JPH07116483B2 - Amorphous alloy powder for corrosion resistant paint and corrosion resistant paint - Google Patents
Amorphous alloy powder for corrosion resistant paint and corrosion resistant paintInfo
- Publication number
- JPH07116483B2 JPH07116483B2 JP63115486A JP11548688A JPH07116483B2 JP H07116483 B2 JPH07116483 B2 JP H07116483B2 JP 63115486 A JP63115486 A JP 63115486A JP 11548688 A JP11548688 A JP 11548688A JP H07116483 B2 JPH07116483 B2 JP H07116483B2
- Authority
- JP
- Japan
- Prior art keywords
- amorphous alloy
- alloy powder
- corrosion resistant
- powder
- major axis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000843 powder Substances 0.000 title claims description 60
- 230000007797 corrosion Effects 0.000 title claims description 51
- 238000005260 corrosion Methods 0.000 title claims description 51
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims description 28
- 239000003973 paint Substances 0.000 title claims description 21
- 238000000576 coating method Methods 0.000 claims description 36
- 239000011248 coating agent Substances 0.000 claims description 34
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000008199 coating composition Substances 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 description 23
- 239000000956 alloy Substances 0.000 description 23
- 239000000463 material Substances 0.000 description 11
- 239000002184 metal Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Description
【発明の詳細な説明】 「産業上の利用分野」 本発明は、耐食性塗料用非晶質合金粉末およびこの合金
粉末を含有する耐食性塗料に関する。TECHNICAL FIELD The present invention relates to an amorphous alloy powder for a corrosion resistant coating and a corrosion resistant coating containing the alloy powder.
「従来の技術」 従来、耐食性を要求される塗料としてステンレス粉末を
含有した塗料が市販されている。このステンレス粉末の
形状は、幅10μｍ、長さ30μｍ、厚さ0.3μｍのフレー
ク状であり、この粉末を樹脂に混合して刷毛塗り、スプ
レー等で塗布するとステンレス粉末が樹脂の硬化時に生
ずる表面張力によって塗布面と平行に積層し、連続した
ステンレス被膜を形成し、素材を外気から遮断し、耐食
性を与えるというものである。“Prior Art” Conventionally, paints containing stainless powder are commercially available as paints that are required to have corrosion resistance. The shape of this stainless steel powder is flakes with a width of 10 μm, a length of 30 μm and a thickness of 0.3 μm. When this powder is mixed with resin and applied by brushing, spraying, etc., the surface tension of the stainless steel powder generated when the resin hardens By laminating in parallel with the coated surface, a continuous stainless film is formed, the material is shielded from the outside air, and corrosion resistance is provided.
しかしながら、ステンレスには、応力腐食割れ、孔食、
隙間腐食、水素脆性などの欠点があるため、上記ステン
レス粉末を含有させた塗料では十分な耐食性が得られな
い場合があった。However, stainless steel has stress corrosion cracking, pitting corrosion,
Due to defects such as crevice corrosion and hydrogen embrittlement, a coating containing the above stainless powder may not have sufficient corrosion resistance.
近年、非晶質合金などのステンレスよりも耐食性に優れ
た合金が開発されており、これらの合金を粉末化して塗
料に混合することにより、上記塗料よりもさらに優れた
耐食性が得られると期待される。このような試みの例と
して、特開昭60−252668号および特開昭60−252669号に
は、縦または横の長さが数10〜数100μｍ、厚さ５μｍ
以下の鱗片状である非晶質合金粉末を用いることが提案
されている。ここで、鱗片状とは、厚さ方向に垂直な平
面に投影した粉末の面積を「広さ」と定義し、「広さ」
≧（「厚さ」）２と定義されている。このように、耐食
性塗料に用いる粉末形状としては、塗布したときに塗布
面と平行に粉末が積層すること、すなわちリーフィング
現象が起こるように、鱗片状もしくはフレーク状粉末で
あることが必要である。In recent years, alloys having better corrosion resistance than stainless steel such as amorphous alloys have been developed, and it is expected that by mixing these alloys into powder and mixing them with paint, even better corrosion resistance than the above paints can be obtained. It As an example of such an attempt, JP-A-60-252668 and JP-A-60-252669 disclose that the length or width is several tens to several hundreds μm and the thickness is 5 μm.
It has been proposed to use the following scale-like amorphous alloy powder. Here, the scale-like shape is defined as the “area” of the powder projected onto a plane perpendicular to the thickness direction.
≧ (“thickness”) 2 As described above, it is necessary that the powder shape used for the corrosion-resistant paint should be a scale-like or flake-like powder so that the powder is laminated parallel to the application surface when applied, that is, the leafing phenomenon occurs.
