JP2010202928A - Method for producing metal shaped-article and metal resin composite powder for rapid prototyping - Google Patents
Method for producing metal shaped-article and metal resin composite powder for rapid prototyping Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 110
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 108
- 239000002184 metal Substances 0.000 title claims abstract description 108
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- 239000000805 composite resin Substances 0.000 title claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 55
- 239000011347 resin Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 47
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920000299 Nylon 12 Polymers 0.000 claims abstract description 35
- 239000005011 phenolic resin Substances 0.000 claims abstract description 34
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 15
- 239000011777 magnesium Substances 0.000 claims abstract description 15
- 229920003986 novolac Polymers 0.000 claims abstract description 13
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 9
- 238000000110 selective laser sintering Methods 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 59
- 239000000654 additive Substances 0.000 claims description 22
- 230000000996 additive effect Effects 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 16
- 239000004677 Nylon Substances 0.000 claims description 15
- 229920001778 nylon Polymers 0.000 claims description 15
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 5
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 5
- 239000010680 novolac-type phenolic resin Substances 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 2
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 2
- 239000011812 mixed powder Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 238000005238 degreasing Methods 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 7
- 238000001764 infiltration Methods 0.000 description 6
- 230000008595 infiltration Effects 0.000 description 6
- 238000003475 lamination Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000756 V alloy Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- -1 titanium-aluminum-vanadium Chemical compound 0.000 description 1
Classifications
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- 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
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Abstract
Description
本発明は、立体形状データから、金属と樹脂との複合粉体を積層し、レーザ照射により成形体（グリーン体）を造形し、その後脱脂及び溶浸を行う選択的レーザ焼結間接法（Selective Laser Sintering間接法）を用いる金属造形物の製造方法に関する。また、本発明は、そのような金属造形物の製造方法において使用する金属と樹脂との複合粉末に関する。 The present invention is a selective laser sintering indirect method (Selective Indirect Method) in which a composite powder of metal and resin is laminated from three-dimensional shape data, a molded body (green body) is formed by laser irradiation, and then degreasing and infiltration are performed. The present invention relates to a method for manufacturing a metal shaped article using a laser indirect method. Moreover, this invention relates to the composite powder of the metal and resin used in the manufacturing method of such a metal molded article.
商品のデザイン／設計／製造の各過程において、デジタル情報を共有する３次元デジタルシステムが応用されつつある。そのなかでも、製造過程ではRP（Rapid Prototyping）法と呼ばれる三次元造型技術が適用されつつある。 In each process of product design / design / manufacturing, a three-dimensional digital system sharing digital information is being applied. In particular, a three-dimensional molding technique called RP (Rapid Prototyping) is being applied in the manufacturing process.
このRP法は、紙又は樹脂の分野における造形技術としては既に確立している。一方、金属分野における造形技術としては、選択的レーザ焼結法（SLS法）がよく利用される。このSLS法は、薄い粉末層を積層し、レーザ光を用いて特定領域を選択的に焼結する作業を繰り返すことにより、３次元形状を造形する技術であり、セラミックへも応用されている。 This RP method has already been established as a modeling technique in the field of paper or resin. On the other hand, a selective laser sintering method (SLS method) is often used as a modeling technique in the metal field. This SLS method is a technique for forming a three-dimensional shape by repeating a process of laminating a thin powder layer and selectively sintering a specific region using a laser beam, and is also applied to ceramics.
ここで、図９に基づいて、SLS間接法の基本原理を説明する。まず、レーザ照射・積層工程として、樹脂配合金属粉末（金属樹脂複合体粉末）を積層する。次に、積層した樹脂配合金属粉末の所定位置に選択的にレーザ照射する。このとき、レーザ出力が小さいため、金属粉末は溶融せず、樹脂のみが溶融する。さらに、樹脂配合金属粉末の積層と選択的なレーザ照射とを繰り返す。その結果、設計した形状を有する、樹脂配合金属粉末からなる成形体（グリーン体）が成形される。 Here, the basic principle of the SLS indirect method will be described with reference to FIG. First, as a laser irradiation / lamination process, a resin-mixed metal powder (metal resin composite powder) is laminated. Next, laser irradiation is selectively performed on a predetermined position of the laminated resin compound metal powder. At this time, since the laser output is small, the metal powder does not melt and only the resin melts. Further, the lamination of the resin compound metal powder and the selective laser irradiation are repeated. As a result, a molded body (green body) made of resin-mixed metal powder having the designed shape is molded.
レーザ照射・積層工程に続いて、脱脂・焼結・溶浸工程が行われる。まず、成形体を不活性ガス存在下で加熱することにより樹脂を分解（脱脂）し、金属粒子を焼結させて焼結体とする。その後、焼結させた金属よりも融点の低い金属を溶融させて、溶融した金属を、毛細管現象を利用して焼結体に溶浸させることにより、金属造形物（溶浸体）が完成する。 Following the laser irradiation / lamination process, a degreasing / sintering / infiltration process is performed. First, the molded body is heated in the presence of an inert gas to decompose (degrease) the resin and sinter the metal particles to obtain a sintered body. Thereafter, a metal having a melting point lower than that of the sintered metal is melted, and the molten metal is infiltrated into the sintered body using a capillary phenomenon, thereby completing a metal shaped article (infiltrated body). .
