JP2582621B2 - Manufacturing method of amorphous alloy powder for corrosion resistant paint - Google Patents
Manufacturing method of amorphous alloy powder for corrosion resistant paintInfo
- Publication number
- JP2582621B2 JP2582621B2 JP63115485A JP11548588A JP2582621B2 JP 2582621 B2 JP2582621 B2 JP 2582621B2 JP 63115485 A JP63115485 A JP 63115485A JP 11548588 A JP11548588 A JP 11548588A JP 2582621 B2 JP2582621 B2 JP 2582621B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- alloy
- corrosion
- major axis
- alloy powder
- 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 66
- 238000005260 corrosion Methods 0.000 title claims description 36
- 230000007797 corrosion Effects 0.000 title claims description 36
- 239000003973 paint Substances 0.000 title claims description 25
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 33
- 239000000956 alloy Substances 0.000 claims description 33
- 238000001816 cooling Methods 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 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
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 101150000971 SUS3 gene Proteins 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
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 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
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】 「産業上の利用分野」 本発明は、耐食性塗料用の顔料として使用する非晶質
合金粉末の製造法に関する。Description: TECHNICAL FIELD The present invention relates to a method for producing an amorphous alloy powder used as a pigment for a corrosion-resistant paint.
「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。"Conventional technology" Conventionally, a paint containing stainless steel powder has been marketed as a paint requiring corrosion resistance. The shape of this stainless steel powder is 10μm wide, 30μm long, and 0.3μm thick flake. When this powder is mixed with resin and applied by brushing, spraying, etc., the surface tension generated when the resin is hardened Thus, a continuous stainless steel film is formed in parallel with the coating surface, and the material is shielded from the outside air to provide corrosion resistance.
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, since stainless steel has drawbacks such as stress corrosion cracking, pitting corrosion, crevice corrosion, and hydrogen embrittlement, a coating containing the above stainless steel powder may not be able to provide sufficient corrosion resistance in some cases.
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５μ
ｍ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。In recent years, alloys such as amorphous alloys that have better corrosion resistance than stainless steel have been developed.By powdering these alloys and mixing them with paint, it is expected that even better corrosion resistance than the above paints will be obtained. You. As an example of such an attempt, JP-A-60-252668 and JP-A-60-252669 disclose that the vertical or horizontal length is several tens to several hundreds μm and the thickness is 5 μm.
It has been proposed to use a scale-like amorphous alloy powder of m or less.
上記従来例にも示されるように、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
が積層するように、フレーク状粉末であることが必要で
ある。ところが、非晶質合金を用いてフレーク状粉末を
製造することは、実際にはかなり困難なことであった。As shown in the above-mentioned conventional example, the powder used for the corrosion-resistant paint needs to be a flake-like powder so that the powder is laminated in parallel with the application surface when applied. However, producing flake-like powder using an amorphous alloy has been quite difficult in practice.
非晶質合金を用いてフレーク状粉末を製造する方法と
しては、従来の単ロール法やキャビテーション法により
作製したりリボンあるいは短冊に水素を吸わせて脆化さ
せ、スタンプミルやボールミルによって粉砕する方法
や、単ロール法においてロール表面に溶湯をアトマイズ
して不規則形状の粉末を得る方法が知られている。しか
し、これらの方法で得られる粉末の厚さは、通常５〜20
μｍ程度であるため、得られた粉末を樹脂に混合して塗
料として使用した場合、塗膜にひび割れが生ずることが
あり、耐食性塗料用の粉末として適したものとはいえな
かった。As a method of producing a flake-like powder using an amorphous alloy, there is a method of producing by a conventional single roll method or cavitation method, embrittlement by absorbing hydrogen into a ribbon or a strip, and pulverizing by a stamp mill or a ball mill. Also, a method is known in which a molten metal is atomized on a roll surface in a single roll method to obtain an irregularly shaped powder. However, the thickness of the powder obtained by these methods is usually 5 to 20
Since it is about μm, when the obtained powder is mixed with a resin and used as a coating material, the coating film may be cracked, which is not suitable as a powder for a corrosion-resistant coating material.