ところが、本発明者らは、さらに詳細な検討をするう
ち、厚さには耐食性を維持するための滴切な範囲があ
り、リーフィング現象を起こさせ、効果を高めるために
は適切なアスペクト比（厚さに対する長径の比）や、
縦、横の比が必要であることがわかった。また、合金組
成についても、耐食性を向上させるためには、特定範囲
の組成があることがわかた。However, the present inventors have made further detailed investigations, and there is a drip range for maintaining the corrosion resistance in the thickness, which causes a leafing phenomenon, and an appropriate aspect ratio (thickness Ratio of major axis to
It turned out that the aspect ratio is needed. Also, regarding the alloy composition, it has been found that there is a specific range of composition in order to improve the corrosion resistance.
「発明が解決しようとする課題」 本発明は、上記従来技術の問題点に鑑みてなされたもの
であり、その目的は、塗膜状態を良好に維持しつつ耐食
性をより高めることができるようにした耐食性塗料用非
晶質合金粉末および耐食性塗料を提供することにある。"Problems to be solved by the invention" The present invention has been made in view of the problems of the above-mentioned conventional techniques, and an object thereof is to further improve the corrosion resistance while maintaining a good coating film state. The present invention provides an amorphous alloy powder for a corrosion resistant coating and a corrosion resistant coating.
「課題を解決するための手段」 本発明による耐食性塗料用非晶質合金粉末は、下記、
、から選ばれた組成の非晶質合金からなり、厚さ0.
5〜５μｍ、短径および長径５〜500μｍ、アスペクト比
（厚さに対する長径の比）５以上、短径と長径の比１〜
10であることを特徴とする。"Means for Solving the Problems" The amorphous alloy powder for corrosion resistant coating according to the present invention is as follows:
It consists of an amorphous alloy with a composition selected from, and has a thickness of 0.
5 to 5 μm, minor axis and major axis 5 to 500 μm, aspect ratio (ratio of major axis to thickness) of 5 or more, ratio of minor axis to major axis 1
It is characterized by being 10.
原子％で５〜12％のNi、５〜25％のCr、0.3〜5.0％の
Mo、８〜13％のＰ、７〜15％のＣ、残部Feおよび不可避
不純物。Atomic% 5-12% Ni, 5-25% Cr, 0.3-5.0%
Mo, 8-13% P, 7-15% C, balance Fe and unavoidable impurities.
原子％で５〜40％のCr、15〜25％のＰ、残部Niおよび
不可避不純物。5-40% Cr in atomic%, 15-25% P, balance Ni and inevitable impurities.
原子％で40〜60％の（Nb,Ta）、残部Niおよび不可避
不純物。40 to 60% (Nb, Ta) in atomic%, the balance Ni and inevitable impurities.
また、本発明の耐食性塗料は、少なくとも塗料用樹脂成
分と上記非晶質合金粉末とを含有することを特徴とす
る。Further, the corrosion-resistant paint of the present invention is characterized by containing at least a paint resin component and the above-mentioned amorphous alloy powder.
「作用」 本発明者らは、より優れた耐食性塗料用非晶質合金粉末
を得るため、種々の組成からなる非晶質合金についてそ
の耐食性を検討した。その結果、上記組成を有する非晶
質合金が優れた耐食性を有していることがわかった。す
なわち、上記組成の非晶質合金を用いることにより、孔
食性、隙間腐食、水素脆性などに優れた耐食性塗料用の
合金粉末を提供することができる。"Function" The present inventors investigated the corrosion resistance of amorphous alloys having various compositions in order to obtain more excellent amorphous alloy powders for corrosion resistant coatings. As a result, it was found that the amorphous alloy having the above composition has excellent corrosion resistance. That is, by using the amorphous alloy having the above composition, it is possible to provide an alloy powder for a corrosion resistant coating which is excellent in pitting corrosion, crevice corrosion, hydrogen embrittlement and the like.
また、粉末の形状についても、厚さ、アスペクト比、短
径および長径の寸法、短径と長径の比について種々検討
した結果、塗膜状態を良好に維持しつつ、リーフィング
現象を良好に起こさせて耐食効果を高めるためには、上
記の範囲とされることが必要であることがわかった。Also, regarding the shape of the powder, as a result of various studies on thickness, aspect ratio, dimensions of minor axis and major axis, and ratio of minor axis and major axis, while maintaining a good coating film state, a leafing phenomenon was caused well. It has been found that the above range is required to enhance the corrosion resistance effect.