このSLS間接法を利用すれば、複雑な形状の金属部品を、寸法精度よく作製可能である。また、木型や金型等の型が不要であり、３次元CADデータを元に積層造形可能なことから、小ロット生産や切削加工できないような複雑な形状の物品製造等に特に有益である。 By using this SLS indirect method, it is possible to manufacture metal parts having complicated shapes with high dimensional accuracy. In addition, it does not require molds such as wooden molds or molds, and can be layered based on 3D CAD data, so it is particularly useful for small-lot production and manufacturing of complicated shapes that cannot be cut. .
SLS間接法に用いる積層造形物の製造方法では、樹脂バインダとしてフェノール樹脂が使用されていた。ここで、特許文献１には、樹脂バインダとしてナイロン樹脂を使用すると、フェノール樹脂を使用する場合と比較して、成形体の強度が高くなることが開示されている。また、特許文献２には、金属粒子の表面に合成樹脂バインダをコーティングすることが開示されている。 In the manufacturing method of the layered object used in the SLS indirect method, a phenol resin is used as the resin binder. Here, Patent Document 1 discloses that when a nylon resin is used as the resin binder, the strength of the molded body is higher than when a phenol resin is used. Patent Document 2 discloses that a surface of metal particles is coated with a synthetic resin binder.
さらに、SLS間接法に使用する積層造形装置及び積層造形用の樹脂配合金属粉末も市販されている。例えば、3Dシステムズ社（米国）が販売している積層造形用の樹脂配合金属粉末は、樹脂を配合したステンレス鋼粉末である。そして、ステンレス鋼粉末を積層造形に用いた場合は、銅を溶浸させる方法が採られている。 Furthermore, a layered manufacturing apparatus used for the SLS indirect method and a resin-mixed metal powder for layered modeling are also commercially available. For example, the resin-mixed metal powder for additive manufacturing sold by 3D Systems (USA) is a stainless steel powder blended with a resin. And when stainless steel powder is used for additive manufacturing, the method of infiltrating copper is taken.
特許文献１では、樹脂バインダとしてナイロン樹脂が好ましいことが開示されてはいるが、実施例が開示されていないため、フェノール樹脂と比較した効果は不明である。また、特許文献２では、樹脂バインダの種類が何ら限定されておらず、どのような樹脂と金属粉末との組み合わせが好ましいのかが全く不明である。 In Patent Document 1, it is disclosed that nylon resin is preferable as a resin binder, but since an example is not disclosed, the effect compared with phenol resin is unclear. Moreover, in patent document 2, the kind of resin binder is not limited at all, and what kind of combination of resin and metal powder is preferable is completely unknown.
また、上述した市販の積層造形装置及び樹脂配合金属粉末を使用して金属造形物を製作する場合には、ステンレス及び銅のどちらも比重が大きな金属であるため、造形物の重量が大きくなってしまうという問題があり、自動車又は航空機部品に求められるような軽量の造形物を作製することは困難であった。 Moreover, when manufacturing a metal modeling thing using the commercially available additive manufacturing apparatus and resin compounding metal powder mentioned above, since both stainless steel and copper are metals with large specific gravity, the weight of a modeling thing becomes large. Therefore, it has been difficult to produce a lightweight shaped object that is required for automobiles or aircraft parts.
本発明は、従来作製できなかった軽量な金属造形物を、選択的レーザ焼結間接法を用いて作製しうる金属造形物の製造方法、及びそのような金属造形物の製造方法に好適な金属と樹脂との複合粉末の提供を目的とする。 The present invention relates to a method for producing a metal shaped article that can be produced using a selective laser sintering indirect method, and a metal suitable for a method for producing such a metal shaped article, which could not be produced conventionally. The purpose is to provide a composite powder of a resin and a resin.
積層造形用の樹脂配合金属粉末は、配合するバインダ樹脂について、低出力レーザ照射によって硬化する熱硬化性と、積層時に適度な流動性を持つ熱可塑性という二つの異なる性質が求められる。特許文献１に開示されているように、熱硬化性樹脂であるフェノール樹脂を金属粉末に配合した場合、積層造形は可能であるが、成形体の強度が低いことは知られている。そこで、本発明者らは、まずナイロンを金属粉末に配合することを試みたが、ナイロンのみを金属粉末に配合しても、レーザ照射によって硬化すべき部分に十分な強度（高温硬さ）が得られず、樹脂配合金属粉末を複数層積層できないことが判明した。 The resin-mixed metal powder for layered molding is required to have two different properties for the binder resin to be blended: thermosetting that is cured by low-power laser irradiation, and thermoplasticity that has appropriate fluidity during lamination. As disclosed in Patent Document 1, when a phenol resin, which is a thermosetting resin, is blended with a metal powder, layered modeling is possible, but it is known that the strength of the molded body is low. Therefore, the inventors first tried to blend nylon with metal powder, but even if only nylon was blended with metal powder, sufficient strength (high temperature hardness) was applied to the portion to be cured by laser irradiation. It was not obtained, and it was found that a plurality of layers of resin-containing metal powder could not be laminated.