また、前述した特開昭60−252668号および特開昭60−
252669号には、予めアトマイズ等の方法で合金化した粉
末を双ロールの上方から落下させ、粉末が落下する途中
で、同心状に配置されたノズルから噴出されるアセチレ
ン炎、酸素水素炎、酸素−プロパン炎等の熱源で粉末を
溶融させ、この溶適を双ロールによって圧延と同時に急
冷することにより、鱗片状すなわちフレーク状の粉末を
得る方法が開示されている。しかし、この方法では、粉
末の落下の途中で溶融させるようにしているので、粉末
の供給量を多くすることができず、フレーク状の粉末を
工業的に大量に生産することができなかった。Further, the above-mentioned JP-A-60-252668 and JP-A-60-252668
No. 252669 discloses that acetylene flame, oxygen-hydrogen flame, and oxygen are sprayed from concentrically arranged nozzles while the powder is dropped from above the twin rolls while the powder is alloyed by a method such as atomization. Disclosed is a method in which a powder is melted by a heat source such as propane flame and quenched simultaneously with rolling by a twin roll to obtain a flaky or flaky powder. However, in this method, since the powder is melted in the middle of falling, the supply amount of the powder cannot be increased, and the flake-like powder cannot be industrially mass-produced.
「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、耐食性塗料に混合するのに適し
たフレーク状の非晶質合金粉末を工業的にかつ高収率で
製造できるようにした耐食性塗料用非晶質合金粉末の製
造法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 above-mentioned problems of the prior art, and an object of the present invention is to provide a flake-like amorphous alloy powder suitable for mixing with a corrosion-resistant paint. An object of the present invention is to provide a method for producing an amorphous alloy powder for a corrosion-resistant paint, which can be produced industrially with a high yield.
「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の製造法
は、非晶質相を形成可能な合金の溶湯をノズルから流出
させ、この溶湯にガスを40kg/cm2以上の圧力で噴霧する
ことによって溶湯の液滴を生成させ、この液滴流方向に
その回転軸を前記ノズルの直下から横方向にずらして配
置された回転数1000〜20000rpmで回転する傘型またはホ
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、こうして得られた凝固粉
末より、厚さ0.5〜５μｍ、短径および長径５〜500μ
ｍ、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のものを分取することを特徴とす
る。`` Means for Solving the Problems''A method for producing an amorphous alloy powder for a corrosion-resistant paint according to the present invention comprises flowing a molten metal of an alloy capable of forming an amorphous phase from a nozzle, and introducing a gas into the molten metal at 40 kg / cm. Molten liquid droplets are generated by spraying at a pressure of 2 or more, and an umbrella type rotating at a rotation speed of 1000 to 20000 rpm arranged with its rotation axis shifted laterally from immediately below the nozzle in the droplet flow direction Alternatively, the droplets collide with the surface of a horn-shaped rotary cooling body before being solidified, and rapidly solidify. The solidified powder thus obtained has a thickness of 0.5 to 5 μm, a minor axis and a major axis of 5 to 500 μm.
m, an aspect ratio (ratio of the major axis to the thickness) of 5 or more, and a minor axis / major axis ratio of 1 to 10 are sorted.
また、本発明の好ましい態様においては、前記合金と
して次のような組成のものを用いる。In a preferred embodiment of the present invention, the alloy has the following composition.
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
不純物からなるもの。5-12% Ni, 5-25% Cr, 0.3-5.0%
Mo, 8 to 13% P, 7 to 15% C, balance Fe and unavoidable impurities.
