粉を敷き詰め、この純銅粉を予備加熱後、電子ビームを走査させて部分的に溶融、凝固させて、第二の層を形成し、この作業を繰り返して積層していく、EB方式の積層造形法による積層造形物の製造方法であって、前記純銅粉として、Siの被膜が形成された純銅粉であって、WDX分析によりSiを分析したとき最大信号強度の1/10以上の部分が粒子全体の40%以上であり、C付着量が15wtppm以上であって、Si付着量とC付着量の重量比率C/Siが3以下であることを特徴とする純銅粉を使用し、前記予備加熱温度を400℃以上800℃未満とすることを特徴とする積層造形物の製造方法。
3)純銅粉を敷き詰め、この純銅粉を予備加熱後、電子ビームを走査させて部分的に溶融、凝固させて、第一の層を形成し、その上に新たに純銅粉を敷き詰め、この純銅粉を予備加熱後、電子ビームを走査させて部分的に溶融、凝固させて、第二の層を形成し、この作業を繰り返して積層していく、EB方式の積層造形法による積層造形物の製造方法であって、前記純銅粉として、Siの被膜が形成された純銅粉であって、Si被膜の膜厚が5nm以上300nm以下、C付着量が15wtppm以上、Si付着量とC付着量の重量比率C/Siが3以下であることを特徴とする純銅粉を使用し、前記予備加熱温度を400℃以上800℃未満とすることを特徴とする積層造形物の製造方法。
4)前記電子ビームの造形条件は、関係式(I):([電圧]×[電流])/([ビーム径]×[スキャンスピード])=2.3以上、6.0以下、を満たすことを特徴とすることを特徴とする上記1)~3)のいずれか一に記載の積層造形物の製造方法。
但し、各パラメータの単位は、以下の通りとする。
電圧(kV)
電流(mA)
スキャンスピード(mm/sec)
ビーム径(直径)(mm)
5)前記電子ビームの造形条件は、関係式(II):([電圧]×[電流])/([ビーム径]×[スキャンスピード]×[粉体1層の厚さ])=45以上、90以下、を満たすことを特徴とすることを特徴とする上記1)~3)いずれか一に記載の積層造形物の製造方法。
但し、各パラメータの単位は、以下の通りとする。
電圧(kV)
電流(mA)
スキャンスピード(mm/sec)
ビーム径(直径)(mm)
粉体1層の厚さ(mm)
6)前記純銅粉の平均粒子径D50(メジアン径)が10~150μmであることを特徴とする上記1)~3)のいずれか一に記載の積層造形物の製造方法。
このような事情に鑑み、本発明者らは、Siの被膜が形成された純銅粉を原料として用いた積層造形物の製造方法であって、この純銅粉に最適な積層造形物の製造方法を提供するものである。
Siの付着量が5wtppm未満の場合、部分焼結を十分に抑制することができない。Siの付着量が200wtppm超の場合、造形物の導電率や密度の低下を引き起こす可能性があるため、Siは200wtppm以下にすることが好ましい。また、純銅粉にSiの皮膜を形成した場合の他、Tiの皮膜を形成した場合も同様の効果を得ることができると考えられる。
WDX(波長分散型X線)分析は、純銅粉のどこに、どの程度Si元素が存在するかを特定することができるため、純銅粉を被覆するSiの被覆率の指標とすることができる。ここで、最大信号強度の1/10以上の部分とはWDXで純銅粉を分析した際に検出器が検出した最大の信号強度の1/10未満の部分を排除した面積を意味する。例えば粒全体をスキャンした時の信号強度が15~400であった場合、該当部は40~400の信号強度をもつ部分になる。
Siの被覆率が40%未満の場合、予備加熱した際に部分焼結によるネッキング部分が大きくなり、EB溶射時に、ネッキングを通じて周囲の純銅粉に熱が逃げてしまい、純銅粉の溶融が困難となることがある。
ここで、被膜の膜厚は、一定のスパッタレートで粉体表面を掘り進めながら、オージェ電子分光法(AES)によりオージェ電子を検出し、Siが検出しなくなるまでにかかった時間とスパッタレートから算出した値である。検出する場所は1個の粒子からランダムに2点選び、実施例の値はその平均値を示す。