本発明者らは、鋭意検討を重ねた結果、熱可塑性樹脂であるナイロン12によって金属粉末を均一に被覆（コーティング）し、さらに熱硬化性樹脂であるフェノール樹脂の粉末を添加して金属樹脂複合体とすれば、成形体を焼結した後にマグネシウム又はマグネシウム合金を溶浸することによって、軽量で複雑な形状の造形物であってもSLS間接法を利用して積層造形しうることを見出し、本発明を完成させるに至った。 As a result of intensive studies, the present inventors have uniformly coated (coated) metal powder with nylon 12 which is a thermoplastic resin, and further added phenol resin powder which is a thermosetting resin to form a metal resin composite. If it is a body, by infiltrating magnesium or a magnesium alloy after sintering the compact, it is found that even a lightweight and complex shaped article can be layered using the SLS indirect method, The present invention has been completed.
具体的に、本発明は、
金属粉末をナイロン樹脂で均一に被覆し、さらにフェノール樹脂粉末を添加した金属樹脂複合粉末を用いて、選択的レーザ焼結間接法を用いて所定形状の金属造形物を製造する方法であって、
前記金属粉末は、チタン粉末又はチタン合金粉末であり、
前記ナイロン樹脂はナイロン12であり、
前記フェノール樹脂はノボラック型フェノール樹脂であり、
前記選択的レーザ焼結間接法において、焼結させたチタン又はチタン合金の焼結体に溶浸させる金属がマグネシウム又はマグネシウム合金である、
ことを特徴とする金属造形物の製造方法に関する。
Specifically, the present invention
A method of producing a metal shaped article of a predetermined shape using a selective laser sintering indirect method using a metal resin composite powder obtained by uniformly coating a metal powder with a nylon resin and further adding a phenol resin powder,
The metal powder is titanium powder or titanium alloy powder,
The nylon resin is nylon 12,
The phenolic resin is a novolac type phenolic resin,
In the selective laser sintering indirect method, the metal to be infiltrated into the sintered body of sintered titanium or titanium alloy is magnesium or magnesium alloy.
The present invention relates to a method for manufacturing a metal shaped article.
本発明の金属造形物の製造方法では、チタン粉末又はチタン合金粉末をナイロン12によって被覆したナイロン被覆金属粉末に、さらにノボラック型フェノール樹脂粉末を添加した金属樹脂複合粉末を積層造形用原料として使用し、SLS間接法によってチタン又はチタン合金からなる成形体を作製する。 In the method for producing a metal shaped article of the present invention, a metal resin composite powder obtained by adding a novolac-type phenol resin powder to a nylon-coated metal powder obtained by coating titanium powder or titanium alloy powder with nylon 12 is used as a raw material for additive manufacturing. Then, a compact made of titanium or a titanium alloy is produced by the SLS indirect method.
ここで、チタン粉末又はチタン合金粉末にナイロン12粉末及びノボラック型フェノール樹脂粉末を単に添加して混合するだけでは、樹脂比率が少なければレーザ照射しても樹脂が硬化せず、樹脂比率を増やしても成形体が積層造形に必要な硬さとはならなかった。また、必要な硬さを得るために樹脂比率をさらに増やすと、その後の脱脂工程及び焼結工程に悪影響を及ぼし、金属造形物の造形が困難となった。 Here, simply adding and mixing nylon 12 powder and novolac-type phenol resin powder to titanium powder or titanium alloy powder, if the resin ratio is small, the resin will not cure even if laser irradiation is performed, and the resin ratio is increased. However, the molded body did not have the hardness required for additive manufacturing. Moreover, when the resin ratio was further increased in order to obtain the required hardness, the subsequent degreasing process and sintering process were adversely affected, making it difficult to form a metal shaped article.
しかし、チタン粉末又はチタン合金粉末をナイロン12によって均一に被覆したナイロン被覆金属粉末に、さらにノボラック型フェノール樹脂粉末を添加した金属樹脂複合粉末を積層造形用原料として使用すれば、少ない樹脂比率でも十分な硬度が得られることが確認された。また、SLS間接法によって成形体を作製し、脱脂工程及び焼結工程を経てマグネシウム又はマグネシウム合金を溶浸させれば、ステンレス粉末の焼結体に銅を溶浸させて作製した金属造形物と比較して、非常に軽量な金属造形物を作製できることが確認された。 However, if a metal resin composite powder obtained by adding a novolac-type phenol resin powder to a nylon-coated metal powder uniformly coated with nylon 12 or titanium powder or titanium alloy powder is used as a raw material for additive manufacturing, a small resin ratio is sufficient. It was confirmed that a high hardness was obtained. In addition, if a molded body is produced by the SLS indirect method and magnesium or a magnesium alloy is infiltrated through a degreasing process and a sintering process, a metal shaped article produced by infiltrating copper into a sintered body of stainless powder and In comparison, it was confirmed that a very lightweight metal model can be produced.
なお、ここでいうチタン合金とは、例えば、チタン−アルミニウム−バナジウム系合金等である。また、ここでいうマグネシウム合金とは、例えば、マグネシウム−アルミニウム系合金、マグネシウム−亜鉛系合金等である。 The titanium alloy here is, for example, a titanium-aluminum-vanadium alloy. The magnesium alloy here is, for example, a magnesium-aluminum alloy, a magnesium-zinc alloy, or the like.