原子％で５〜40％のCr、15〜25％のＰ、残部Niおよび
不可避不純物からなるもの 原子％で40〜60％の（Nb,Ta）、残部Niおよび不可避
不純物からなるもの 「作用」 本発明者らは、耐食性塗料に適したフレーク状の非晶
質合金粉末を得るため、合金の溶湯にガスを噴霧するこ
とにより液適を形成し、この液適を種々の回転冷却体に
衝突させて急冷凝固させる実験を行なった。その結果、
従来の単ロール法などで用いられている円筒状の回転冷
却体に従来の方法で液適を衝突させても、厚さが不揃い
でしかも不定形な粉末が多く形成されてしまい、目的と
するフレーク状の粉末を効率的に得ることができなかっ
た。ところが、非晶質相を形成可能な合金の溶湯にガス
を40kg/cm2以上の圧力で噴霧して溶湯の液適を形成し、
この液適を回転数1000〜20000rpmで回転する傘型または
ホーン型の回転冷却体に衝突させると、厚さが薄い木の
葉形をなすフレーク状の非晶質粉末が極めて高収率で得
られることがわかった。Atomic% of 5 to 40% Cr, 15 to 25% of P, balance of Ni and inevitable impurities Atomic% of 40 to 60% of (Nb, Ta), balance of Ni and inevitable impurities "Action" The present inventors formed a liquid alloy by spraying a gas onto a molten alloy in order to obtain a flake-shaped amorphous alloy powder suitable for a corrosion-resistant paint, and then collided the liquid alloy with various rotary cooling bodies. An experiment was conducted in which the mixture was rapidly cooled and solidified. as a result,
Even if the liquid is made to impinge on the cylindrical rotary cooling body used in the conventional single roll method or the like by the conventional method, a large amount of irregularly-shaped and irregular-shaped powder is formed. Flaky powder could not be obtained efficiently. However, a gas is sprayed onto a molten alloy of an alloy capable of forming an amorphous phase at a pressure of 40 kg / cm 2 or more to form a liquid suitable for the molten metal.
When this liquid is collided with an umbrella-type or horn-type rotary cooling body rotating at a rotation speed of 1,000 to 20,000 rpm, a thin leaf-shaped amorphous flake-like powder having a thin leaf can be obtained at an extremely high yield. I understood.
この理由はよくわからないが、傘型またはホーン型の
回転冷却体を用いることにより、冷却体表面が液適流方
向に対して傾斜して配置されることになり、液適が傾斜
した冷却対表面に衝突すると冷却体の回転方向に広がる
と共に傾斜面に沿っても広がることになり、その結果、
液適がより大きく広げられて薄い木の葉形のフレーク状
粉末となると考えられる。The reason for this is not clear, but by using an umbrella-type or horn-type rotary cooling body, the surface of the cooling body is arranged inclined with respect to the appropriate flow direction of the liquid. When it collides with, it spreads in the rotation direction of the cooling body and also spreads along the inclined surface, and as a result,
It is considered that the liquid is spread more widely to form a thin tree leaf-shaped flake powder.
こうして得られたフレーク状の非晶質合金粉末を塗料
に混合することにより、優れた特性を有する耐食性塗料
を得ることができる。すなわち、薄いフレーク状をなし
ているので、塗膜の乾燥中に偏平に配列するリーフィン
グが良好に起こり、被塗布面が非晶質合金のフレーク状
粉末で良好に覆われる。その結果、苛酷な腐食環境にも
十分に耐えられる塗膜が形成される。また、フレーク状
粉末の厚さが薄いので、表面歪みなどの応力に対して割
れを生じにくい塗膜が形成される。By mixing the flake-shaped amorphous alloy powder thus obtained into a paint, a corrosion-resistant paint having excellent properties can be obtained. That is, since the film is in a thin flake shape, leafing which is arranged flatly during drying of the coating film occurs favorably, and the surface to be coated is well covered with the amorphous alloy flake powder. As a result, a coating film that can sufficiently withstand a severe corrosive environment is formed. Further, since the thickness of the flake-like powder is small, a coating film that is not easily cracked by stress such as surface distortion is formed.