被膜の膜厚が5nm以下の場合、予備加熱時に部分焼結を抑制することができない。被膜の膜厚が300nm以上の場合、ネッキングを形成しづらく、チャージアップの原因となるため、被膜の膜厚は5nm以上300nm以下にすることが好ましい。
まず、必要量の純銅粉を準備する。純銅粉は、平均粒子径D50(メジアン径)が10~150μmのものを用いることが好ましい。平均粒子径は、篩別することで目標とする粒度のものを得ることができる。純銅粉は、アトマイズ法を用いて作製することができるが、本発明の実施形態に係る純銅粉は、他の方法で作製されたものでもよく、これに限定されるものではない。
本実施形態に係る積層造形物は、電子ビーム(EB)方式の積層造形法によって製造することができる。まず、1)純銅粉を敷き詰め、2)この純銅粉を予備加熱し、3)電子ビームを走査させて部分的に溶融、凝固させて、第一の層を形成する。その上に、1)新たに純銅粉を敷き詰め、2)この純銅粉を予備加熱し、3)電子ビームを走査させて部分的に溶融、凝固させて、第二の層を形成する。
このように1)→2)→3)→1)・・・の作業を繰り返して積層していくことで、三次元の金属造形物を製造することができる。なお、電子ビームの照射は、積層造形物の形状に関する三次元データ(設計図)に基づいて行うことができる。
通常、表面処理を施さない純銅粉を用いた場合、チャージアップを防ぐために300~400℃程度で予備加熱を行う必要があるが、本実施形態に係る純銅粉を用いることにより、400℃以上の予備加熱が可能となる。銅は、熱伝導率の高い材料であるため、熱拡散によって造形物の温度低下が起こり、造形条件を困難にするが、このように高温での予備加熱が可能となることで、そのような温度低下を抑制することができる。
関係式(I):([電圧]×[電流])/([ビーム径]×[スキャンスピード])=2.3以上、6.0以下
または、
関係式(II):([電圧]×[電流])/([ビーム径]×[スキャンスピード]×[粉体1層の厚さ])=45以上、90以下
但し、各パラメータの単位は以下の通りとする。
電圧(kV)
電流(mA)
スキャンスピード(mm/sec)
ビーム径(直径)(mm)
粉体1層の厚さ(mm)
(平均粒子径D50について)
平均粒子径D50(体積基準)は、以下の装置及び条件で測定した。
メーカー:スペクトリス株式会社(マルバーン事業部)
装置名:乾式粒子画像分析装置 Morphologi G3
測定条件:
粒子導入量:11mm3
射出圧:0.8bar
測定粒径範囲:3.5-210μm
測定粒子数:20000個
純銅粉の比表面積は、以下の装置及び条件で測定した。
メーカー:ユアサイオニクス株式会社
装置名:モノソーブ
測定原理:BET1点法
メーカー:SII社製
装置名:SPS3500DD
分析法:ICP-OES(高周波誘導結合プラズマ発光分析法)
測定サンプル量:1g
測定回数:2回として、その平均値を付着量とする。
メーカー:LECO社製
装置名:TCH600
分析法:不活性ガス融解法
測定サンプル量:1g
測定回数:2回として、その平均値を付着量、濃度とする。
純銅粉は大気に曝されていると表面に自然酸化膜が形成される。そのような酸化膜が形成された純銅粉をAM造形に用いた場合、電子ビームやレーザーの反射率や吸収率が変化して、酸化膜が形成されていない純銅粉と熱吸収が異なり、同一条件で造形しても造形物の密度など物理的性質がばらついて安定しないという問題がある。純銅粉の表面にSiを含む有機被膜があることで大気中の水分と反応しづらく、酸化を抑制することが可能となる。酸化抑制の検証として、Si被膜が形成された純銅粉を加熱(150℃、24時間)した後の酸素濃度の変化量を調べ、酸素濃度の変化量(加熱後/加熱前)が5以下のものをマル(〇)、5を超えるものをバツ(×)、と判定した。
WDX分析によりSiを分析したとき、最大信号強度の1/10以上の部分が粒子全体に占める割合を「Siの被覆率」と呼ぶ。サンプルとして1粒子を分析し、WDX内の画像処理機能を用いて、Siの被覆率を測定する。具体的には、WDXによる画面上にある1個の粒子の1画面すべてをスキャンして、Siの信号強度を計測する。但し、粒子の裏面側はスキャンできないため、正確には、粒子を一方向から見た像の面積を100%としたときに、その像に占めるSi(最大信号強度の1/10以上の部分)の面積比率を、被覆率としている。