前記金属樹脂複合体は、最大粒径75μｍ以下のチタン粉末又はチタン合金粉末の表面を0.5重量％以上2.0重量％以下のナイロン12で被覆したナイロン被覆金属粉末に、中位径3μｍ以上10μｍ以下のノボラック型フェノール樹脂粉末を1.0重量％以上3.0重量％以下で添加したものであることが好ましい。 The metal resin composite has a median diameter of 3 μm or more and 10 μm or less on a nylon-coated metal powder having a surface of titanium powder or titanium alloy powder having a maximum particle size of 75 μm or less coated with nylon 12 of 0.5 wt% or more and 2.0 wt% or less. It is preferable that the novolac type phenol resin powder is added at 1.0 wt% or more and 3.0 wt% or less.
ここでいう中位径とは、粉末の体積平均径のうち累積の50％粒子径を示す。また、ここでいう最大粒径とは、篩にかけたチタン粉末又はチタン合金粉末を使用する場合に、その篩の目開きの寸法を示す。 The median diameter here refers to the cumulative 50% particle diameter of the powder volume average diameter. In addition, the maximum particle size referred to here indicates the size of the sieve opening when using a sieved titanium powder or titanium alloy powder.
前記金属樹脂複合体は、中位径100 nm以下のチタン酸化物粉末又はチタン炭化物粉末を0.01重量部以上0.2重量部以下含有することが好ましい。流動助剤として中位径100 nm以下のチタン酸化物粉末又はチタン炭化物粉末を0.01重量部以上0.2重量部以下で金属樹脂複合体に添加することにより、積層工程において金属樹脂複合粉末がより均一となるためである。 The metal resin composite preferably contains 0.01 to 0.2 parts by weight of titanium oxide powder or titanium carbide powder having a median diameter of 100 nm or less. By adding a titanium oxide powder or titanium carbide powder having a median diameter of 100 nm or less as a flow aid to the metal resin composite in an amount of 0.01 parts by weight or more and 0.2 parts by weight or less, the metal resin composite powder is more uniform in the lamination process. It is to become.
また、本発明は、
最大粒径75μｍ以下のチタン粉末又はチタン合金粉末の表面を0.5重量％以上2.0重量％以下のナイロン12で被覆したナイロン被覆金属粉末に、さらに中位径3μｍ以上10μｍ以下のノボラック型フェノール樹脂粉末を1.0重量％以上3.0重量％以下で添加したことを特徴とする、積層造形用の金属樹脂複合体粉末に関する。
The present invention also provides:
A nylon-coated metal powder with a surface of titanium powder or titanium alloy powder with a maximum particle size of 75 μm or less coated with 0.5 to 2.0 wt% nylon 12 and a novolac type phenol resin powder with a median diameter of 3 to 10 μm. The present invention relates to a metal resin composite powder for additive manufacturing, characterized by being added in an amount of 1.0 wt% or more and 3.0 wt% or less.
本発明の積層造形用の金属樹脂複合体粉末は、流動助剤として中位径100 nm以下のチタン酸化物粉末又はチタン炭化物粉末を0.01重量部以上0.2重量部以下で含有することが好ましい。 The metal-resin composite powder for additive manufacturing of the present invention preferably contains 0.01 to 0.2 parts by weight of titanium oxide powder or titanium carbide powder having a median diameter of 100 nm or less as a flow aid.
本発明の金属造形物の製造方法及び積層造形用の金属樹脂複合体粉末によれば、従来は不可能であった複雑な形状の軽量、かつ、高強度の金属造形物の製造が可能である。 According to the method of manufacturing a metal structure and the metal resin composite powder for additive manufacturing according to the present invention, it is possible to manufacture a light and high-strength metal structure having a complicated shape that has been impossible in the past. .
以下、本発明の実施の形態について、適宜図面を参酌しながら説明する。なお、本発明は、以下に限定されない。 Hereinafter, embodiments of the present invention will be described with reference to the drawings as appropriate. The present invention is not limited to the following.
（予備的検討）
１．ナイロン12被覆チタン粉末
本発明者らは、まず金属粉末として軽量なチタン粉末を選択し、特許文献１に開示されているように、ナイロン12をバインダ樹脂として使用することを試みた。最大粒径45μｍ以下のチタン粉末（(株)大阪チタニウムテクノロジーズ社製「TILOP-45」）をナイロン12で被覆したナイロン12被覆チタン粉末を作製し、SLS間接法を用いる金属造形物の作製を試みた。チタン粉末に対するナイロン12の重量割合は、3.0重量％とした。
(Preliminary examination)
1. Nylon 12-coated titanium powder The inventors first selected a light titanium powder as the metal powder, and attempted to use nylon 12 as the binder resin as disclosed in Patent Document 1. Nylon 12-coated titanium powder coated with nylon 12 with titanium powder with a maximum particle size of 45 μm or less (“TILOP-45” manufactured by Osaka Titanium Technologies Co., Ltd.) was prepared, and metal fabrication using the SLS indirect method was attempted. It was. The weight ratio of nylon 12 to titanium powder was 3.0% by weight.
このナイロン12被覆チタン粉末を用いて、3Dシステムズ社（米国）の積層造形装置（Sinterstation HiQ SLS）を使用して積層造形物の作製を試みた。しかし、レーザ照射後に得られる造形体はペラペラの軟体であり、造形対が装置内部のローラーに巻き込まれてしまった。また、二層目以降を積層することも不可能であった（後述する比較例１）。 Using this nylon 12-coated titanium powder, an attempt was made to produce a layered object using a 3D Systems (USA) additive manufacturing apparatus (Sinterstation HiQ SLS). However, the modeled body obtained after laser irradiation is a soft body of a slick surface, and the modeled pair has been caught in a roller inside the apparatus. Moreover, it was impossible to laminate the second and subsequent layers (Comparative Example 1 described later).