また、凝固粉末より、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のものを分取するの
で、耐食性塗料により適したフレーク状粉末を得ること
ができる。この場合、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
るの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。In addition, from the coagulated powder, those having a thickness of 0.5 to 5 μm, a minor axis and a major axis of 5 to 500 μm, an aspect ratio (ratio of major axis to thickness) of 5 or more, and a minor axis to major axis ratio of 1 to 10 are collected. Flake powders more suitable for corrosion resistant paints can be obtained. In this case, if the thickness is less than 0.5 μm, there is a problem in maintaining the corrosion resistance over a long period of time, and if the thickness exceeds 5 μm, the coating film has poor smoothness. If the minor axis is less than 5 μm, the powders overlap non-uniformly, and if the major axis exceeds 500 μm, the strength of the coating film decreases. If the aspect ratio is less than 5 or the ratio of the minor axis to the major axis exceeds 10, leafing is less likely to occur. On the other hand, when the ratio of the minor axis to the major axis exceeds 10, the flake-like powders are not sufficiently overlapped with each other, and the corrosion resistance tends to decrease. The ratio between the minor axis and the major axis is more preferably in the range of 1 to 5.
さらに、合金組成として前述したものを用いることに
より、急冷凝固させたときに非晶質相を形成しやすくな
り、かつ、苛酷な腐食環境にも耐える優れた耐食性を付
与することができる。Further, by using the above-mentioned alloy composition, an amorphous phase can be easily formed when rapidly solidified, and excellent corrosion resistance that can withstand a severe corrosive environment can be imparted.
「実施例」 第１図には、本発明を実施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。FIG. 1 shows an example of an apparatus for carrying out the present invention. That is, a nozzle 2 for flowing out a molten metal 1 of an alloy melted in a crucible (not shown) is provided,
An atomizing nozzle 3 for blowing a high-pressure injection gas to the falling molten metal 1 is provided. The atomizing nozzle 3 is arranged, for example, in a circular shape so as to surround the nozzle 2, and has a structure in which high-speed gas is ejected from a number of ejection ports toward the flow of the molten metal 1. An umbrella-shaped rotary cooling body 4 is provided below the nozzle 2.
Are arranged so that their rotation axes are slightly shifted laterally 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の液適５が形成される。
この液適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 blown from the atomizing nozzle 3 to the flow of the molten metal 1 flowing out of the nozzle 2 and falling, thereby forming the liquid 5 of the molten metal 1.
The liquid 5 spreads downward and spreads, collides with the conical surface of the rotary cooling body 4, rapidly solidifies, and forms a flat flake-like alloy powder 6. In this embodiment, an umbrella-shaped rotary cooling body 4 as shown in FIG. 2A is used, but a horn-shaped rotary cooling body 4 as shown in FIG. 2B may be used. Alternatively, the inner periphery as shown in FIG. 2 (c) may be of an umbrella type.
なお、噴霧化ノズル３からの噴射ガス圧は、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
れることが好ましい。また、回転数は、1000〜20000rpm
とされる。The pressure of the gas injected from the atomizing nozzle 3 is 40 kg / cm 2
That is all. Further, as the injection gas, various types such as argon, helium, nitrogen, air, or a mixed gas can be used. Further, it is preferable that the rotary cooling body 4 is cooled to at least 50 ° C. or less by, for example, water cooling. Also, the rotation speed is 1000-20000rpm
It is said.
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0.4m
m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 alloy) Various alloys having the compositions shown in Table 1 were melted in vacuum and the pore size was 0.4m.
An argon gas injection pressure of 1.0 kg / cm 2 was ejected from a quartz nozzle having a diameter of 1.0 m, 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 was about 1 mm in width and about 30 μm in thickness, and as a result of X-ray diffraction, it was confirmed that each of them was an amorphous single phase.
得られた各種の薄帯について、6N−HCl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10mol−FeCl3中に40℃で１時間浸漬後における腐食テ
ストに行なった。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。Each of the obtained ribbons was placed in 6N-HCl at 30 ° C. for 24 hours.
