JP2003239057A - Member for melting aluminum and/or zinc - Google Patents
Member for melting aluminum and/or zincInfo
- Publication number
- JP2003239057A JP2003239057A JP2002041325A JP2002041325A JP2003239057A JP 2003239057 A JP2003239057 A JP 2003239057A JP 2002041325 A JP2002041325 A JP 2002041325A JP 2002041325 A JP2002041325 A JP 2002041325A JP 2003239057 A JP2003239057 A JP 2003239057A
- Authority
- JP
- Japan
- Prior art keywords
- aluminum
- zinc
- nickel
- melting
- plating film
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、アルミニウムおよ
び／または亜鉛溶融用部材、該部材を備えたアルミニウ
ムおよび／または亜鉛溶融炉、溶融アルミニウムおよび
／または溶融亜鉛メッキ設備に関する。TECHNICAL FIELD The present invention relates to an aluminum and / or zinc melting member, an aluminum and / or zinc melting furnace equipped with the member, a molten aluminum and / or hot dip galvanizing facility.
【０００２】[0002]
【従来の技術】アルミニウムおよび／または亜鉛を溶融
する溶融炉、溶融アルミニウムメッキおよび／または溶
融亜鉛メッキに使用する溶融鍋または溶融槽には、黒
鉛、普通鋼、鋳鉄等が使用されている。一般的には亜鉛
溶融鍋または溶融槽には普通鋼、ＮＡＧＰ鋼が、アルミ
ニウム溶融鍋または溶融槽には鋳鉄が使用されている。
しかし、普通鋼や鋳鉄製の溶融鍋の内面は溶融した亜鉛
合金やアルミニウム合金により湯溶浸食され、外面は高
温酸化により劣化するという問題があった。溶融鍋また
は溶融槽の内面のライニングとしてセラミックコーティ
ング等を施す方法もあるが、基材との密着性が十分でな
く、両者の熱膨張率が大きく異なるため、熱履歴により
セラミックコーティング層が剥がれるという問題があっ
た。2. Description of the Related Art Graphite, ordinary steel, cast iron, etc. are used in a melting furnace for melting aluminum and / or zinc, a melting pot or a melting tank used for molten aluminum plating and / or galvanizing. Generally, ordinary steel and NAGP steel are used for the zinc melting pot or the melting tank, and cast iron is used for the aluminum melting pot or the melting tank.
However, there is a problem that the inner surface of the melting pot made of ordinary steel or cast iron is hot-water eroded by the molten zinc alloy or aluminum alloy, and the outer surface is deteriorated by high temperature oxidation. There is also a method of applying ceramic coating etc. as the lining of the inner surface of the melting pot or the melting tank, but the adhesion to the base material is not sufficient and the coefficient of thermal expansion of both is greatly different, so the ceramic coating layer peels off due to thermal history. There was a problem.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、湯溶
浸食、高温酸化などに対し優れた耐性を発揮し、簡便な
方法により低コストで製造できるアルミニウムおよび／
または亜鉛溶融用部材、該部材を備えたアルミニウムお
よび／または亜鉛溶融炉、溶融アルミニウムおよび／ま
たは溶融亜鉛メッキ設備を提供するものである。DISCLOSURE OF THE INVENTION An object of the present invention is to exhibit excellent resistance to hot water erosion, high temperature oxidation, etc., and aluminum and / or aluminum which can be produced by a simple method at low cost.
Alternatively, the present invention provides a member for zinc melting, an aluminum and / or zinc melting furnace equipped with the member, a molten aluminum and / or hot dip galvanizing facility.
【０００４】[0004]
【課題を解決するための手段】本発明者は、上記の様な
従来技術の問題点に鑑みて鋭意研究を重ねた結果、特定
組成の合金メッキ皮膜を溶融鍋等の溶融用部材の金属基
体上に形成させる場合には、従来技術の問題点を大幅に
軽減あるいは実質的に解消し得ることを見出した。DISCLOSURE OF THE INVENTION As a result of intensive studies conducted by the present inventor in view of the problems of the prior art as described above, an alloy plating film of a specific composition is formed on a metal substrate of a melting member such as a melting pot. It has been found that the problems of the prior art can be greatly reduced or substantially eliminated when formed on top.
【０００５】本発明は、
項１．ニッケル−リン系合金メッキ皮膜を金属基体上に
有することを特徴とするアルミニウムおよび／または亜
鉛溶融用部材、
項２．ニッケル−リン系合金メッキ皮膜中のリンの含有
率が１〜２０重量％である項１に記載のアルミニウムお
よび／または亜鉛溶融用部材、
項３．ニッケル−リン系合金メッキ皮膜中のリンの含有
率が３〜１７重量％である項１に記載のアルミニウムお
よび／または亜鉛溶融用部材、
項４．アルミニウムおよび／または亜鉛溶融用部材が、
溶融鍋、溶融槽、撹拌棒、湯くみ、とりべ、かす取り、
熱電対保護管から選ばれる部材である項１〜３のいずれ
かに記載のアルミニウムおよび／または亜鉛溶融用部
材、
項５．前記項１〜４のいずれかに記載の部材を備えるこ
とを特徴とするアルミニウムおよび／または亜鉛溶融
炉、および、
項６．前記項１〜４のいずれかに記載の部材を備えるこ
とを特徴とする溶融アルミニウムおよび／または溶融亜
鉛メッキ設備、に関する。The present invention relates to item 1. 1. A member for melting aluminum and / or zinc, characterized by having a nickel-phosphorus alloy plating film on a metal substrate. Item 3. The aluminum and / or zinc melting member according to Item 1, wherein the content of phosphorus in the nickel-phosphorus alloy plating film is 1 to 20% by weight. Item 3. The aluminum and / or zinc melting member according to Item 1, wherein the content of phosphorus in the nickel-phosphorus alloy plating film is 3 to 17% by weight. The aluminum and / or zinc melting member is
Melting pot, melting tank, stirring rod, hot water tank, ladle, debris removal,
Item 4. The aluminum and / or zinc melting member according to any one of Items 1 to 3, which is a member selected from thermocouple protection tubes. Item 5. An aluminum and / or zinc melting furnace comprising the member according to any one of Items 1 to 4, and Item 6. Item 4. A hot-dip aluminum and / or hot-dip galvanizing facility comprising the member according to any one of Items 1 to 4.
