JP6232524B1 - サーメット粉末、保護皮膜被覆部材及びその製造方法、並びに電気めっき浴中ロール及びその製造方法 - Google Patents
サーメット粉末、保護皮膜被覆部材及びその製造方法、並びに電気めっき浴中ロール及びその製造方法 Download PDFInfo
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- 239000011195 cermet Substances 0.000 title claims abstract description 97
- 239000000843 powder Substances 0.000 title claims abstract description 41
- 238000009713 electroplating Methods 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 239000011253 protective coating Substances 0.000 title claims description 12
- 239000002245 particle Substances 0.000 claims abstract description 90
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 23
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910039444 MoC Inorganic materials 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims description 36
- 239000011248 coating agent Substances 0.000 claims description 33
- 230000001681 protective effect Effects 0.000 claims description 33
- 239000010935 stainless steel Substances 0.000 claims description 33
- 229910001220 stainless steel Inorganic materials 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 21
- 238000005507 spraying Methods 0.000 claims description 21
- 238000007749 high velocity oxygen fuel spraying Methods 0.000 claims description 15
- 238000007751 thermal spraying Methods 0.000 claims description 15
- 230000003746 surface roughness Effects 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 7
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 claims description 5
- 239000007888 film coating Substances 0.000 claims description 5
- 238000009501 film coating Methods 0.000 claims description 5
- 229910003470 tongbaite Inorganic materials 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 abstract description 51
- 230000007797 corrosion Effects 0.000 abstract description 51
- 239000002253 acid Substances 0.000 abstract description 36
- 229910045601 alloy Inorganic materials 0.000 abstract description 21
- 239000000956 alloy Substances 0.000 abstract description 21
- 239000011651 chromium Substances 0.000 abstract description 19
- 229910052804 chromium Inorganic materials 0.000 abstract description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 description 37
- 238000007747 plating Methods 0.000 description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 229910000975 Carbon steel Inorganic materials 0.000 description 19
- 239000010962 carbon steel Substances 0.000 description 19
- 229910000831 Steel Inorganic materials 0.000 description 13
- 239000010959 steel Substances 0.000 description 13
- 239000004020 conductor Substances 0.000 description 11
- 239000011247 coating layer Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000007654 immersion Methods 0.000 description 7
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- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- 238000010286 high velocity air fuel Methods 0.000 description 5
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010285 flame spraying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910001120 nichrome Inorganic materials 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
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- 230000003247 decreasing effect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
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- 239000012528 membrane Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910001432 tin ion Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 238000006748 scratching Methods 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
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- 238000004381 surface treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
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- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
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- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