２．ナイロン12及びフェノール樹脂を含む乾式混合粉末
次に、本発明者らは、上記最大粒径45μｍ以下のチタン粉末に、乳鉢で粉砕したナイロン12粉末とフェノール樹脂（ノボラック型、住友ベークライト社製「スミライトレジンPR-50731」）粉末を添加し、乾式混合粉末を３種類作製した。ナイロン12粉末とフェノール樹脂（ノボラック型）粉末との比率は1:1.7とし、チタン粉末に対する樹脂の添加量は、2.7重量％、4.7重量％及び6.0重量％とした。
2. Dry mixed powder containing nylon 12 and phenolic resin Next, the inventors of the present invention applied the nylon 12 powder and phenolic resin (Novolac type, Sumitomo Bakelite Co. Light Resin PR-50731 ") powder was added to prepare three types of dry mixed powders. The ratio of nylon 12 powder to phenolic resin (novolak type) powder was 1: 1.7, and the amount of resin added to titanium powder was 2.7 wt%, 4.7 wt% and 6.0 wt%.
この乾式混合粉末３種類を、内径25.4mm、高さ6mmのリファインテック社製ピストンシリンダ内に充填し、昇温速度20℃／分で200℃まで加熱し、乾式混合粉末の硬さをデュロメーター（ゴム硬度計）によって経時的に測定した。その結果を、図１に示す。 Three types of this dry-mixed powder are filled into a refined-tech piston cylinder with an inner diameter of 25.4mm and a height of 6mm, and heated to 200 ° C at a heating rate of 20 ° C / min. The hardness of the dry-type mixed powder is measured using a durometer ( It was measured over time by a rubber hardness meter. The result is shown in FIG.
樹脂添加量が2.7重量％の場合、200℃で加熱を続けても硬度（デュロメーター硬度タイプＡ）は変化せず、積層造形には利用不可であった。樹脂添加量が4.7重量％及び6.0重量％の場合には、経時的に硬度が増加したが、200℃で１時間加熱しても、積層造形に必要とされる硬度90に到達しなかった。このため、積層造形に必要な高温時の硬度を得るためには、チタン粉末に大量の樹脂を添加する必要があり、積層造形用途には使用できないと推察された。 When the amount of resin added was 2.7% by weight, the hardness (durometer hardness type A) did not change even when heating was continued at 200 ° C., and was not usable for additive manufacturing. When the resin addition amount was 4.7 wt% and 6.0 wt%, the hardness increased with time, but even when heated at 200 ° C. for 1 hour, the hardness of 90 required for additive manufacturing was not reached. For this reason, in order to obtain the hardness at the high temperature required for additive manufacturing, it is necessary to add a large amount of resin to the titanium powder, and it was assumed that it cannot be used for additive manufacturing.
３．ナイロン12を被覆し、さらにフェノール樹脂を添加した被覆混合粉末
次に、本発明者らは、上記最大粒径45μｍ以下のチタン粉末をナイロン12によって被覆し、ナイロン被覆チタン粉末とした。さらに、乳鉢で粉砕したフェノール樹脂粉末を添加し、被覆混合粉末（金属樹脂複合粉末）３種類を作製した。ナイロン12粉末とフェノール樹脂（ノボラック型）粉末との比率は1:1.7とし、チタン粉末に対する樹脂の添加量は、2.5重量％、4.7重量％及び6.0重量％とした。
3. Coated mixed powder coated with nylon 12 and further added with phenol resin Next, the present inventors coated the above-mentioned titanium powder having a maximum particle size of 45 μm or less with nylon 12 to obtain a nylon-coated titanium powder. Furthermore, phenol resin powder pulverized in a mortar was added to produce three types of coated mixed powder (metal resin composite powder). The ratio of nylon 12 powder to phenolic resin (novolak type) powder was 1: 1.7, and the amount of resin added to the titanium powder was 2.5%, 4.7% and 6.0% by weight.
この被覆混合粉末３種類を、上述したピストンシリンダ内に充填し、昇温速度20℃／分で200℃まで加熱し、被覆混合粉末の硬さをデュロメーター（ゴム硬度計）によって経時的に測定した。その結果を、図２に示す。 Three types of the coating mixed powder were filled in the above-described piston cylinder, heated to 200 ° C. at a temperature rising rate of 20 ° C./min, and the hardness of the coating mixed powder was measured over time with a durometer (rubber hardness meter). . The result is shown in FIG.
いずれの樹脂添加量の場合でも、加熱開始から30分以内に硬度90に到達し、乾式混合粉末の場合と比較して、同じ樹脂を使用しても、少ない樹脂添加量で積層造形に必要な高温時の硬度を得ることが可能であった。 Regardless of the amount of resin added, the hardness reaches 90 within 30 minutes from the start of heating, and even if the same resin is used, it is necessary for additive manufacturing with a small amount of resin added compared to the case of dry mixed powder. It was possible to obtain hardness at high temperatures.