【０００６】[0006]
【発明の実施の形態】本発明のアルミニウムおよび／ま
たは亜鉛溶融用部材は、金属基体上にニッケル−リン合
金メッキ皮膜を形成した構成を有する。ここで、アルミ
ニウムおよび／または亜鉛溶融用部材とは、アルミニウ
ムおよび／または亜鉛を溶融する際に用いられる部材の
ことをいい、該部材としては、溶融鍋、溶融槽、撹拌
棒、湯くみ、とりべ、かす取り、熱電対保護管などが例
示される。BEST MODE FOR CARRYING OUT THE INVENTION The aluminum and / or zinc melting member of the present invention has a structure in which a nickel-phosphorus alloy plating film is formed on a metal substrate. Here, the member for melting aluminum and / or zinc means a member used when melting aluminum and / or zinc, and examples of the member include a melting pot, a melting tank, a stirring rod, a hot water tank, and a tray. Examples thereof include shavings, debris removal, and thermocouple protection tubes.
【０００７】本発明の部材の基体となる金属の種類とし
ては、通常アルミニウムおよび亜鉛溶融用部材を形成し
うる金属であれば特に制限されず、例えば、鋳鉄、鋳
鋼、炭素鋼、特殊鋼、耐熱鋼、ステンレス鋼などが挙げ
られる。具体例として、ＳＳ４００、ＮＡＧＰ鋼、ＦＣ
２００等が挙げられる。There are no particular restrictions on the type of metal used as the base material of the member of the present invention, so long as it is a metal capable of forming a member for melting aluminum and zinc, and examples thereof include cast iron, cast steel, carbon steel, special steel, and heat resistance. Examples include steel and stainless steel. As a specific example, SS400, NAGP steel, FC
200 etc. are mentioned.
【０００８】ニッケル−リン系合金メッキ皮膜の厚さ
は、部材の材質および形状、該部材を使用する環境およ
び条件、合金の組成比などにより異なるが、通常1〜100
0μm程度であり、より好ましくは10〜100μm程度であ
る。The thickness of the nickel-phosphorus alloy plating film varies depending on the material and shape of the member, the environment and conditions in which the member is used, the composition ratio of the alloy, etc., but it is usually 1 to 100.
It is about 0 μm, and more preferably about 10 to 100 μm.
【０００９】ニッケル−リン系合金メッキ皮膜中のリン
含有率は、通常１〜２０重量％程度であり、好ましくは
３〜１７重量％程度であり、より好ましくは５〜１５重
量％程度である。リン含有率が低すぎる場合には、湯溶
浸食や高温酸化による部材の劣化防止という所期の効果
が十分に発揮されない。また、リンの含有率が多すぎる
場合にはメッキ皮膜が脆くなるので、リンの含有量は、
２０重量％以下とすることが好ましい。The phosphorus content in the nickel-phosphorus alloy plating film is usually about 1 to 20% by weight, preferably about 3 to 17% by weight, and more preferably about 5 to 15% by weight. If the phosphorus content is too low, the intended effect of preventing deterioration of the member due to hot metal infiltration or high temperature oxidation cannot be fully exerted. Also, if the phosphorus content is too high, the plating film becomes brittle, so the phosphorus content is
It is preferably 20% by weight or less.
【００１０】ニッケル−リン系合金メッキ皮膜は、ニッ
ケルとリンの２成分の合金メッキ皮膜だけではなく、ニ
ッケルとリンに加えてクロム、モリブデン、タングステ
ン、マンガン、テクネチウム、レニウム、鉄、ルテニウ
ム、オスミウム、コバルト、ロジウム、イリジウム、パ
ラジウム、白金、銅、銀、金、亜鉛、カドミウム、イン
ジウム、スズ、鉛、ホウ素などの元素の１種または２種
以上を含有するニッケル−リン系合金メッキ皮膜であっ
ても良い。好ましくは、クロム、モリブデン、タングス
テン、コバルト、銅、スズ等である。The nickel-phosphorus alloy plating film is not only a binary alloy plating film of nickel and phosphorus, but in addition to nickel and phosphorus, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, A nickel-phosphorus alloy plating film containing one or more elements such as cobalt, rhodium, iridium, palladium, platinum, copper, silver, gold, zinc, cadmium, indium, tin, lead and boron. Is also good. Preferred are chromium, molybdenum, tungsten, cobalt, copper, tin and the like.
【００１１】この様なニッケル−リン系合金メッキ皮膜
では、主となるニッケルの含有率は、ニッケル−リン系
合金メッキ皮膜中、ニッケル、リンおよびその他の元素
からなる合金金属を基準として、５０重量％程度以上、
具体的には５０〜９７重量％程度であることが好まし
い。In such a nickel-phosphorus alloy plating film, the main nickel content is 50 wt% based on the alloy metal consisting of nickel, phosphorus and other elements in the nickel-phosphorus alloy plating film. % Or more,
Specifically, it is preferably about 50 to 97% by weight.
【００１２】さらに、このニッケル−リン系合金メッキ
皮膜中には断熱効果を有する酸化アルミニウム、酸化イ
ットリウム、酸化クロム、酸化ジルコニウム、酸化ケイ
素、酸化チタン、炭化ケイ素、炭化タングステン等の無
機微粒子が含まれていても良い。好ましくは、酸化アル
ミニウム、酸化ジルコニウム、酸化チタン、炭化ケイ素
等である。これら無機微粒子の大きさは、平均粒径が、
０．０１〜２０μm、好ましくは０．０５〜１０μmのも
のがよい。これらの元素または酸化物の含有率は、メッ
キ皮膜中１〜２０重量％程度とすることが好ましい。Further, the nickel-phosphorus alloy plating film contains inorganic fine particles such as aluminum oxide, yttrium oxide, chromium oxide, zirconium oxide, silicon oxide, titanium oxide, silicon carbide and tungsten carbide which have a heat insulating effect. It may be. Preferred are aluminum oxide, zirconium oxide, titanium oxide, silicon carbide and the like. The average particle size of these inorganic fine particles is
The thickness is preferably 0.01 to 20 μm, more preferably 0.05 to 10 μm. The content of these elements or oxides is preferably about 1 to 20% by weight in the plating film.