すなわち、厚さが0.5μｍ未満では長期間にわたる耐食
性の維持に問題があり、厚さが５μｍを超えると塗膜の
平滑度が悪くなる。短径が５μｍ未満では粉末相互の重
なりが不均一となり、長径が500μｍを超えると塗膜の
強度が低下する。アスペクト比が５未満あるいは短径と
長径の比が10を超えると、リーフィングが起こりにくく
なる。また、短径と長径の比が10を超えると、フレーク
状の粉末どうしの重なり合いが不十分となり、耐食性が
低下する傾向がある。なお、短径と長径の比は、１〜５
の範囲とされることがより好ましい。That is, if the thickness is less than 0.5 μm, there is a problem in maintaining corrosion resistance for a long period of time, and if the thickness exceeds 5 μm, the smoothness of the coating film deteriorates. If the minor axis is less than 5 μm, the powders will not overlap with each other, and if the major axis exceeds 500 μm, the strength of the coating film will decrease. If the aspect ratio is less than 5 or the ratio of the short diameter to the long diameter exceeds 10, the leafing is less likely to occur. Further, when the ratio of the short diameter to the long diameter exceeds 10, the flaky powder particles are insufficiently overlapped with each other and the corrosion resistance tends to decrease. The ratio of the short diameter to the long diameter is 1 to 5
It is more preferable that the range is set to.
また、本発明の耐食性塗料は、上記の非晶質合金粉末を
含有するので、塗布したときにリーフィング現象により
被塗布面が非晶質合金粉末で覆われ、優れた耐食性が得
られる。さらに、塗布作業性や塗膜状態も良好に維持さ
れる。Further, since the corrosion-resistant coating material of the present invention contains the above-mentioned amorphous alloy powder, the surface to be coated is covered with the amorphous alloy powder due to the leafing phenomenon when applied, and excellent corrosion resistance is obtained. Further, the coating workability and the state of the coating film are maintained well.
「発明の好ましい態様」 本発明の非晶質合金粉末の好ましい製造方法としては、
前述した〜の組成を有する合金の溶湯をノズルから
流出させ、この溶湯にガスを噴霧することによって溶湯
の液適を生成させ、この液滴流方向に配置された傘型ま
たはホーン型の回転冷却体の表面に、前記液滴を凝固し
ないうちに衝突させて急冷凝固させる方法が挙げられ
る。そして、必要に応じて得られた粉末から前述した形
状特性を有するものを分取すればよい。この方法によれ
ば、前述した形状特性を有する粉末を70％以上の収率で
製造することができる。"Preferred embodiment of the invention" As a preferred method for producing the amorphous alloy powder of the present invention,
The molten alloy of the above-mentioned composition is discharged from the nozzle, gas is sprayed into the molten alloy to generate a liquid solution, and the umbrella-type or horn-type rotary cooling is arranged in the direction of the droplet flow. There is a method of causing the droplets to collide with the surface of the body before solidifying to rapidly solidify. Then, if necessary, powder having the above-mentioned shape characteristics may be collected from the obtained powder. According to this method, the powder having the above-mentioned shape characteristics can be produced in a yield of 70% or more.
本発明の耐食性塗料において、非晶質合金粉末は５〜20
vol％含有されていることが好ましい。非晶質合金粉末
の含有量が5vol％未満では、塗布の際に塗膜内において
基材塗料のみの部分が多くなり、粉末混入の効果がでな
い。また、20vol％を超えると、塗膜の強度が弱くな
り、クラックや剥離などを起こしたり、加工密着性が悪
くなるため好ましくない。In the corrosion resistant paint of the present invention, the amorphous alloy powder is 5 to 20.
It is preferable that the content is vol%. If the content of the amorphous alloy powder is less than 5 vol%, the amount of only the base material coating increases in the coating film at the time of coating, and the effect of powder mixing is not obtained. On the other hand, if it exceeds 20 vol%, the strength of the coating film is weakened, cracks and peeling are caused, and the processing adhesion is deteriorated, which is not preferable.
塗料用樹脂成分としては、塗料に用いられる各種の合成
樹脂が自由に使用できるが、例えばビニル樹脂、アクリ
ル樹脂、ポリウレタン樹脂、エポキシ樹脂などが好まし
く用いられる。ただし、本発明における塗料用樹脂成分
とは、塗布した後に硬化させるものにおいては、それら
の樹脂のモノマーやオリゴマーを含む意味である。As the resin component for paint, various synthetic resins used for paint can be freely used, but for example, vinyl resin, acrylic resin, polyurethane resin, epoxy resin and the like are preferably used. However, the resin component for coating material in the present invention is meant to include monomers and oligomers of those resins in the case of being cured after being applied.