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- B22—CASTING; POWDER METALLURGY
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- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
- B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
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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
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Abstract
Description
(1)40質量%以上の炭化タングステン粒子と、
10〜40質量%の炭化モリブデン粒子と、
マトリックス金属としての、Ni又はNi合金と、
を含み、
さらに、クロムを炭化物又は前記マトリックス金属中の金属若しくは合金元素として8質量%以上含有することを特徴とするサーメット粉末。
前記サーメット皮膜は、Ni又はNi合金からなるマトリックス中に炭化タングステン粒子及び炭化モリブデン粒子が分散してなり、
前記サーメット皮膜中、前記炭化タングステン粒子の含有量が40質量%以上、前記炭化モリブデン粒子の含有量が10〜40質量%であり、さらに、クロムを炭化物又は前記マトリックス中の金属若しくは合金元素として8質量%以上含有することを特徴とする保護皮膜被覆部材。
本発明の一実施形態によるサーメット粉末は、40質量%以上の炭化タングステン粒子と、10〜40質量%の炭化モリブデン粒子と、マトリックス金属としてのNi又はNi合金を含み、さらに、クロムを炭化物又は前記マトリックス金属に含まれる金属若しくは合金元素として8質量%以上含有することを特徴とする。このサーメット粉末によれば、高い耐摩耗性とpHが1未満となる強酸に対する高い耐食性とを両立したサーメット皮膜を作製可能である。以下、本開示のサーメット粉末の各要素について説明する。
図1を参照して、本発明の一実施形態による保護皮膜被覆部材100は、ステンレス鋼基材10と、このステンレス鋼基材上に形成されたサーメット皮膜20と、を有する。サーメット皮膜20は、上記本開示のサーメット粉末を溶射材料として基材10上に溶射することにより形成される。その結果、サーメット皮膜20は、Ni又はNi合金からなるマトリックス22中に、炭化タングステン粒子及び炭化モリブデン粒子、さらに任意に炭化クロムを含む炭化物粒子24が分散した状態となる。サーメット皮膜20中における、炭化タングステン粒子の含有量及び粒度範囲、炭化モリブデン粒子の含有量及び粒度範囲、Ni含有量、クロム含有量、並びに炭化クロム粒子の粒度範囲に関しては、上記サーメット粉末に関して説明したものと同様である。また、本発明の一実施形態による電気めっき浴中ロールは、上記保護皮膜被覆部材100を含む。このような、本開示の保護皮膜被覆部材及び電気めっき浴中ロールは、高い耐摩耗性とpHが1未満となる強酸に対する高い耐食性とを両立できる。
カソード反応: Sn2+ + 2e- → Sn (1)
アノード反応: Fe → Fe2+ + 2e- (2)
従来型のロール仕様と本発明によるロール仕様の試料を作製し、pH<1となるように調整した強酸めっき溶液(メタンスルホン酸50g/L、錫イオン濃度25g/L)中で20日間の浸漬試験を行った。試料は、表1に示す5種類を作製した。すなわち、No.1は基材が従来型の炭素鋼であり、保護皮膜も従来型の試料である。これに対し、No.2〜5の試料では、基材をステンレス鋼とした。保護皮膜については、No.2ではNo.1と同じ従来型の皮膜を採用し、No.3〜No.5では、NiあるいはNi基合金をマトリックスとした各種炭化物サーメットのHVOF皮膜を採用しており、この内No.5が本発明例のサーメット仕様にあたる。No.5の皮膜において、Mo含有量は9.4質量%、Cr含有量は8.7質量%であり、WC粒子の粒度は最小0.1μm、最大6μmであり、Mo2C粒子の粒度は最小0.1μm、最大6μmであり、表面粗さRaは3.0μmであった。各試料は基材が露出した部分と保護皮膜部分がほぼ等しい表面積を持つように作製し、皮膜と基材の継ぎ目部分の特性も評価できるよう工夫した。
◎:ほとんど変化なし
○:若干の変化あり
△:変化あり
×:大きく変化あり
実施例1に示したNo.5仕様の保護皮膜の配合比に着目して、マトリックスとしてNi又はNi-20Cr合金を含み、粒度が0.1〜6μmの範囲に調整されたWC粒子、Cr3C2粒子、およびMo2C粒子を含む種々のサーメット粉末を作製した。ステンレス鋼上に得られたサーメット粉末をHVOF溶射して、保護皮膜を形成した。各試料における皮膜組成を表2に示す。実施例1と同様の浸漬試験を行うとともに、スガ摩耗試験を実施した。評価結果を表2に示す。
電気めっきラインのコンダクターロールに、従来品と本発明品を適用して比較した例について述べる。図2(A),(B)は、従来ロールの構造と本発明によるロールの構造を比較して示したものである。図2(A)に示す従来ロールでは、銅製の軸芯に炭素鋼管を焼嵌めして軸部を構成する一方、溶射により保護皮膜を形成した炭素鋼製スリーブを、炭素鋼管で形成したロール胴部に焼嵌めして胴部を構成し、これらを組み合わせてロール本体としていた。これに対し、図2(B)に示す本発明では、ステンレス鋼で構成したロール本体に溶射皮膜を形成するだけでよく、ロール本体の作製が極めて容易になっていることがわかる。本発明による皮膜の仕様は実施例2のNo.6を採用した。
10 基材(ステンレス鋼)
20 サーメット皮膜
22 マトリックス
24 炭化物粒子(WC粒子、Mo2C粒子、任意でCr3C2粒子)
300 電気めっき浴中ロール
30 ロール軸部
32 ロール胴部
34 サーメット皮膜(溶射皮膜)
Claims (15)
- 40質量%以上の炭化タングステン粒子と、
10〜40質量%の炭化モリブデン粒子と、
マトリックス金属としての、Ni又はNi合金と、
を含み、
さらに、炭化クロムを10質量%以上含有することを特徴とするサーメット粉末。 - 前記炭化タングステン粒子の含有量が70質量%以下である、請求項1に記載のサーメット粉末。
- 前記炭化タングステン粒子の粒度範囲が0.1〜6μmの範囲内にある、請求項1又は2に記載のサーメット粉末。
- 前記炭化モリブデン粒子の粒度範囲が0.1〜6μmの範囲内にある、請求項1〜3のいずれか一項に記載のサーメット粉末。
- ステンレス鋼基材と、該ステンレス鋼基材上に形成されたサーメット皮膜と、を有する保護皮膜被覆部材であって、
前記サーメット皮膜は、Ni又はNi合金からなるマトリックス中に炭化タングステン粒子及び炭化モリブデン粒子が分散してなり、
前記サーメット皮膜中、前記炭化タングステン粒子の含有量が40質量%以上、前記炭化モリブデン粒子の含有量が10〜40質量%であり、さらに、炭化クロムを10質量%以上含有することを特徴とする保護皮膜被覆部材。 - 前記炭化タングステン粒子の含有量が70質量%以下である、請求項5に記載の保護皮膜被覆部材。
- 前記サーメット皮膜中、前記炭化タングステン粒子の粒度範囲が0.1〜6μmの範囲内にある、請求項5又は6に記載の保護皮膜被覆部材。
- 前記サーメット皮膜中、前記炭化モリブデン粒子の粒度範囲が0.1〜6μmの範囲内にある、請求項5〜7のいずれか一項に記載の保護皮膜被覆部材。
- 前記サーメット皮膜の表面粗さRaが0.5〜10μmである、請求項5〜8のいずれか一項に記載の保護皮膜被覆部材。
- 請求項1〜4のいずれか一項に記載のサーメット粉末をステンレス鋼基材上に溶射する工程を含む、保護皮膜被覆部材の製造方法。
- 前記溶射は、HVOF溶射である、請求項10に記載の保護皮膜被覆部材の製造方法。
- 請求項5〜9のいずれか一項に記載の保護皮膜被覆部材を含むことを特徴とする電気めっき浴中ロール。
- ロール軸部及びロール胴部がともにステンレス鋼からなり、前記ロール胴部のみが請求項5〜9のいずれか一項に記載の保護皮膜被覆部材から構成されることを特徴とする電気めっき浴中ロール。
- ロール軸部及びロール胴部がともにステンレス鋼からなるロール部材の前記ロール胴部上にのみ、請求項1〜4のいずれか一項に記載のサーメット粉末を溶射してサーメット皮膜を形成することを特徴とする電気めっき浴中ロールの製造方法。
- 前記溶射は、HVOF溶射である、請求項14に記載の電気めっき浴中ロールの製造方法。
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