After time immersion, after 24 hours immersion at 30 ° C. in 1N-H 2 SO 4, and were performed corrosion tests after 1 hour immersion at 40 ° C. in 10 mol-FeCl 3. The evaluation was × × severely corroded, Δ ...
The criterion was as follows: pits were observed,…: no change was observed on the surface. The toughness of each of the obtained ribbons was evaluated based on whether or not 180 ° bending was possible. The comprehensive evaluation was based on the evaluation results of corrosion resistance and toughness described above. ◎: suitable for alloy powder for corrosion-resistant paint, x: 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、SUS3
16L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 above-mentioned amorphous alloy ribbon, commercially available austenitic stainless steel SUS304, SUS3
The same test evaluation was performed for 16L. The results are shown in Table 1 (described below).
第１票から、原子％で５〜12％のNi、５〜25％のC
r、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 the first vote, 5-12% Ni and 5-25% C in atomic%
r, 0.3 to 5.0% Mo, 8 to 13% P, 7 to 15% C, balance Fe and unavoidable impurities, 5 to 40% atomic% of Cr,
~ 25% P, balance Ni and unavoidable impurities, 40 in atomic%
Samples Nos. 9, 10, 16 to 21 and 24 to 28 having compositions of up to 60% (Nb, Ta), the balance of Ni and inevitable impurities have characteristics suitable for alloy powders for corrosion resistant paints. You can see that it is doing.
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。Example (1) Preparation of alloy powder Using the apparatus shown in FIG.
500 g of an alloy having a composition of 9, 10, 17, 19, 21, 24, 25, and 26 was placed in a crucible and melted at 1200 ° C. to obtain a 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/
cm2の圧力で吹き付け、液適５を形成した。この液適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。The molten metal 1 is flowed down from the nozzle 2 and is lowered.
It was sprayed at a pressure of cm 2 to form a liquid layer 5. This liquid 5
Was impinged on a rotary cooling body having a roll diameter of 200 mmφ, a cone angle of 90 °, and a rotation speed of 7200 rpm to obtain a leaf-shaped flake-like 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。FIG. 3 shows a scanning electron micrograph of the alloy powder obtained by the above method using the alloy of Sample No. 9 at a magnification of 100 times.
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、本発明の製造方法における最終製品である厚
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である粉末の収率は、いずれも70％を超えてい
た。The alloy powders having the respective compositions obtained by the above method were classified, and those having shape characteristics as shown in Table 2 were collected. The final product in the production method of the present invention has a thickness of 0.5 to 5 μm, a minor axis and a major axis of 5 to 500 μm, an aspect ratio (ratio of major axis to thickness) of 5 or more, and a minor to major axis ratio of 1 to 10. Powder yields 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。The powder obtained by using the alloy of sample No. 9 has a thickness of 1 to 4 μm, an aspect ratio (ratio of a major axis to a thickness) of 10 to 100, a ratio of a minor axis to a major axis of 1 to 5, and a minor axis. And one 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) 5 or more,
One having a ratio of minor axis to major axis of 1 to 5, minor axis and major axis of 10 to 400 μm (sample No. 9-2), thickness of 1 to 4 μm, aspect ratio (ratio of major axis to thickness) of less than 5, minor axis And major axis ratio 1
~ 10, minor axis and major axis 5-36μm (Sample No.9-
3), spherical powder (sample No. 9-4), thickness 1-4
μm, aspect ratio (ratio of major axis to thickness) 5 or more,
The ratio of the minor axis to the major axis was 1 to 5, and the major axis exceeded 500 μm (Sample No. 9-5).
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.1
3）。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。Further, for comparison, a stainless steel SUS304 powder used for a commercially available corrosion-resistant paint was prepared (sample No. 1).