本発明の塗料には、非晶質合金粉末と塗料用樹脂成分の
他に、必要に応じて溶剤、硬化剤、顔料、増粘剤、分散
剤、安定剤などを自由に添加することができる。溶剤
は、使用する樹脂に応じて適宜選択されるが、例えばキ
シレン、トルエン、アルコール、アセトン、酢酸エチル
などが用いられる。また、塗料の形式としても、溶剤
型、エマルジョン型、無溶剤型、粉体型など各種のもの
を採用することができる。In addition to the amorphous alloy powder and the resin component for coating, a solvent, a curing agent, a pigment, a thickener, a dispersant, a stabilizer and the like can be freely added to the coating material of the present invention. . The solvent is appropriately selected according to the resin used, but for example, xylene, toluene, alcohol, acetone, ethyl acetate, etc. are used. Also, as the type of paint, various types such as solvent type, emulsion type, solventless type, and powder type can be adopted.
本発明の塗料は、例えば刷毛塗り法、スプレー法などの
各種の方法で塗布することができる。この場合、非晶質
合金粉末を分散させて良好に密着させるために、塗布に
先立って界面活性剤、カバーリング材等の表面処理剤、
表面改質材を用いて表面処理を行なってもよい。The coating material of the present invention can be applied by various methods such as a brush coating method and a spray method. In this case, in order to disperse the amorphous alloy powder for good adhesion, a surface treatment agent such as a surfactant or a covering material prior to coating,
You may perform surface treatment using a surface modifier.
「実施例」 第１図には、本発明の非晶質合金粉末を製造するための
装置の一例が示されている。すなわち、図示しないルツ
ボにて溶融された合金の溶湯１を流出するノズル２が設
置されており、落下する溶湯１に対して高圧の噴射ガス
を吹き付ける噴霧化ノズル３が設置されている。噴霧化
ノズル３は、ノズル２を囲むように例えば円形に配置さ
れ、多数の噴出口から溶湯１の流れに向けて高速ガスを
噴出する構造となっている。ノズル２の下方には、傘型
の回転冷却体４がその回転軸をノズル２の直下からやや
横方向にずらして配置されている。"Example" FIG. 1 shows an example of an apparatus for producing the amorphous alloy powder of the present invention. That is, a nozzle 2 for flowing out a molten alloy 1 melted in a crucible (not shown) is installed, and an atomizing nozzle 3 for blowing a high-pressure injection gas to the falling molten metal 1 is installed. The atomizing nozzle 3 is arranged, for example, in a circular shape so as to surround the nozzle 2, and has a structure for ejecting a high-speed gas from a large number of ejection ports toward the flow of the molten metal 1. Below the nozzle 2, an umbrella-shaped rotary cooling body 4 is disposed with its rotation axis slightly laterally displaced from directly below the nozzle 2.
したがって、ノズル２から流出し落下する溶湯１の流れ
に対して、噴霧化ノズル３から高圧の噴出ガスが吹き付
けられ、これによって溶湯１の液滴５が形成される。こ
の液滴５は、下方に向けて広がりながら飛散し、回転冷
却体４の円錐面に衝突し急冷凝固し、偏平化されたフレ
ーク状の合金粉末６が形成される。なお、この実施例に
おいては、回転冷却体４として第２図（ａ）に示すよう
な傘型のものが用いられているが、第２図（ｂ）に示す
ようなホーン型のものでもよく、あるいは第２図（ｃ）
に示すような内周が傘型をなすものであってもよい。Therefore, a high-pressure jet gas is sprayed from the atomizing nozzle 3 to the flow of the molten metal 1 flowing out of the nozzle 2 and falling, whereby droplets 5 of the molten metal 1 are formed. The droplets 5 spread and spread downward, collide with the conical surface of the rotary cooling body 4 and rapidly solidify to form flattened flaky alloy powder 6. In this embodiment, as the rotary cooling body 4, an umbrella type one as shown in FIG. 2 (a) is used, but a horn type one as shown in FIG. 2 (b) may be used. , Or Fig. 2 (c)
The inner circumference may have an umbrella shape as shown in FIG.
なお、噴霧化ノズル３からの噴射ガス圧は、好ましくは
40kg/cm2以上とされる。また、噴射ガスとしては、例え
ばアルゴン、ヘリウム、窒素、空気あるいは混合ガスな
ど各種のものが使用可能である。さらに、回転冷却体４
は、例えば水冷などの手段によって少なくとも50℃以下
に冷却され、回転数は1000〜20000rpmとされることが好
ましい。The pressure of the gas injected from the atomizing nozzle 3 is preferably
40kg / cm 2 or more. Further, as the injection gas, various kinds such as argon, helium, nitrogen, air or mixed gas can be used. Further, the rotary cooling body 4
Is preferably cooled to at least 50 ° C. or lower by means such as water cooling, and the rotation speed is preferably 1000 to 20000 rpm.