メーカー:日本電子製
装置名:FE-EPMA
加速電圧:15kV
出力電流:15μA
スキャン速度:10mm/sec
被膜の膜厚は、一定のスパッタレートで粉体表面を掘り進めながら、オージェ電子分光法(AES)によりオージェ電子を検出し、Siが検出しなくなるまでにかかった時間とスパッタレートから算出した値である。検出する場所は、1つの粒子からランダムに2点選び、実施例の値はその平均値を示す。
メーカー:日本電子 株式会社
装置名:AES(JAMP-7800F)
フィラメント電流:2.22A
プローブ電圧:10kV
プローブ電流:1.0×10-8A
プローブ径:約500nm
スパッタリングレート:7.2nm/min(SiO2換算)
加熱により焼結が進行した粉は、粉末同士が結合してサイズが大きくなるため、所定サイズの篩を通ることができない。したがって、篩を通ることができれば、加熱による焼結抑制効果の発現があると判断した。その検証として、φ50mmのアルミナ坩堝に50gの純銅粉を入れ、真空度1×10-3Pa以下の雰囲気で、500℃、4時間、加熱し、加熱後の純銅粉が目開き250μmの篩を通過するかどうかを確認し、通過したものを良、通過しなかったものを不良、と判定した。
C(炭素)の比率が高い純銅粉では、造形時に有機皮膜の一部が熱によって分解した気体が異臭の原因となる。また、分解したCが装置内に飛散するため、真空度が一時的に低下する。低い真空度では、EB(電子ビーム)による加熱が不十分になり、積層造形物に欠陥が生じることにもつながる。真空度の変化の検証として、造形時に真空度が2.5×10-3Pa以下で推移したものをマル(〇)、真空度が2.5×10-3Pa超に変化したものをバツ(×)、と判定した。
造形物の良、不良は、造形物の表面状態で観察し、表面がフラットな場合を良好とし、表面に溶け残りや表面の凹凸が激しい場合を不良とした。
純銅粉として、アトマイズ法で作製した平均粒子径(D50)が72μm、比表面積が0.0024m2/gの純銅粉を用意し、この純銅粉を希硫酸水溶液に浸漬して、表面の自然酸化膜を除去した。次に、純水で希釈したカップリング剤水溶液(5%)に純銅粉を60分間浸漬した後、真空中又は大気中、70~120℃で乾燥させた。乾燥後、この純銅粉を真空中、550~800℃で加熱処理した(実施例1-1、1-2)。一方、比較例1-1、1-2は、加熱処理はしていない。
以上の処理より、被膜が形成された純銅粉の、Si付着量、Si被覆率、Si膜厚、C付着量、及び重量比C/Siをまとめたものを表1に示す。
純銅粉として、アトマイズ法で作製した平均粒子径(D50)が72μm、比表面積が0.0028m2/gの純銅粉を用意し、この純銅粉を希硫酸水溶液に浸漬して、表面の自然酸化膜を除去した。次に、純水で希釈しエポキシシラン水溶液(5%)に純銅粉を60分間浸漬した後、真空中又は大気中、70~120℃で乾燥させた。乾燥後、この純銅粉を真空中、800℃で加熱処理した(実施例2-1)。以上の処理より、Siの被膜が形成された純銅粉の、Si付着量、C付着量、及び、重量比C/Siをまとめたものを表2に示す。
これらSiの被膜が形成された純銅粉について、「仮焼結試験後の粉の状態」の検証を行った結果、良好な結果を示した。以上の結果を表2に示す。
純銅粉として、アトマイズ法で作製した平均粒子径(D50)が38μm、の純銅粉を用意し、この純銅粉を希硫酸水溶液に浸漬して、表面の自然酸化膜を除去した。次に、純水で希釈しジアミノシラン水溶液(5%)に純銅粉を60分間浸漬した後、真空中又は大気中、70~120℃で乾燥させた。乾燥後、この純銅粉を真空中、550℃で加熱処理した(実施例3-1)以上の処理より、Siの被膜が形成された純銅粉の、Si付着量、C付着量、及び、重量比C/Siをまとめたものを表3に示す。
これらSiの被膜が形成された純銅粉について、「仮焼結試験後の粉の状態」の検証を行った結果、良好な結果を示した。以上の結果を表3に示す。