ここで、乾式混合粉末（樹脂添加量4.7重量％）と被覆混合粉末（樹脂添加量4.0重量％）をレーザ照射によって熱硬化させた後の走査電子顕微鏡写真、及びチタン粒子と樹脂との結合状態を表す概念図を、図３に示す。 Here, dry mixed powder (resin addition amount 4.7% by weight) and coating mixed powder (resin addition amount 4.0% by weight) after thermosetting by laser irradiation, and bonding state of titanium particles and resin FIG. 3 shows a conceptual diagram representing.
図３(a)に示す乾式混合粉末の場合、チタン粒子（チタン粉末）と樹脂とは不均一な状態であり、チタン粒子同士が樹脂によって結着されていない部分も多く存在するため、成形体の強度は低い。一方、図３(b)に示す被覆混合粉末の場合、チタン粒子が樹脂によって均一に被覆された状態であり、チタン粒子同士も樹脂によって均一に結着されているため、成形体の強度は高い。 In the case of the dry mixed powder shown in FIG. 3 (a), the titanium particles (titanium powder) and the resin are in a non-uniform state, and there are many portions where the titanium particles are not bound by the resin. The strength of is low. On the other hand, in the case of the coated mixed powder shown in FIG. 3 (b), the titanium particles are uniformly coated with the resin, and the titanium particles are also uniformly bonded with the resin. .
［実施例１］
最大粒径45μｍ以下のチタン粉末を、チタン粉末の重量に対して0.75重量％のナイロン12で、湿式法によって均一に被覆した。さらに、チタン粉末の重量に対して1.25重量％のノボラック型フェノール樹脂粉末（中位径6μｍ）を添加した金属樹脂複合粉末を調製した。この、金属樹脂複合粉末を原料として、SLS造形装置として3Dシステムズ社Sinterstation HiQ SLSを使用して積層造形を行い、金属造形物を作製した。
[Example 1]
A titanium powder having a maximum particle size of 45 μm or less was uniformly coated with 0.75 wt% nylon 12 based on the weight of the titanium powder by a wet method. Furthermore, a metal resin composite powder to which 1.25% by weight of novolak type phenol resin powder (median diameter 6 μm) was added with respect to the weight of the titanium powder was prepared. Using this metal resin composite powder as a raw material, additive fabrication was performed using 3D Systems Sinterstation HiQ SLS as an SLS modeling apparatus to produce a metal model.
具体的には、金属樹脂複合粉末を、供給トレイ温度66℃、造形ステージ雰囲気温度110℃、CO2レーザ出力23Wという条件下でブロック状の成形体とした後、高純度アルゴンガス雰囲気下、500℃で100分間加熱処理することにより脱脂工程を行い、樹脂を加熱分解した。さらに、700℃で金属マグネシウム（融点650℃）を焼結体に溶浸させた。 Specifically, the metal-resin composite powder, the feed tray temperature 66 ° C., the modeling stage atmospheric temperature 110 ° C., after the block-shaped molded body under the condition that the CO 2 laser output 23W, a high purity argon gas atmosphere, 500 A degreasing process was performed by heat treatment at 100 ° C. for 100 minutes to thermally decompose the resin. Furthermore, metallic magnesium (melting point 650 ° C.) was infiltrated into the sintered body at 700 ° C.
［実施例２］
チタン粉末の重量に対して1.1重量％のナイロン12で均一に被覆し、チタン粉末の重量に対して1.9重量％のノボラック型フェノール樹脂粉末を添加した金属樹脂複合粉末を調製すること以外、すべて実施例１と同様にして、金属造形物を作製した。
[Example 2]
Except for preparing a metal resin composite powder that is uniformly coated with nylon 12% by weight of titanium powder and 1.9% by weight of novolac type phenolic resin powder with respect to the weight of titanium powder. A metal shaped article was produced in the same manner as in Example 1.
［実施例３］
流動助剤として中位径25 nmのチタン酸化物粉末をチタン粉末の質量に対して0.05重量部添加する以外、すべて実施例２と同様にして、金属造形物を作製した。
[Example 3]
A metal shaped article was produced in the same manner as in Example 2 except that 0.05 part by weight of titanium oxide powder having a median diameter of 25 nm was added as a flow aid to the mass of the titanium powder.
［実施例４］
チタン粉末の重量に対して1.5重量％のナイロン12で均一に被覆し、チタン粉末の重量に対して2.5重量％のノボラック型フェノール樹脂粉末を添加する以外、すべて実施例１と同様にして、金属造形物を作製した。
[Example 4]
The metal was coated in the same manner as in Example 1 except that 1.5% by weight of nylon 12 was uniformly coated with respect to the weight of the titanium powder, and 2.5% by weight of the novolac type phenol resin powder was added with respect to the weight of the titanium powder. A model was produced.
［比較例１］
チタン粉末の重量に対して3.0重量％のナイロン12で均一に被覆し、ノボラック型フェノール樹脂粉末を添加しないこと以外、すべて実施例１と同様にして、金属造形物を作製した。
[Comparative Example 1]
A metal shaped article was produced in the same manner as in Example 1 except that 3.0% by weight of nylon 12 was uniformly coated with respect to the weight of the titanium powder and no novolac type phenol resin powder was added.
［比較例２］
チタン粉末の重量に対してノボラック型フェノール樹脂粉末（中位径3μｍ）を2.2重量％添加し、ナイロン12でチタン粉末を被覆しないこと以外、すべて実施例１と同様にして、金属造形物を作製した。
[Comparative Example 2]
A metal shaped article was prepared in the same manner as in Example 1 except that 2.2% by weight of novolac-type phenol resin powder (median diameter 3 μm) was added to the weight of the titanium powder, and the titanium powder was not covered with nylon 12. did.