試験例（アモルファス合金の耐食性評価） 第１表に組成を示す各種合金を真空溶解後、孔径0.4mm
の石英ノズルから、アルゴンガス噴射圧1.0kg/cm2で噴
出し、この溶湯を周速30m/secで回転する単ロールに衝
突させて薄帯を得た。得られた薄帯は、幅約1mm、厚さ
約30μｍであり、ｘ−ray回折の結果、いずれもアモル
ファス単相であることが確認された。Test example (Evaluation of corrosion resistance of amorphous alloys) Various alloys whose compositions are shown in Table 1 were vacuum melted, and then the hole diameter was 0.4 mm
Argon gas was ejected from the quartz nozzle at 1.0 kg / cm 2 and the molten metal was collided with a single roll rotating at a peripheral speed of 30 m / sec to obtain a ribbon. The obtained ribbon had a width of about 1 mm and a thickness of about 30 μm, and as a result of x-ray diffraction, it was confirmed that all of them had an amorphous single phase.
得られた各種の薄帯について、6N−HC1中に30℃で24時
間浸漬後、1N−H2SO4中に30℃で24時間浸漬後、および1
0mol−FeCl3中に40℃で１時間浸漬後における腐食テス
トを行なった。評価は、×…腐食が激しいもの、△…ピ
ットがみられるもの、○…表面に変化が認められないも
の、という基準で行なった。また、得られた各種の薄帯
について、180゜密着曲げができるかどうかにより靭性
の評価を行なった。総合評価は、上記の耐食性および靭
性の評価結果から、◎…耐食性塗料用の合金粉末に好適
なもの、×…耐食性塗料用の合金粉末として不満足なも
のとした。The ribbons obtained various, after 24 hours immersion at 30 ° C. in 6N-HC1, 24 hours after immersion at 30 ° C. in 1N-H 2 SO 4, and 1
A corrosion test was performed after immersion in 0 mol-FeCl 3 at 40 ° C. for 1 hour. The evaluation was made on the basis of ×: severe corrosion, Δ: pits were observed, ◯: no change was observed on the surface. Further, the toughness of each of the obtained thin strips was evaluated by determining whether or not 180 ° contact bending was possible. From the above-mentioned evaluation results of corrosion resistance and toughness, a comprehensive evaluation was made as ⊚ ... suitable for alloy powder for corrosion-resistant paint, and × unsatisfactory as alloy powder for corrosion-resistant paint.
また、比較のため、上記のアモルファス合金の薄帯の他
に、市販のオーステナイト系ステンレスSUS304、SUS316
Lについても同様なテスト評価を行なった。これらの結
果を第１表（後に記載する）に示す。For comparison, in addition to the amorphous alloy ribbon described above, commercially available austenitic stainless steels SUS304 and SUS316 are also available.
The same test evaluation was performed for L as well. The results are shown in Table 1 (described later).
第１表から、原子％で５〜12％のNi、５〜25％のCr、
0.3〜5.0％のMo、８〜13％のＰ、７〜15％のＣ、残部Fe
および不可避不純物。原子％で５〜40％のCr、15〜25
％のＰ、残部Niおよび不可避不純物、原子％で40〜60
％の（Nb,Ta）、残部Niおよび不可避不純物の範囲とさ
れた組成の試料NO.9、10、16〜21、24〜28は、耐食性塗
料用の合金粉末に適した特性を有していることがわか
る。From Table 1, atomic% 5-12% Ni, 5-25% Cr,
0.3-5.0% Mo, 8-13% P, 7-15% C, balance Fe
And inevitable impurities. 5-40% Cr in atomic%, 15-25
% P, balance Ni and unavoidable impurities, 40 to 60% by atom
% (Nb, Ta), balance Ni and inevitable impurities ranged sample NO.9, 10, 16-21, 24-28 have suitable properties for alloy powder for corrosion resistant paint. You can see that
実施例 （１）合金粉末の作成 第１図に示した装置を用い、第１表における試料No.9、
10、17、19、21、24、25、26の組成の合金500gをそれぞ
れルツボに入れ、1200℃で溶融させて溶湯１とした。Examples (1) Preparation of alloy powder Using the apparatus shown in FIG. 1, sample No. 9 in Table 1,
500 g of alloys having compositions of 10, 17, 19, 21, 24, 25, and 26 were placed in crucibles and melted at 1200 ° C. to obtain molten metal 1.
この溶湯１をノズル２から流出適下させ、適下する溶湯
１に対して噴霧化ノズル３よりアルゴンガスを100kg/cm
2の圧力で吹き付け、液滴５を形成した。この液滴５
を、ロール径200mmφ、円錐角度90゜、回転数7200rpmの
回転冷却体に衝突させ、木の葉形のフレーク状合金粉末
を得た。This molten metal 1 is appropriately discharged from the nozzle 2, and argon gas is supplied from the atomizing nozzle 3 to the molten metal 1 which is appropriately lowered to 100 kg / cm.