Arcam社製の金属積層造形装置A2Xを用い、35mm角、厚さ35mm、の造形物を作製した。原料として、実施例1-2(Siの被膜が形成された純銅粉)の純銅粉を用い、基板として、200mm角、厚さ20mmの銅板を用いた。また、基板の裏側の中央に熱電対を配置し、予備加熱温度をモニターした。
実施例4-1~実施例4-13、比較例4-1~比較例4-10は、表4に示すように、予備加熱温度を650℃とし、EBの加速電圧、ビーム電流、スキャン速度を変化させて造形を行った。その結果、実施例4-1から4-13までは、造形物の表面に解け残りがなく、平坦な表面が得られた。一方、比較例4-1から4-10では、造形物の表面に解け残りが発生し、また、表面に激しい凹凸が確認された。これらは、造形条件(電子ビームなどの条件)が適切でなかったためである。以上の結果を表4に示す。
Claims (6)
- 純銅粉を敷き詰め、この純銅粉を予備加熱後、電子ビームを走査させて部分的に溶融、凝固させて、第一の層を形成し、その上に新たに純銅粉を敷き詰め、この純銅粉を予備加熱後、電子ビームを走査させて部分的に溶融、凝固させて、第二の層を形成し、この作業を繰り返して積層していく、EB方式の積層造形法による積層造形物の製造方法であって、前記純銅粉として、Siの被膜が形成された純銅粉であって、Si付着量が5~200wtppm、C付着量が15wtppm以上であり、重量比率C/Siが3以下である純銅粉を使用し、前記予備加熱温度を400℃以上800℃未満とすることを特徴とする積層造形物の製造方法。
- 純銅粉を敷き詰め、この純銅粉を予備加熱後、電子ビームを走査させて部分的に溶融、凝固させて、第一の層を形成し、その上に新たに純銅粉を敷き詰め、この純銅粉を予備加熱後、電子ビームを走査させて部分的に溶融、凝固させて、第二の層を形成し、この作業を繰り返して積層していく、EB方式の積層造形法による積層造形物の製造方法であって、前記純銅粉として、Siの被膜が形成された純銅粉であって、WDX分析によりSiを分析したとき最大信号強度の1/10以上の部分が粒子全体の40%以上であり、C付着量が15wtppm以上であって、Si付着量とC付着量の重量比率C/Siが3以下であることを特徴とする純銅粉を使用し、前記予備加熱温度を400℃以上800℃未満とすることを特徴とする積層造形物の製造方法。
- 純銅粉を敷き詰め、この純銅粉を予備加熱後、電子ビームを走査させて部分的に溶融、凝固させて、第一の層を形成し、その上に新たに純銅粉を敷き詰め、この純銅粉を予備加熱後、電子ビームを走査させて部分的に溶融、凝固させて、第二の層を形成し、この作業を繰り返して積層していく、EB方式の積層造形法による積層造形物の製造方法であって、前記純銅粉として、Siの被膜が形成された純銅粉であって、Si被膜の膜厚が5nm以上300nm以下、C付着量が15wtppm以上、Si付着量とC付着量の重量比率C/Siが3以下であることを特徴とする純銅粉を使用し、前記予備加熱温度を400℃以上800℃未満とすることを特徴とする積層造形物の製造方法。
- 前記電子ビームの造形条件は、関係式(I):([電圧]×[電流])/([ビーム径]×[スキャンスピード])=2.3以上、6.0以下、を満たすことを特徴とすることを特徴とする請求項1~3のいずれか一項に記載の積層造形物の製造方法。
但し、各パラメータの単位は、以下の通りとする。
電圧(kV)
電流(mA)
スキャンスピード(mm/sec)
ビーム径(直径)(mm) - 記電子ビームの造形条件は、関係式(II):([電圧]×[電流])/([ビーム径]×[スキャンスピード]×[粉体1層の厚さ])=45以上、90以下、を満たすことを特徴とすることを特徴とする請求項1~3のいずれか一項に記載の積層造形物の製造方法。
但し、各パラメータの単位は、以下の通りとする。
電圧(kV)
電流(mA)
スキャンスピード(mm/sec)
ビーム径(直径)(mm)
粉体1層の厚さ(mm) - 前記純銅粉の平均粒子径D50(メジアン径)が10~150μmであることを特徴とする請求項1~3のいずれか一項に記載の積層造形物の製造方法。
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