【００１３】金属基体上にニッケル−リン系合金メッキ
層を形成する方法は、特に限定されず、常法に従って、
金属基体を脱脂、酸洗などの前処理に供した後、ニッケ
ル塩とリン酸、亜リン酸などを含有する電解メッキ液ま
たはニッケル塩と次亜リン酸塩を含有する無電解メッキ
液を用いて、金属基体に対するメッキ処理を行えばよ
い。電解メッキ液および無電解メッキ液の種類も、特に
限定されず、公知の各種組成の電解メッキ液あるいは無
電解メッキ液を使用することができる。The method for forming the nickel-phosphorus alloy plating layer on the metal substrate is not particularly limited, and may be according to a conventional method.
After subjecting the metal substrate to pretreatment such as degreasing and pickling, use an electroplating solution containing nickel salt and phosphoric acid, phosphorous acid, or an electroless plating solution containing nickel salt and hypophosphite. Then, the metal substrate may be plated. The types of electrolytic plating solution and electroless plating solution are not particularly limited, and known electrolytic plating solutions or electroless plating solutions of various compositions can be used.
【００１４】また、金属基体に対するニッケル−リン系
合金メッキ皮膜の密着性を向上させるために、必要に応
じて、公知の方法により金属基体を予めストライクメッ
キ処理した後、合金メッキ皮膜を形成しても良い。さら
に、金属基体上に通常の電解ニッケルメッキ皮膜あるい
は無電解ニッケルメッキ皮膜を形成させた後、合金メッ
キ皮膜を形成させても良い。無電解メッキに対する触媒
活性のない金属基体上に直接無電解メッキを行う場合に
は、常法に従って、触媒を付与した後、無電解メッキを
行えばよい。In order to improve the adhesion of the nickel-phosphorus alloy plating film to the metal substrate, if necessary, the metal substrate may be previously strike-plated by a known method, and then the alloy plating film may be formed. Is also good. Further, the alloy plating film may be formed after the usual electrolytic nickel plating film or electroless nickel plating film is formed on the metal substrate. When performing electroless plating directly on a metal substrate having no catalytic activity for electroless plating, electroless plating may be performed after applying a catalyst according to a conventional method.
【００１５】この様な電解メッキ法あるいは無電解メッ
キ法によれば、簡単な方法により低コストで、アルミニ
ウムおよび／または亜鉛溶融用部材を得ることができ
る。そして、ニッケル-リン系合金メッキ皮膜が形成さ
れた部材は、長期にわたり溶融した亜鉛合金やアルミニ
ウムニウム合金に対する耐湯溶浸食、耐高温酸化性など
を発揮する。According to such electrolytic plating method or electroless plating method, a member for melting aluminum and / or zinc can be obtained at a low cost by a simple method. The member on which the nickel-phosphorus alloy plating film is formed exhibits hot-water erosion resistance, high-temperature oxidation resistance, and the like with respect to the molten zinc alloy or aluminum-nium alloy for a long period of time.
【００１６】特に、無電解メッキ法により皮膜形成を行
う場合には、複雑な形状の部材表面にも、均一な合金メ
ッキ皮膜を容易に形成することができる。In particular, when the film is formed by the electroless plating method, a uniform alloy plating film can be easily formed on the surface of a member having a complicated shape.
【００１７】また、電解メッキ方法による場合にも、適
当な補助電極を用いることにより、複雑な形状の部材表
面に均一な合金メッキ皮膜を形成することができる。Also in the case of the electrolytic plating method, a uniform alloy plating film can be formed on the surface of a member having a complicated shape by using an appropriate auxiliary electrode.
【００１８】電解メッキ法によってニッケル-リン系合
金メッキ皮膜を形成させる方法として、ニッケル塩とし
て硫酸ニッケルを用い、かつリン供給源としてリン酸、
亜リン酸を用いる場合の浴組成およびメッキ条件の一例
を下記に示す。
＜ニッケル−リン系メッキ液の浴組成およびメッキ条件
＞
硫酸ニッケル １２０〜２００ｇ／Ｌ
塩化ニッケル ３０〜６０ｇ／Ｌ
リン酸 ２０〜６０ｇ／Ｌ
亜リン酸 ２０〜６０ｇ／Ｌ
ｐＨ ０．５〜１．５
温度 ５０〜７０℃
陰極電流密度 ５〜１５Ａ／ｄｍ2
また、無電解メッキ法によってニッケル−リン系合金メ
ッキ皮膜を形成する場合には、公知の組成の無電解メッ
キ液を用いて、通常の無電解メッキ条件と同様にして、
ニッケル-リン系合金メッキ皮膜を形成すればよい。As a method for forming a nickel-phosphorus alloy plating film by electrolytic plating, nickel sulfate is used as a nickel salt and phosphoric acid is used as a phosphorus supply source.
An example of bath composition and plating conditions when using phosphorous acid is shown below. <Bath composition of nickel-phosphorus plating solution and plating conditions> Nickel sulfate 120 to 200 g / L nickel chloride 30 to 60 g / L phosphoric acid 20 to 60 g / L phosphorous acid 20 to 60 g / L pH 0.5 to 1. 5 Temperature 50 to 70 ° C. Cathode current density 5 to 15 A / dm 2 When a nickel-phosphorus alloy plating film is formed by an electroless plating method, an electroless plating solution having a known composition is used, Similar to electroless plating conditions,
A nickel-phosphorus alloy plating film may be formed.
【００１９】上記のいずれかの方法を用いて、金属基体
上にニッケル−リン系合金メッキ皮膜を形成することに
より、本発明によるアルミニウムおよび／または亜鉛溶
融用部材が得られる。A member for melting aluminum and / or zinc according to the present invention can be obtained by forming a nickel-phosphorus alloy plating film on a metal substrate using any of the above methods.