Spraying at a pressure of 2 formed droplets 5. This droplet 5
Was collided with a rotary cooling body having a roll diameter of 200 mmφ, a cone angle of 90 °, and a rotation number of 7200 rpm to obtain a leaf-shaped flake-shaped alloy powder.
試料No.9の合金を用いて上記方法で得られた合金粉末の
100倍の走査型電子顕微鏡写真を第３図に示す。Of the alloy powder obtained by the above method using the alloy of sample No. 9
A 100 times scanning electron micrograph is shown in FIG.
上記方法で得られたそれぞれの組成の合金粉末を分級
し、第２表に示すような形状特性を有するものを分取し
た。なお、本発明の形状特性とされる厚さ0.5〜５μ
ｍ、短径および長径５〜500μｍ、アスペクト比（厚さ
に対する長径の比）５以上、短径と長径の比１〜10であ
る粉末の収率は、いずれも70％を超えていた。The alloy powders of the respective compositions obtained by the above method were classified, and those having the shape characteristics shown in Table 2 were separated. In addition, the thickness which is the shape characteristic of the present invention is 0.5 to 5 μm.
The yields of powders having m, minor axis and major axis of 5 to 500 μm, aspect ratio (ratio of major axis to thickness) of 5 or more, and minor axis to major axis ratio of 1 to 10 were all over 70%.
また、試料No.9の合金を用いて得られた粉末について
は、厚さ１〜４μｍ、アスペクト比（厚さに対する長径
の比）10〜100、短径と長径の比１〜５、短径および長
径10〜400μｍのもの（試料No.9−１）と、厚さ0.5μｍ
未満、アスペクト比（厚さに対する長径の比）５以上、
短径と長径の比１〜５、短径および長径10〜400μｍの
もの（試料No.9−２）と、厚さ１〜４μｍ、アスペクト
比（厚さに対する長径の比）５未満、短径と長径の比１
〜10、短径および長径５〜36μｍのもの（試料No.9−
３）と、球状粉のもの（試料No.9−４）と、厚さ１〜４
μｍ、アスペクト比（厚さに対する長径の比）５以上、
短径と長径の比１〜５、長径500μｍを超えるもの（試
料No.9−５）とをそれぞれ調製した。Further, regarding the powder obtained by using the alloy of Sample No. 9, the thickness is 1 to 4 μm, the aspect ratio (ratio of major axis to thickness) 10 to 100, the ratio of minor axis to major axis 1 to 5, minor axis And those with a major axis of 10 to 400 μm (Sample No. 9-1) and a thickness of 0.5 μm
Less than, aspect ratio (ratio of major axis to thickness) of 5 or more,
Minor axis to major axis ratio 1 to 5, minor axis and major axis 10 to 400 μm (Sample No. 9-2), thickness 1 to 4 μm, aspect ratio (ratio of major axis to thickness) less than 5, minor axis And major axis ratio 1
-10, minor axis and major axis 5-36 μm (Sample No. 9-
3), spherical powder (Sample No. 9-4), and thickness 1 to 4
μm, aspect ratio (ratio of major axis to thickness) of 5 or more,
The ratio of the minor axis to the major axis of 1 to 5 and the major axis exceeding 500 μm (Sample No. 9-5) were prepared.
さらに、比較のため、市販の耐食性塗料に用いられてい
るステンレスSUS304の粉末を用意した（試料NO.13）。
この粉末は、厚さ0.5未満、アスペクト比（厚さに対す
る長径の比）５以上、短径と長径の比１〜10、短径およ
び長径36μｍ未満である。Furthermore, for comparison, a powder of stainless SUS304 used in a commercially available corrosion resistant paint was prepared (Sample No. 13).
This powder has a thickness of less than 0.5, an aspect ratio (ratio of major axis to thickness) of 5 or more, a ratio of minor axis to major axis of 1 to 10, minor axis and major axis of less than 36 μm.
（２）塗料の調製 樹脂バインダとしてポリ酢酸ビニル系樹脂85Vol％、上
記で得られたそれぞれの金属粉末15Vol％を混合して塗
料を作成した。(2) Preparation of coating material A coating material was prepared by mixing 85 vol% of polyvinyl acetate resin as a resin binder and 15 vol% of each metal powder obtained above.