［比較例３］
チタン粉末の重量に対して0.75重量％のナイロン12で均一に被覆し、チタン粉末の重量に対して1.95重量％のノボラック型フェノール樹脂粉末（中位径3μｍ）を添加する以外、すべて実施例１と同様にして、金属造形物を作製した。
[Comparative Example 3]
Example 1 all except that 0.75% by weight of nylon 12 is uniformly coated with respect to the weight of the titanium powder, and 1.95% by weight of novolac-type phenol resin powder (median diameter 3 μm) is added with respect to the weight of the titanium powder. In the same manner, a metal shaped article was produced.
［比較例４］
チタン粉末の重量に対して1.0重量％のナイロン12で均一に被覆し、チタン粉末の重量に対して1.7重量％のノボラック型フェノール樹脂粉末（中位径3μｍ）を添加する以外、すべて実施例１と同様にして、金属造形物を作製した。
[Comparative Example 4]
Example 1 all except that uniform coating with nylon 12 of 1.0% by weight with respect to the weight of titanium powder and addition of 1.7% by weight of novolac phenolic resin powder (median diameter 3 μm) with respect to the weight of titanium powder In the same manner, a metal shaped article was produced.
［比較例５］
チタン粉末の重量に対して1.5重量％のナイロン12で均一に被覆し、チタン粉末の重量に対して1.2重量％のノボラック型フェノール樹脂粉末（中位径3μｍ）を添加する以外、すべて実施例１と同様にして、金属造形物を作製した。
[Comparative Example 5]
Example 1 all except that uniform coating with 1.5% nylon 12 by weight of titanium powder and addition of 1.2% by weight of novolac phenolic resin powder (median diameter 3 μm) to the weight of titanium powder In the same manner, a metal shaped article was produced.
［比較例６］
チタン粉末の重量に対して1.75重量％のナイロン12で乾式法によって不均一に被覆し、チタン粉末の重量に対して2.95重量％のノボラック型フェノール樹脂粉末（中位径6μｍ）を添加する以外、すべて実施例１と同様にして、金属造形物を作製した。
[Comparative Example 6]
Other than adding 1.75% by weight of nylon 12 non-uniformly by dry method with respect to the weight of titanium powder and adding 2.95% by weight of novolac phenol resin powder (median diameter 6 μm) to the weight of titanium powder. All in the same manner as in Example 1, a metal shaped article was produced.
＜性能評価＞
実施例１〜４及び比較例１〜６の複合粉末状態と性能評価の結果を、表１に示す。
<Performance evaluation>
Table 1 shows the composite powder states and performance evaluation results of Examples 1 to 4 and Comparative Examples 1 to 6.
まず、実施例１〜４によって作製されたブロック状の成形体は、ローラーへの巻付きはなく、成形体の強度も十分であり、ハンドリングは良好であった。また、脱脂工程の状態及び金属マグネシウムの溶浸性も良好であり、設計通りの軽量な金属造形物が作製できた。 First, the block-shaped molded bodies produced in Examples 1 to 4 were not wound around a roller, the molded bodies had sufficient strength, and the handling was good. Moreover, the state of a degreasing process and the infiltration property of metallic magnesium were also favorable, and the lightweight metal modeling thing as designed was able to be produced.
一方、ナイロン12で均一にチタン粉末を被覆したのみである比較例１では、レーザ照射後に得られる造形体はペラペラの軟体であり、装置内部のローラーに巻き込まれてしまった。二層目以降を積層することも不可能であった。 On the other hand, in Comparative Example 1 in which the titanium powder was only uniformly coated with nylon 12, the shaped body obtained after the laser irradiation was a pliable soft body and was caught in a roller inside the apparatus. It was impossible to laminate the second and subsequent layers.
また、中位径3μmであるフェノール樹脂のみをチタン粉末に添加した比較例２は、熱硬化によって十分な硬さの成形体を作製できたが、非常に脆く、取り出す時点で破損してハンドリングが悪かった。このため、脱脂工程以降の工程を実施することは不可能であった。チタン粉末をナイロン12で均一に被覆し、さらに中位径3μmであるフェノール樹脂を添加した比較例３〜５でも、粉末の流動性が悪く、比較例２と同様に、成形体の強度が低かった。 Further, Comparative Example 2 in which only a phenol resin having a median diameter of 3 μm was added to titanium powder was able to produce a molded body having sufficient hardness by thermosetting, but it was very brittle and was damaged when taken out and handled. It was bad. For this reason, it was impossible to carry out the steps after the degreasing step. Even in Comparative Examples 3 to 5 in which the titanium powder was uniformly coated with nylon 12 and a phenol resin having a median diameter of 3 μm was added, the powder was poor in fluidity and, as in Comparative Example 2, the strength of the molded product was low. It was.