【００２０】本発明のアルミニウムおよび／または亜鉛
溶融用部材を備えることを特徴とするアルミニウムおよ
び／または亜鉛溶融炉としては、例えば、本発明のアル
ミニウムおよび／または亜鉛溶融鍋、加熱装置、加熱制
御装置、集塵装置、排気ガス浄化装置等を備えているも
のであればよい。As the aluminum and / or zinc melting furnace characterized by including the aluminum and / or zinc melting member of the present invention, for example, the aluminum and / or zinc melting pot of the present invention, a heating device, and a heating control device can be used. Any device that includes a dust collector, an exhaust gas purifier, and the like may be used.
【００２１】本発明のアルミニウムおよび／または亜鉛
溶融用部材を備えることを特徴とする溶融アルミニウム
および／または溶融亜鉛メッキ設備としては、例えば、
本発明のアルミニウムおよび／または亜鉛溶融槽、加熱
装置、加熱制御装置、集塵装置、排気ガス浄化装置等を
備えているものであればよい。Examples of the molten aluminum and / or galvanizing equipment equipped with the aluminum and / or zinc melting member of the present invention include:
It may be provided with the aluminum and / or zinc melting tank of the present invention, a heating device, a heating control device, a dust collector, an exhaust gas purifying device, and the like.
【００２２】[0022]
【実施例】以下に実施例を示し、本発明をさらに詳細に
説明する。The present invention will be described in more detail with reference to the following examples.
【００２３】実施例１
２種の形態の試験材料を用いて、電解メッキを行った。
なお、以下の各実施例および比較例においても、同様の
試験材料を使用した。
試験材料１：材質ＳＳ４００の正方形板材（50mm×50mm
×3mm）
試験材料２：材質ＮＡＧＰ鋼の溶融鍋（直径500mm、深
さ300mm、厚さ35mm）
試験材料３：材質ＦＣ２００の溶融鍋（直径500mm、深
さ300mm、厚さ35mm）
上記の試験材料１、２および３を用いて電解メッキを行
った。Example 1 Electroplating was performed using two forms of test material.
In addition, the same test material was used also in each of the following Examples and Comparative Examples. Test material 1: Material SS400 square plate (50mm x 50mm
Test material 2: Material NAGP steel melting pot (diameter 500 mm, depth 300 mm, thickness 35 mm) Test material 3: Material FC200 melting pot (diameter 500 mm, depth 300 mm, thickness 35 mm) The above test materials Electroplating was performed using Nos. 1, 2 and 3.
【００２４】試験材料１、２および３をアルカリ脱脂液
で脱脂した後、下記組成の表１に示す組成の電解ニッケ
ル−リン合金メッキ液を含むメッキ槽を用いて、液温６
５℃、pH１．０、電流密度５A/dm2の条件下にスクリュ
ー撹拌しつつ、膜厚が２０μmとなるまで電解メッキ処
理を行って、試験材料１、２および３それぞれの表面に
電解ニッケル−リン合金メッキ皮膜を形成させた。メッ
キ処理終了後、試験材料１、２および３を水洗し、乾燥
させた。After the test materials 1, 2 and 3 were degreased with an alkaline degreasing liquid, a liquid temperature of 6 was obtained using a plating bath containing an electrolytic nickel-phosphorus alloy plating liquid having the composition shown in Table 1 below.
While stirring with a screw under the conditions of 5 ° C., pH 1.0, and current density 5 A / dm 2 , electrolytic plating treatment is performed until the film thickness reaches 20 μm, and electrolytic nickel on the surface of each of test materials 1, 2 and 3 A phosphorus alloy plating film was formed. After completion of the plating treatment, the test materials 1, 2 and 3 were washed with water and dried.
【００２５】＜表１＞
硫酸ニッケル１６０ｇ／Ｌ
塩化ニッケル ４５ｇ／Ｌ
リン酸 ４０ｇ／Ｌ
亜リン酸 ４０ｇ／Ｌ
試験材料１を使用して、エネルギー分散型Ｘ線分析装置
(（株）堀場製作所製、“EMAX-5700”)により、合金メ
ッキ皮膜中のリン含有率を求めたところ、１７重量％で
あった。<Table 1> Nickel sulfate 160 g / L Nickel chloride 45 g / L Phosphoric acid 40 g / L Phosphorous acid 40 g / L Using the test material 1, an energy dispersive X-ray analyzer
The phosphorus content in the alloy plating film was determined by using "EMAX-5700" (manufactured by Horiba, Ltd.) and found to be 17% by weight.
【００２６】一方、合金メッキ皮膜を形成した試験材料
２を亜鉛溶融炉に設置して５００℃にて1000時間加熱を
行った。また、試験材料３をアルミニウム溶融炉に設置
して７００℃にて1000時間加熱を行った。On the other hand, the test material 2 having the alloy plating film formed thereon was placed in a zinc melting furnace and heated at 500 ° C. for 1000 hours. Further, the test material 3 was placed in an aluminum melting furnace and heated at 700 ° C. for 1000 hours.
【００２７】1000時間の加熱後、試験材料２、３の底部
の断面を切り出し、金属顕微鏡にて調べた。ニッケル−
リン合金メッキ皮膜により溶融鍋基体が保護されている
ため、基体の内側は湯溶浸食劣化が、基体の外側は高温
酸化劣化が認められなかった。After heating for 1000 hours, the bottom sections of the test materials 2 and 3 were cut out and examined with a metallurgical microscope. Nickel-
Since the base material of the melting pot was protected by the phosphorus alloy plating film, no deterioration due to hot metal erosion was observed inside the base material, and no deterioration due to high temperature oxidation was observed outside the base material.
【００２８】実施例２
実施例１と同様にして脱脂処理した試験材料１、２およ
び３に電解ニッケル−リン合金メッキ皮膜を形成させ
た。Example 2 Test materials 1, 2 and 3 degreased in the same manner as in Example 1 were formed with electrolytic nickel-phosphorus alloy plating films.