（３）塗膜性能の評価 厚さ3mm、幅20mm、長さ50mmのSS41鋼板を用意し、サン
ドブラスト処理した後、トリクレン中で超音波洗浄し、
上記で調製したそれぞれの塗料を塗膜の厚さが100μｍ
前後になるように刷毛塗り塗装した。乾燥後、塗膜状態
を観察すると共に、耐食性テストを行なった。耐食性テ
ストは、20℃の王水中に浸漬して母材が溶出する時間を
調べることによって行なった。この結果を第２表（後に
記載する）に示す。(3) Evaluation of coating film performance A SS41 steel plate having a thickness of 3 mm, a width of 20 mm and a length of 50 mm is prepared, subjected to sandblasting, and then ultrasonically cleaned in trichlene,
Each coating prepared above has a coating thickness of 100 μm
Brush painting was applied to the front and back. After drying, the state of the coating film was observed and a corrosion resistance test was conducted. The corrosion resistance test was carried out by immersing it in aqua regia at 20 ° C and examining the time for the base material to elute. The results are shown in Table 2 (described later).
第２表から、非晶質合金粉末を含有する試料No.9−１、
９−２、９−３、９−５、10、17、19、21、24、25、26
は、従来のステンレスSUS304の粉末を含有する試料No.1
3に比べて優れた耐食性が得られることがわかる。しか
し、塗膜状態や耐食性を総合的に評価すると、厚さ0.5
〜５μｍ、短径および長径５〜500μｍ、アスペクト比
（厚さに対する長径の比）５以上、短径と長径の比１〜
10の範囲とされた本発明で特定した粉末を含有する試料
No.9−１、10、17、19、21、24、25、26が特に好ましい
ことがわかる。From Table 2, sample No. 9-1 containing amorphous alloy powder,
9-2, 9-3, 9-5, 10, 17, 19, 21, 24, 25, 26
Is the sample No.1 containing the conventional stainless SUS304 powder.
It can be seen that superior corrosion resistance can be obtained compared to 3. However, a comprehensive evaluation of the coating film condition and corrosion resistance shows that the thickness is 0.5
〜5 μm, minor axis and major axis 5 to 500 μm, aspect ratio (ratio of major axis to thickness) of 5 or more, ratio of minor axis to major axis 1
Samples containing the powder specified in the invention in the range of 10
It can be seen that Nos. 9-1, 10, 17, 19, 21, 24, 25 and 26 are particularly preferable.
「発明の効果」 以上説明したように、本発明による非晶質合金粉末は、
特定の組成を有するので耐食性に優れ、また、特定の形
状特性を有するので塗膜の状態を良好に維持しつつ、リ
ーフィング現象を効果的に起こさせることができる。し
たがって、この非晶質合金粉末を含有する本発明の耐食
性塗料は、塗膜状態を良好に維持しつつ、優れた耐食性
を付与することができる。 "Effects of the Invention" As described above, the amorphous alloy powder according to the present invention is
Since it has a specific composition, it has excellent corrosion resistance, and since it has specific shape characteristics, it can effectively cause the leafing phenomenon while maintaining a good state of the coating film. Therefore, the corrosion-resistant coating material of the present invention containing this amorphous alloy powder can impart excellent corrosion resistance while maintaining a good coating film state.
第１図は本発明の非晶質合金粉末を製造するための装置
の一例を示す概略断面図、第２図（ａ）、（ｂ）、
（ｃ）は同装置で用いられる回転冷却体のそれぞれ異な
る例を示す図、第３図は本発明の実施例で得られた非晶
質合金粉末の粒子構造を示す100倍の走査型電子顕微鏡
写真である。 図中、１は溶湯、２はノズル、３は噴霧化ノズル、４は
回転冷却体、５は液滴、６はフレーク状の合金粉末であ
る。FIG. 1 is a schematic cross-sectional view showing an example of an apparatus for producing the amorphous alloy powder of the present invention, FIGS. 2 (a), (b),
(C) is a view showing different examples of rotary cooling bodies used in the same apparatus, and FIG. 3 is a 100 × scanning electron microscope showing the particle structure of the amorphous alloy powder obtained in the example of the present invention. It is a photograph. In the figure, 1 is a molten metal, 2 is a nozzle, 3 is an atomizing nozzle, 4 is a rotary cooling body, 5 is a droplet, and 6 is a flake-like alloy powder.
Claims (4)
合金からなり、厚さ0.5〜５μｍ、短径および長径５〜5
00μｍ、アスペクト比（厚さに対する長径の比）５以
上、短径と長径の比１〜10であることを特徴とする耐食
性塗料用非晶質合金粉末。 原子％で５〜12％のNi、５〜25％のCr、0.3〜5.0％の
Mo、８〜13％のＰ、７〜15％のＣ、残部Feおよび不可避
不純物。 原子％で５〜40％のCr、15〜25％のＰ、残部Niおよび
不可避不純物。 原子％で40〜60％の（Nb,Ta）、残部Niおよび不可避
不純物。1. An amorphous alloy having a composition selected from the following, having a thickness of 0.5 to 5 μm, a minor axis and a major axis of 5 to 5.