3). 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 paint 85% by volume of polyvinyl acetate resin as resin binder,
A paint was prepared by mixing 15 Vol% of each of the metal powders 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100
μｍ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 Prepare SS41 steel plate of thickness 3mm, width 20mm, length 50mm, after sand blasting, ultrasonic cleaning in trichlene, and apply each paint prepared above to coating thickness. Saga 100
Brush coating was performed so as to be about μm. After drying, the state of the coating film was observed, and a corrosion resistance test was performed. The corrosion resistance test was performed by immersing in aqua regia at 20 ° C. and examining the time required for the base material to elute. The results are shown in Table 2 (described below).
第２表から、本発明の製造方法で得られた非晶質合金
粉末を含有する試料No.9−１、10、17、19、21、24、2
5、26は、従来のステンレスSUS304の粉末を含有する試
料No.13および粉末の形状が本発明で規定する範囲から
外れた試料No.9−２、９−３、９−４に比べて優れた耐
食性が得られることがわかる。また、短径及び長径が本
発明で規定する範囲よりも大きな粉末を含有する試料N
o.9−５は、塗膜の平滑性が損なわれることがわかる。From Table 2, it can be seen that Sample Nos. 9-1, 10, 17, 19, 21, 24, 2 containing the amorphous alloy powder obtained by the production method of the present invention were used.
5 and 26 are superior to Sample No. 13 containing conventional stainless steel SUS304 powder and Sample Nos. 9-2, 9-3 and 9-4 in which the shape of the powder is out of the range specified by the present invention. It can be seen that high corrosion resistance is obtained. Further, the sample N containing a powder whose minor axis and major axis are larger than the range specified in the present invention.
o.9-5 shows that the smoothness of the coating film was impaired.
「発明の効果」 以上説明したように、本発明によれば、非晶質相を形
成可能な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滴を生成させ、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、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のものを分取することによ
り、耐食性塗料の顔料として適した形状を有する非晶質
合金粉末を工業的にかつ高収率で製造することができ
る。 [Effects of the Invention] As described above, according to the present invention, a melt of an alloy capable of forming an amorphous phase is caused to flow out of a nozzle, and a gas is sprayed on the melt to generate droplets of the melt. On the surface of the umbrella-type or horn-type rotary cooling body arranged in the direction of the droplet flow, the droplets are crushed and solidified rapidly without being solidified before being solidified, and have a thickness of 0.5 to 5 μm, a minor axis and a major axis of 5 to Five
An amorphous alloy powder having a shape suitable for a pigment of a corrosion-resistant paint can be produced by sorting those having a thickness of 00 μm, 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. It can be produced efficiently and in high yield.
第１図は本発明を実施するための装置の一例を示す概略
断面図、第２図（ａ）、（ｂ）、（ｃ）は本発明を実施
するための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 carrying out the present invention, and FIGS. 2 (a), (b) and (c) show a rotary cooling body used in the apparatus for carrying out the present invention. FIG. 3 is a scanning electron micrograph (× 100) showing the particle structure of the amorphous alloy powder obtained in the example of the present invention. 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.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭57−70206（ＪＰ，Ａ) 特開 昭59−159903（ＪＰ，Ａ) 特開 昭52−56061（ＪＰ，Ａ) 特開 昭53−70966（ＪＰ，Ａ) 特開 昭64−75607（ＪＰ，Ａ) 特開 昭63−114901（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-57-70206 (JP, A) JP-A-59-159903 (JP, A) JP-A-52-56061 (JP, A) 70966 (JP, A) JP-A-64-75607 (JP, A) JP-A-63-114901 (JP, A)
Claims (4)
から流出させ、この溶湯にガスを40kg/cm2以上の圧力で
噴霧することによって溶湯の液滴を生成させ、この液滴
流方向にその回転軸を前記ノズルの直下から横方向にず
らして配置された回転数1000〜20000rpmで回転する傘型
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、こうして得られ
た凝固粉末より、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のものを分取することを特
徴とする耐食性塗料用非晶質合金粉末の製造法。1. A molten metal of an alloy capable of forming an amorphous phase is caused to flow out of a nozzle, and gas is sprayed on the molten metal at a pressure of 40 kg / cm 2 or more to generate molten liquid droplets. The droplet collides with the surface of an umbrella-type or horn-type rotary cooling body that rotates at a rotation speed of 1,000 to 20,000 rpm, the rotation axis of which is laterally shifted from immediately below the nozzle in the flow direction, without solidifying the droplets. And then rapidly solidified. From the solidified powder thus obtained, a thickness of 0.5 to 5 μm, a minor axis and a major axis 5
~ 500μm, aspect ratio (ratio of major axis to thickness) 5
As described above, a method for producing an amorphous alloy powder for a corrosion-resistant paint, wherein fractions having a ratio of the short diameter to the long diameter of 1 to 10 are collected.