【００２９】すなわち、表２に示す電解ニッケル−リン
合金メッキ液を含むメッキ槽を用いて、試験材料１、２
および３に対し、液温６５℃、pH１．０、電流密度５A/
dm2の条件下にスクリュー撹拌しつつ、膜厚が２０μmと
なるまで電解メッキ処理を行って、試験材料１、２およ
び３それぞれの表面に電解ニッケル−リン複合メッキ皮
膜を形成させた。メッキ処理終了後、試験材料１、２お
よび３を水洗し、乾燥させた。That is, using the plating bath containing the electrolytic nickel-phosphorus alloy plating solution shown in Table 2, test materials 1 and 2 were prepared.
For 3 and 3, liquid temperature 65 ℃, pH 1.0, current density 5A /
While stirring with a screw under the condition of dm 2 , electrolytic plating treatment was carried out until the film thickness became 20 μm to form an electrolytic nickel-phosphorus composite plating film on each surface of the test materials 1, 2 and 3. After completion of the plating treatment, the test materials 1, 2 and 3 were washed with water and dried.
【００３０】＜表２＞
硫酸ニッケル１６０ｇ／Ｌ
塩化ニッケル ４５ｇ／Ｌ
リン酸 ４０ｇ／Ｌ
亜リン酸 １０ｇ／Ｌ
試験材料１についてメッキ皮膜中のリン含有率を求めた
ところ、１２重量％であった。<Table 2> Nickel sulfate 160 g / L Nickel chloride 45 g / L Phosphoric acid 40 g / L Phosphorous acid 10 g / L The phosphorus content in the plating film of the test material 1 was determined to be 12% by weight. .
【００３１】一方、合金メッキ皮膜を形成した試験材料
２を亜鉛溶融炉に設置して５００℃にて1000時間加熱を
行った。また、試験材料３をアルミニウム溶融炉に設置
して７００℃にて1000時間加熱を行った。On the other hand, the test material 2 having the alloy plating film formed thereon was placed in a zinc melting furnace and heated at 500 ° C. for 1000 hours. Further, the test material 3 was placed in an aluminum melting furnace and heated at 700 ° C. for 1000 hours.
【００３２】1000時間の加熱後、試験材料２、３の底部
の断面を切り出し、金属顕微鏡にて調べた。ニッケル−
リン合金メッキ皮膜により溶融鍋基体が保護されている
ため、基体の内側は湯溶浸食劣化が、基体の外側は高温
酸化劣化が認められなかった。After heating for 1000 hours, the bottom sections of the test materials 2 and 3 were cut out and examined with a metallurgical microscope. Nickel-
Since the base material of the melting pot was protected by the phosphorus alloy plating film, no deterioration due to hot metal erosion was observed inside the base material, and no deterioration due to high temperature oxidation was observed outside the base material.
【００３３】実施例３
実施例１と同様にして脱脂処理した試験材料１、２およ
び３に電解ニッケル−リン合金メッキ皮膜を形成させ
た。Example 3 Electrolytic nickel-phosphorus alloy plating films were formed on the test materials 1, 2 and 3 degreased in the same manner as in Example 1.
【００３４】すなわち、表３に示す電解ニッケル−リン
合金メッキ液を含むメッキ槽を用いて、試験材料１、２
および３に対し、液温６５℃、pH１．０、電流密度５A/
dm2の条件下にスクリュー撹拌しつつ、膜厚が２０μmと
なるまで電解メッキ処理を行って、試験材料１、２およ
び３それぞれの表面に電解ニッケル−リン合金メッキ皮
膜を形成させた。メッキ処理終了後、試験材料１、２お
よび３を水洗し、乾燥させた。That is, using the plating bath containing the electrolytic nickel-phosphorus alloy plating solution shown in Table 3, test materials 1 and 2 were prepared.
For 3 and 3, liquid temperature 65 ℃, pH 1.0, current density 5A /
While stirring with a screw under the condition of dm 2 , electrolytic plating treatment was performed until the film thickness became 20 μm to form an electrolytic nickel-phosphorus alloy plating film on each surface of the test materials 1, 2 and 3. After completion of the plating treatment, the test materials 1, 2 and 3 were washed with water and dried.
【００３５】＜表３＞
硫酸ニッケル１６０ｇ／Ｌ
塩化ニッケル ４５ｇ／Ｌ
リン酸 ４０ｇ／Ｌ
亜リン酸 ５ｇ／Ｌ
試験材料１についてメッキ皮膜中のリン含有率を求めた
ところ、９重量％であった。<Table 3> Nickel sulfate 160 g / L Nickel chloride 45 g / L Phosphoric acid 40 g / L Phosphorous acid 5 g / L The phosphorus content in the plating film of the test material 1 was determined to be 9% by weight. .
【００３６】一方、合金メッキ皮膜を形成した試験材料
２を亜鉛溶融炉に設置して５００℃にて1000時間加熱を
行った。また、試験材料３をアルミニウム溶融炉に設置
して７００℃にて1000時間加熱を行った。On the other hand, the test material 2 having the alloy plating film formed thereon was placed in a zinc melting furnace and heated at 500 ° C. for 1000 hours. Further, the test material 3 was placed in an aluminum melting furnace and heated at 700 ° C. for 1000 hours.
【００３７】1000時間の加熱後、試験材料２、３の底部
の断面を切り出し、金属顕微鏡にて調べた。ニッケル−
リン合金メッキ皮膜により溶融鍋基体が保護されている
ため、基体の内側は湯溶浸食劣化が、基体の外側は高温
酸化劣化が認められなかった。After heating for 1000 hours, the bottom sections of the test materials 2 and 3 were cut out and examined with a metallurgical microscope. Nickel-
Since the base material of the melting pot was protected by the phosphorus alloy plating film, no deterioration due to hot metal erosion was observed inside the base material, and no deterioration due to high temperature oxidation was observed outside the base material.