さらに、中位径6μmであるフェノール樹脂を添加しても、チタン粉末をナイロン12で不均一に被覆した比較例６（樹脂合計4.7重量％）は、比較例２〜５と異なり成形体を取り出して脱脂工程以降を実施することは可能であったが、図３(a)及び図３(b)に示したように、樹脂同士の凝集が起こっているために、成形体の強度は不十分であった。また、凝集した樹脂は均一被覆した樹脂に比べて脱脂効率が悪く、残存した炭素成分とマグネシウムとの濡れ性が悪いことが相まって、空孔の多い溶浸体となるという問題を生じた。 Further, even when phenol resin having a median diameter of 6 μm was added, Comparative Example 6 (total resin 4.7% by weight) in which titanium powder was unevenly coated with nylon 12 was different from Comparative Examples 2 to 5 in that the molded product was taken out. Although it was possible to carry out the degreasing process and thereafter, as shown in FIGS. 3 (a) and 3 (b), the resin is agglomerated, so the strength of the molded body is insufficient. Met. In addition, the agglomerated resin has a problem that the degreasing efficiency is lower than that of the uniformly coated resin, and the wettability between the remaining carbon component and magnesium is reduced, resulting in an infiltrated with many voids.
ここで、実施例１で金属マグネシウムを溶浸させる前後の焼結体の状態を、図４に示す。また、実施例４のマグネシウム溶浸後の造形物の組織断面を、図５に示す。実施例１の金属造形物は、チタン粒子の空隙にマグネシウムが十分に溶浸しており、気泡等は確認されなかった。 Here, the state of the sintered body before and after infiltrating metallic magnesium in Example 1 is shown in FIG. Moreover, the structure | tissue cross section of the molded article after the magnesium infiltration of Example 4 is shown in FIG. In the metal shaped article of Example 1, magnesium was sufficiently infiltrated into the voids of the titanium particles, and bubbles and the like were not confirmed.
また、実施例３について、設計寸法との誤差（単位mm）、密度、硬さ（HRB）、引張強さ及び破断伸びを測定した結果を、図６に示す。図６に示したブロック状の金属造形物の場合、設計寸法との誤差は最大でも2.0％であり、非常に小さかった。積層造形時のパラメータを変更することで、さらなる高精度化も可能である。また、硬さ、引張強さ及び破断伸びの測定値も、積層造形物として機械的強度は十分実用に耐えるレベルであった。 Moreover, about Example 3, the result of having measured the difference | error (unit mm) with a design dimension, a density, hardness (HRB), tensile strength, and breaking elongation is shown in FIG. In the case of the block-shaped metal shaped article shown in FIG. 6, the error from the design dimension was 2.0% at the maximum, which was very small. Higher accuracy can be achieved by changing the parameters during additive manufacturing. In addition, the measured values of hardness, tensile strength, and elongation at break were such that the mechanical strength of the layered product was sufficiently practical.
さらに、実施例４で使用した金属樹脂複合粉末を用いて積層造形を行うことによって、図７に示すような各種形状のチタン粉末成形体を製造することが可能であった。 Furthermore, by performing additive manufacturing using the metal resin composite powder used in Example 4, it was possible to manufacture variously shaped titanium powder compacts as shown in FIG.
図８は、図７の右端に写っている成形体のマグネシウム溶浸後の接写写真である。一辺2cmの立方体に収納できるような小型で、複雑な形状を有する金属造形物であるが、本発明では、欠損等を生じることなく、製造することが可能であった。 FIG. 8 is a close-up photograph after magnesium infiltration of the molded body shown in the right end of FIG. Although it is a small and complex metal shape that can be stored in a cube with a side of 2 cm, in the present invention, it can be produced without causing defects or the like.
本発明の金属造形物の製造方法及び積層造形用の金属樹脂複合体粉末は、金属積層造形分野において、軽量の金属造形物を作製する方法及び原料粉末として有用である。 The method for producing a metal shaped article and the metal resin composite powder for additive manufacturing of the present invention are useful as a method for producing a lightweight metal article and raw material powder in the metal additive manufacturing field.
Claims (5)
前記金属粉末は、チタン粉末又はチタン合金粉末であり、
前記ナイロン樹脂はナイロン12であり、
前記フェノール樹脂はノボラック型フェノール樹脂であり、
前記選択的レーザ焼結間接法において、焼結させたチタン又はチタン合金に溶浸させる金属がマグネシウム又はマグネシウム合金である、
ことを特徴とする金属造形物の製造方法。 A method of producing a metal shaped article of a predetermined shape using a selective laser sintering indirect method using a metal resin composite powder obtained by uniformly coating a metal powder with a nylon resin and further adding a phenol resin powder,
The metal powder is titanium powder or titanium alloy powder,
The nylon resin is nylon 12,
The phenolic resin is a novolac type phenolic resin,
In the selective laser sintering indirect method, the metal to be infiltrated into the sintered titanium or titanium alloy is magnesium or a magnesium alloy.
The manufacturing method of the metal molded object characterized by the above-mentioned.
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| WO2016031279A1 (en) * | 2014-08-27 | 2016-03-03 | 株式会社日立製作所 | Powder for layer-by-layer additive manufacturing, and process for producing object by layer-by-layer additive manufacturing |
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| JP2018505299A (en) * | 2014-12-12 | 2018-02-22 | マテリオン コーポレイション | Additive manufacture of articles containing beryllium |
| US11904391B2 (en) | 2014-12-12 | 2024-02-20 | Materion Corporation | Additive manufacturing of articles comprising beryllium |
| CN106583711A (en) * | 2016-12-31 | 2017-04-26 | 扬州立德粉末冶金股份有限公司 | Preparation method of low-friction piston for electric automobile shock absorber |
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