An amorphous alloy powder for a corrosion resistant coating, which has an aspect ratio (ratio of major axis to thickness) of 5 or more and a ratio of minor axis to major axis of 1 to 10. Atomic% 5-12% Ni, 5-25% Cr, 0.3-5.0%
Mo, 8-13% P, 7-15% C, balance Fe and unavoidable impurities. 5-40% Cr in atomic%, 15-25% P, balance Ni and inevitable impurities. 40 to 60% (Nb, Ta) in atomic%, the balance Ni and inevitable impurities.
の非晶質合金粉末とを含有することを特徴とする耐食性
塗料。2. A corrosion resistant paint comprising at least a resin component for paint and the amorphous alloy powder according to claim 1.
る請求項２記載の耐食性塗料。3. The corrosion resistant coating composition according to claim 2, which contains the amorphous alloy powder in an amount of 5 to 20 vol%.
ル樹脂、ポリウレタン樹脂、エポキシ樹脂から選ばれた
ものである請求項２または３記載の耐食性塗料。4. The corrosion-resistant paint according to claim 2, wherein the resin component for paint is selected from vinyl resin, acrylic resin, polyurethane resin and epoxy resin.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63115486A JPH07116483B2 (en) | 1988-05-12 | 1988-05-12 | Amorphous alloy powder for corrosion resistant paint and corrosion resistant paint |
| US07/261,972 US4891068A (en) | 1988-05-12 | 1988-10-24 | Additive powders for coating materials or plastics |
| AU24407/88A AU613288B2 (en) | 1988-05-12 | 1988-10-26 | Additive powders for coating materials or plastics |
| CA000582072A CA1308275C (en) | 1988-05-12 | 1988-11-03 | Additive powders for coating materials or plastics |
| EP89302353A EP0345921B1 (en) | 1988-05-12 | 1989-03-09 | Powder additives for coating materials or for plastics |
| DE68916591T DE68916591T2 (en) | 1988-05-12 | 1989-03-09 | Powdery additives for coating substances or plastics. |
| US07/419,153 US5013346A (en) | 1988-05-12 | 1989-10-10 | Method of making additive powders for coating materials or plastics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63115486A JPH07116483B2 (en) | 1988-05-12 | 1988-05-12 | Amorphous alloy powder for corrosion resistant paint and corrosion resistant paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01287201A JPH01287201A (en) | 1989-11-17 |
| JPH07116483B2 true JPH07116483B2 (en) | 1995-12-13 |
Family
ID=14663714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63115486A Expired - Fee Related JPH07116483B2 (en) | 1988-05-12 | 1988-05-12 | Amorphous alloy powder for corrosion resistant paint and corrosion resistant paint |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07116483B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8999454B2 (en) | 2012-03-22 | 2015-04-07 | General Electric Company | Device and process for producing a reinforced hollow fibre membrane |
| US9022229B2 (en) | 2012-03-09 | 2015-05-05 | General Electric Company | Composite membrane with compatible support filaments |
| US9227362B2 (en) | 2012-08-23 | 2016-01-05 | General Electric Company | Braid welding |
| US9321014B2 (en) | 2011-12-16 | 2016-04-26 | Bl Technologies, Inc. | Hollow fiber membrane with compatible reinforcements |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2544963B2 (en) * | 1988-07-22 | 1996-10-16 | 健 増本 | Flaky powder |
| JPH07103454B2 (en) * | 1989-08-11 | 1995-11-08 | 三井造船株式会社 | High corrosion resistance amorphous alloy |
| JP4710577B2 (en) * | 2005-12-05 | 2011-06-29 | セイコーエプソン株式会社 | Powder for grinding, method for producing powder for grinding and grinding method |
| JP4904847B2 (en) * | 2006-02-24 | 2012-03-28 | Ｊｆｅスチール株式会社 | Steel material with excellent acid corrosion resistance |
| CN112126312A (en) * | 2020-09-15 | 2020-12-25 | 常州大学 | Preparation method of amorphous/organic silicon modified epoxy corrosion-resistant coating |
-
1988
- 1988-05-12 JP JP63115486A patent/JPH07116483B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9321014B2 (en) | 2011-12-16 | 2016-04-26 | Bl Technologies, Inc. | Hollow fiber membrane with compatible reinforcements |
| US9022229B2 (en) | 2012-03-09 | 2015-05-05 | General Electric Company | Composite membrane with compatible support filaments |
| US8999454B2 (en) | 2012-03-22 | 2015-04-07 | General Electric Company | Device and process for producing a reinforced hollow fibre membrane |
| US9227362B2 (en) | 2012-08-23 | 2016-01-05 | General Electric Company | Braid welding |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01287201A (en) | 1989-11-17 |
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