【００３８】実施例４
実施例１と同様にして脱脂処理した試験材料１、２およ
び３に電解ニッケル-リン合金メッキ皮膜を形成させ
た。Example 4 The electrolytic nickel-phosphorus alloy plating film was formed on each of the test materials 1, 2 and 3 degreased in the same manner as in Example 1.
【００３９】すなわち、表４に示す電解ニッケル−リン
合金メッキ液を含むメッキ槽を用いて、試験材料１、２
および３に対し、液温６５℃、pH１．０の条件下にスク
リュー撹拌しつつ、膜厚が２０μmとなるまで電解メッ
キ処理を行って、試験材料１、２および３それぞれの表
面に電解ニッケル−リン合金メッキ皮膜を形成させた。
メッキ処理終了後、試験材料１、２および３を水洗し、
乾燥させた。That is, using the plating bath containing the electrolytic nickel-phosphorus alloy plating solution shown in Table 4, test materials 1, 2
And 3 were subjected to electrolytic plating treatment with a screw stirring under the conditions of liquid temperature of 65 ° C. and pH of 1.0 until the film thickness became 20 μm, and electrolytic nickel was applied to the surface of each of test materials 1, 2 and 3. A phosphorus alloy plating film was formed.
After finishing the plating treatment, wash the test materials 1, 2 and 3 with water,
Dried.
【００４０】＜表４＞
硫酸ニッケル１６０ｇ／Ｌ
塩化ニッケル ４５ｇ／Ｌ
リン酸 ４０ｇ／Ｌ
亜リン酸 ２ｇ／Ｌ
試験材料１についてメッキ皮膜中のリン含有率を求めた
ところ、５重量％であった。<Table 4> Nickel sulfate 160 g / L Nickel chloride 45 g / L Phosphoric acid 40 g / L Phosphorous acid 2 g / L The phosphorus content in the plating film of the test material 1 was determined to be 5% by weight. .
【００４１】一方、合金メッキ皮膜を形成した試験材料
２を亜鉛溶融炉に設置して５００℃にて1000時間加熱を
行った。また、試験材料３をアルミニウム溶融炉に設置
して７００℃にて1000時間加熱を行った。On the other hand, the test material 2 having the alloy plating film formed thereon was placed in a zinc melting furnace and heated at 500 ° C. for 1000 hours. Further, the test material 3 was placed in an aluminum melting furnace and heated at 700 ° C. for 1000 hours.
【００４２】1000時間の加熱後、試験材料２、３の底部
の断面を切り出し、金属顕微鏡にて調べた。ニッケル−
リン合金メッキ皮膜により溶融鍋基体が保護されている
ため、基体の内側は湯溶浸食劣化が、基体の外側は高温
酸化劣化が認められなかった。After heating for 1000 hours, the bottom sections of the test materials 2 and 3 were cut out and examined with a metallurgical microscope. Nickel-
Since the base material of the melting pot was protected by the phosphorus alloy plating film, no deterioration due to hot metal erosion was observed inside the base material, and no deterioration due to high temperature oxidation was observed outside the base material.
【００４３】実施例５
実施例１と同様にして脱脂処理した試験材料１、２およ
び３に無電解ニッケル−リン合金メッキ皮膜を形成させ
た。Example 5 Test materials 1, 2 and 3 degreased in the same manner as in Example 1 were coated with an electroless nickel-phosphorus alloy plating film.
【００４４】すなわち、表５に示す無電解ニッケル−リ
ン合金メッキ液を含むメッキ槽を用いて、試験材料１、
２および３に対し、液温９０℃、pH９．０の条件下にス
クリュー撹拌しつつ、膜厚が２０μmとなるまで無電解
メッキ処理を行って、試験材料１および２それぞれの表
面に無電解ニッケル−リン合金メッキ皮膜を形成させ
た。メッキ処理終了後、試験材料１、２および３を水洗
し、乾燥させた。That is, using the plating bath containing the electroless nickel-phosphorus alloy plating solution shown in Table 5, the test material 1,
2 and 3 were subjected to electroless plating treatment with screw stirring under the conditions of liquid temperature 90 ° C. and pH 9.0, until the film thickness became 20 μm, and electroless nickel was applied to the surface of each of test materials 1 and 2. -A phosphorus alloy plating film was formed. After completion of the plating treatment, the test materials 1, 2 and 3 were washed with water and dried.
【００４５】＜表５＞
硫酸ニッケル ２６ｇ／Ｌ
次亜リン酸ナトリウム ２１ｇ／Ｌ
塩化アンモニウム ６５ｇ／Ｌ
クエン酸ナトリウム ６０ｇ／Ｌ
試験材料１についてメッキ皮膜中のリン含有率を求めた
ところ、３重量％であった。<Table 5> Nickel sulfate 26 g / L Sodium hypophosphite 21 g / L Ammonium chloride 65 g / L Sodium citrate 60 g / L For the test material 1, the phosphorus content in the plating film was determined to be 3% by weight. Met.
【００４６】一方、合金メッキ皮膜を形成した試験材料
２を亜鉛溶融炉に設置して５００℃にて1000時間加熱を
行った。また、試験材料３をアルミニウム溶融炉に設置
して７００℃にて1000時間加熱を行った。On the other hand, the test material 2 having the alloy plating film formed thereon was placed in a zinc melting furnace and heated at 500 ° C. for 1000 hours. Further, the test material 3 was placed in an aluminum melting furnace and heated at 700 ° C. for 1000 hours.
【００４７】1000時間の加熱後、試験材料２、３の底部
の断面を切り出し、金属顕微鏡にて調べた。ニッケル−
リン合金メッキ皮膜により溶融鍋基体が保護されている
ため、基体の内側は湯溶浸食劣化が、基体の外側は高温
酸化劣化が認められなかった。After heating for 1000 hours, the bottom sections of the test materials 2 and 3 were cut out and examined with a metallurgical microscope. Nickel-
Since the base material of the melting pot was protected by the phosphorus alloy plating film, no deterioration due to hot metal erosion was observed inside the base material, and no deterioration due to high temperature oxidation was observed outside the base material.