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からなるものを用い
る請求項１記載の耐食性塗料用非晶質合金粉末の製造
法。2. The alloy according to claim 1, wherein said alloy contains 5 to 12% of Ni by atomic%.
5-25% Cr, 0.3-5.0% Mo, 8-13% P, 7-15
2. The method for producing an amorphous alloy powder for a corrosion-resistant paint according to claim 1, wherein the alloy comprises a C content of 0.1%, the balance being Fe and unavoidable impurities.
15〜25％のＰ、残部Niおよび不可避不純物からなるもの
を用いる請求項１記載の耐食性塗料用非晶質合金粉末の
製造法。3. The alloy according to claim 1, wherein the alloy contains 5 to 40% of Cr in atomic%.
2. The method for producing an amorphous alloy powder for a corrosion-resistant coating according to claim 1, wherein a material comprising 15 to 25% of P, the balance of Ni and unavoidable impurities is used.
b,Ta）、残部Niおよび不可避不純物からなるものを用い
る請求項１記載の耐食性塗料用非晶質合金粉末の製造
法。4. The alloy according to claim 1, wherein said alloy contains 40 to 60% of (N
2. The method for producing an amorphous alloy powder for a corrosion-resistant paint according to claim 1, wherein the amorphous alloy powder comprises b, Ta), the balance being Ni and unavoidable impurities.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63115485A JP2582621B2 (en) | 1988-05-12 | 1988-05-12 | Manufacturing method of amorphous alloy powder for 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 |
|---|---|---|---|
| JP63115485A JP2582621B2 (en) | 1988-05-12 | 1988-05-12 | Manufacturing method of amorphous alloy powder for corrosion resistant paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01287209A JPH01287209A (en) | 1989-11-17 |
| JP2582621B2 true JP2582621B2 (en) | 1997-02-19 |
Family
ID=14663689
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63115485A Expired - Fee Related JP2582621B2 (en) | 1988-05-12 | 1988-05-12 | Manufacturing method of amorphous alloy powder for corrosion resistant paint |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2582621B2 (en) |
Families Citing this family (4)
| 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 |
| JPH0556924U (en) * | 1992-01-17 | 1993-07-30 | 帝国ピストンリング株式会社 | Powder manufacturing equipment |
| JPH07166212A (en) * | 1993-12-09 | 1995-06-27 | Teikoku Piston Ring Co Ltd | Production and apparatus for production of flat metallic powder |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5256061A (en) * | 1975-11-04 | 1977-05-09 | Nissan Motor | Method and device to manufacture metal powder |
| JPS5370966A (en) * | 1976-12-07 | 1978-06-23 | Nippon Steel Corp | Lengthened and flat minute piece manufacturing process and device |
| JPS5770206A (en) * | 1980-10-20 | 1982-04-30 | Matsushita Electric Ind Co Ltd | Preparation of metal alloy powder |
| JPS59159903A (en) * | 1983-03-01 | 1984-09-10 | Sumitomo Electric Ind Ltd | Method and device for producing metallic powder |
-
1988
- 1988-05-12 JP JP63115485A patent/JP2582621B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01287209A (en) | 1989-11-17 |
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