【００４８】実施例６
実施例１と同様にして脱脂処理した試験材料１、２およ
び３に無電解ニッケル−リン合金メッキ皮膜を形成させ
た。Example 6 Test materials 1, 2 and 3 degreased in the same manner as in Example 1 were coated with an electroless nickel-phosphorus alloy plating film.
【００４９】すなわち、表６に示す無電解ニッケル−リ
ン合金メッキ液を含むメッキ槽を用いて、試験材料１、
２および３に対し、液温９０℃、pH４．４の条件下にス
クリュー撹拌しつつ、膜厚が２０μmとなるまで無電解
メッキ処理を行って、試験材料１、２および３それぞれ
の表面に無電解ニッケル−リン合金メッキ皮膜を形成さ
せた。メッキ処理終了後、試験材料１、２および３を水
洗し、乾燥させた。That is, using the plating bath containing the electroless nickel-phosphorus alloy plating solution shown in Table 6, the test material 1,
2 and 3 were subjected to electroless plating until the film thickness reached 20 μm while screw stirring under the conditions of a liquid temperature of 90 ° C. and a pH of 4.4. An electrolytic nickel-phosphorus alloy plating film was formed. After completion of the plating treatment, the test materials 1, 2 and 3 were washed with water and dried.
【００５０】＜表６＞
硫酸ニッケル ２１ｇ／Ｌ
次亜リン酸ナトリウム ２５ｇ／Ｌ
乳酸 ２７ｇ／Ｌ
プロピオン酸 ２．２ｇ／Ｌ
試験材料１についてメッキ皮膜中のリン含有率を求めた
ところ、９重量％であった。<Table 6> Nickel sulfate 21 g / L Sodium hypophosphite 25 g / L Lactic acid 27 g / L Propionic acid 2.2 g / L The phosphorus content in the plating film of the test material 1 was determined to be 9% by weight. Met.
【００５１】一方、合金メッキ皮膜を形成した試験材料
２を亜鉛溶融炉に設置して５００℃にて1000時間加熱を
行った。また、試験材料３をアルミニウム溶融炉に設置
して７００℃にて1000時間加熱を行った。On the other hand, the test material 2 having the alloy plating film formed thereon was placed in a zinc melting furnace and heated at 500 ° C. for 1000 hours. Further, the test material 3 was placed in an aluminum melting furnace and heated at 700 ° C. for 1000 hours.
【００５２】1000時間の加熱後、試験材料２、３の底部
の断面を切り出し、金属顕微鏡にて調べた。ニッケル−
リン合金メッキ皮膜により溶融鍋基体が保護されている
ため、基体の内側は湯溶浸食劣化が、基体の外側は高温
酸化劣化が認められなかった。After heating for 1000 hours, the bottom sections of the test materials 2 and 3 were cut out and examined with a metallurgical microscope. Nickel-
Since the base material of the melting pot was protected by the phosphorus alloy plating film, no deterioration due to hot metal erosion was observed inside the base material, and no deterioration due to high temperature oxidation was observed outside the base material.
【００５３】実施例７
実施例１と同様にして脱脂処理した試験材料１、２およ
び３に無電解ニッケル−リン合金メッキ皮膜を形成させ
た。Example 7 Test materials 1, 2 and 3 degreased in the same manner as in Example 1 were formed with an electroless nickel-phosphorus alloy plating film.
【００５４】すなわち、表７に示す無電解ニッケル−リ
ン合金メッキ液を含むメッキ槽を用いて、試験材料１、
２および３に対し、液温９０℃、pHの条件下にスクリュ
ー撹拌しつつ、膜厚が２０μmとなるまで無電解メッキ
処理を行って、試験材料１および２それぞれの表面に無
電解ニッケル−リン合金メッキ皮膜を形成させた。メッ
キ処理終了後、試験材料１、２および３を水洗し、乾燥
させた。That is, using the plating bath containing the electroless nickel-phosphorus alloy plating solution shown in Table 7, the test material 1,
2 and 3 were subjected to electroless plating until the film thickness reached 20 μm with screw stirring under the conditions of a liquid temperature of 90 ° C. and pH, and electroless nickel-phosphorus was applied to the surface of each of test materials 1 and 2. An alloy plating film was formed. After completion of the plating treatment, the test materials 1, 2 and 3 were washed with water and dried.
【００５５】＜表７＞
硫酸ニッケル ２６ｇ／Ｌ
次亜リン酸ナトリウム ２５ｇ／Ｌ
クエン酸ナトリウム ６０ｇ／Ｌ
ホウ酸 ３０ｇ／Ｌ
試験材料１についてメッキ皮膜中のリン含有率を求めた
ところ、１３重量％であった。<Table 7> Nickel sulfate 26 g / L Sodium hypophosphite 25 g / L Sodium citrate 60 g / L Boric acid 30 g / L For the test material 1, the phosphorus content in the plating film was determined to be 13% by weight. Met.
【００５６】一方、合金メッキ皮膜を形成した試験材料
２を亜鉛溶融炉に設置して５００℃にて1000時間加熱を
行った。また、試験材料３をアルミニウム溶融炉に設置
して７００℃にて1000時間加熱を行った。On the other hand, the test material 2 having the alloy plating film formed thereon was placed in a zinc melting furnace and heated at 500 ° C. for 1000 hours. Further, the test material 3 was placed in an aluminum melting furnace and heated at 700 ° C. for 1000 hours.
【００５７】1000時間の加熱後、試験材料２、３の底部
の断面を切り出し、金属顕微鏡にて調べた。ニッケル−
リン合金メッキ皮膜により溶融鍋基体が保護されている
ため、基体の内側は湯溶浸食劣化が、基体の外側は高温
酸化劣化が認められなかった。After heating for 1000 hours, the bottom sections of the test materials 2 and 3 were cut out and examined with a metallurgical microscope. Nickel-
Since the base material of the melting pot was protected by the phosphorus alloy plating film, no deterioration due to hot metal erosion was observed inside the base material, and no deterioration due to high temperature oxidation was observed outside the base material.
【００５８】比較例
メッキを行っていない試験材料２を亜鉛溶融炉に設置し
て５００℃にて1000時間加熱を行った。また、試験材料
３をアルミニウム溶融炉に設置して７００℃にて1000時
間加熱を行った。Comparative Example The test material 2 which was not plated was placed in a zinc melting furnace and heated at 500 ° C. for 1000 hours. Further, the test material 3 was placed in an aluminum melting furnace and heated at 700 ° C. for 1000 hours.
【００５９】1000時間の加熱後、試験材料２、３の底部
の断面を切り出し、金属顕微鏡にて調べた。試験材料２
の基体の内側は約５０００μｍの亜鉛湯溶浸食劣化層
が、基体の外側は１００μｍの高温酸化劣化層が認めら
れた。また、試験材料３の基体の内側は約３０００μｍ
のアルミニウム湯溶浸食劣化層が、基体の外側は２００
μｍの高温酸化劣化層が認められた。After heating for 1000 hours, the bottom sections of the test materials 2 and 3 were cut out and examined with a metallurgical microscope. Test material 2
It was recognized that the inside of the substrate of No. 1 was about 5000 μm in the infiltration deterioration layer and the outside of the substrate was 100 μm in the high temperature oxidation deterioration layer. The inside of the base material of the test material 3 is about 3000 μm
The aluminum erosion corrosion deterioration layer of
A high temperature oxidative deterioration layer having a thickness of μm was observed.
【００６０】[0060]
【発明の効果】本発明によるアルミニウムおよび／また
は亜鉛溶融用部材は、溶融した亜鉛合金やアルミニウム
ニウム合金に対する湯溶浸食、高温酸化などに対して、
長期にわたり優れた耐性を発揮する。The member for melting aluminum and / or zinc according to the present invention is resistant to hot-water erosion, high-temperature oxidation, etc. of molten zinc alloy and aluminum-nium alloy.
Exhibits excellent resistance over a long period of time.
【００６１】また、本発明によるアルミニウムおよび／
または亜鉛溶融用部材は、簡便な方法により低コストで
製造することができる。In addition, according to the present invention, aluminum and / or
Alternatively, the zinc melting member can be manufactured at a low cost by a simple method.
【００６２】また、本発明で採用するニッケル−リン系
合金メッキ法によれば、複雑な形状部分の部材表面に
も、簡単にメッキ皮膜を形成することができる。Further, according to the nickel-phosphorus alloy plating method used in the present invention, it is possible to easily form a plating film on the surface of a member having a complicated shape.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 清水 行男 大阪府大阪市中央区平野町四丁目１番２号 大阪瓦斯株式会社内 Ｆターム(参考） 4K027 AD04 AD08 AD13 4K044 AA03 AA04 AB10 BA02 BA04 BA06 BA08 BA10 BA19 BB01 BC02 CA15 CA18 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Yukio Shimizu 4-1-2 Hirano-cho, Chuo-ku, Osaka-shi, Osaka Prefecture Within Osaka Gas Co., Ltd. F-term (reference) 4K027 AD04 AD08 AD13 4K044 AA03 AA04 AB10 BA02 BA04 BA06 BA08 BA10 BA19 BB01 BC02 CA15 CA18
Claims (6)
基体上に有することを特徴とするアルミニウムおよび／
または亜鉛溶融用部材。1. Aluminum and / or a nickel-phosphorus alloy plating film on a metal substrate.
Or a member for melting zinc.
ンの含有率が１〜２０重量％である請求項１に記載のア
ルミニウムおよび／または亜鉛溶融用部材。2. The member for melting aluminum and / or zinc according to claim 1, wherein the content of phosphorus in the nickel-phosphorus alloy plating film is 1 to 20% by weight.
ンの含有率が３〜１７重量％である請求項１に記載のア
ルミニウムおよび／または亜鉛溶融用部材。3. The aluminum and / or zinc melting member according to claim 1, wherein the content of phosphorus in the nickel-phosphorus alloy plating film is 3 to 17% by weight.
部材が、溶融鍋、溶融槽、撹拌棒、湯くみ、とりべ、か
す取り、熱電対保護管から選ばれる部材である請求項１
〜３のいずれかに記載のアルミニウムおよび／または亜
鉛溶融用部材。4. The member for melting aluminum and / or zinc is a member selected from a melting pot, a melting tank, a stirring bar, a hot water tank, a ladle, a debris remover, and a thermocouple protection tube.
A member for melting aluminum and / or zinc according to any one of 3 to 3.
備えることを特徴とするアルミニウムおよび／または亜
鉛溶融炉。5. An aluminum and / or zinc melting furnace comprising the member according to any one of claims 1 to 4.
備えることを特徴とする溶融アルミニウムおよび／また
は溶融亜鉛メッキ設備。6. A hot dip aluminum and / or hot dip galvanizing facility comprising the member according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002041325A JP2003239057A (en) | 2002-02-19 | 2002-02-19 | Member for melting aluminum and/or zinc |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002041325A JP2003239057A (en) | 2002-02-19 | 2002-02-19 | Member for melting aluminum and/or zinc |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003239057A true JP2003239057A (en) | 2003-08-27 |
Family
ID=27781776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002041325A Pending JP2003239057A (en) | 2002-02-19 | 2002-02-19 | Member for melting aluminum and/or zinc |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003239057A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018079188A1 (en) * | 2016-10-25 | 2018-05-03 | 石原ケミカル株式会社 | Heat-treatment-type method for forming electroconductive coating on passive-state-forming light metal |
| US20180363674A1 (en) * | 2017-06-20 | 2018-12-20 | Metal Industries Research And Development Centre | Pump device for casting processes |
-
2002
- 2002-02-19 JP JP2002041325A patent/JP2003239057A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018079188A1 (en) * | 2016-10-25 | 2018-05-03 | 石原ケミカル株式会社 | Heat-treatment-type method for forming electroconductive coating on passive-state-forming light metal |
| US20180363674A1 (en) * | 2017-06-20 | 2018-12-20 | Metal Industries Research And Development Centre | Pump device for casting processes |
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