JPH07145473A - Method for plating of vapor deposited alloy - Google Patents
Method for plating of vapor deposited alloyInfo
- Publication number
- JPH07145473A JPH07145473A JP29369093A JP29369093A JPH07145473A JP H07145473 A JPH07145473 A JP H07145473A JP 29369093 A JP29369093 A JP 29369093A JP 29369093 A JP29369093 A JP 29369093A JP H07145473 A JPH07145473 A JP H07145473A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- composition
- bath
- metal
- vapor
- 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.)
- Withdrawn
Links
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、連続真空蒸着めっき法
において、蒸発源となる合金浴から金属を蒸発させて蒸
着合金めっき皮膜を形成するに際し、所望の合金めっき
組成を工業的に安定して得ることのできる蒸着合金めっ
き法に関するものである。BACKGROUND OF THE INVENTION The present invention relates to a method for continuously stabilizing a desired alloy plating composition industrially when a vapor deposition alloy plating film is formed by evaporating a metal from an alloy bath serving as an evaporation source in a continuous vacuum vapor deposition plating method. The present invention relates to a vapor deposition alloy plating method that can be obtained.
【０００２】[0002]
【従来の技術】蒸発槽内の蒸発金属原料を真空または希
薄ガス雰囲気下で加熱蒸発させ、被処理基材の表面に蒸
着金属めっき層を施す所謂真空蒸着めっき法は、工業的
に広く実用化されている。該真空蒸着めっき法を利用し
て合金めっき層を形成する方法は、下記の２種に大別さ
れる。2. Description of the Related Art A so-called vacuum vapor deposition plating method, in which a vaporized metal raw material in an evaporation tank is heated and vaporized in a vacuum or a dilute gas atmosphere to form a vapor deposited metal plating layer on the surface of a substrate to be treated, is widely industrially applied. Has been done. The method of forming an alloy plating layer using the vacuum deposition plating method is roughly classified into the following two types.
【０００３】所望の合金めっき皮膜を構成する各蒸発
原料を個別の蒸発槽内に装入し、これらを各々に同時に
加熱蒸発させて、被処理基材表面に合金めっき層として
形成させる方法。 所望の合金めっき皮膜を構成する蒸発原料を、１つの
蒸発槽内に装入して合金浴を形成し、該合金浴から所望
の混合蒸気を発生させることにより、被処理基材表面に
合金めっき層を形成させる方法。A method in which each evaporation raw material forming a desired alloy plating film is charged into an individual evaporation tank, and these are simultaneously heated and evaporated to form an alloy plating layer on the surface of the substrate to be treated. The evaporation raw material forming the desired alloy plating film is charged into one evaporation tank to form an alloy bath, and a desired mixed vapor is generated from the alloy bath, whereby the surface of the substrate to be treated is alloy plated. Method of forming layers.
【０００４】上記の方法では、所望の合金めっき皮膜
組成となる様に、各蒸発原料の蒸発速度（単位時間当た
りの蒸発量：kg／分）を個別に調整する必要があり、各
蒸発原料の蒸気圧を考慮して各蒸発原料に投入される加
熱源のエネルギーを適正に制御する技術が必要となる。
例えば加熱源として電子線を使用する場合には、各蒸発
原料浴表面に照射する電子線の出力または浴表面での電
子線照射時間比率を調整しなければならない。この様に
各蒸発原料を個別に蒸発させる方法では、合金めっき組
成に応じて個別に複数個の蒸発槽を設け、且つ電子線等
の加熱蒸発源を複数個設ける必要があるため、工業的生
産の観点からすると設備コストが高くなる。また、１個
の加熱源を使用する場合は、各蒸発原料に対して加熱エ
ネルギーを適正に配分する必要があり、例えば加熱源と
して電子銃を用いる場合には、１つの電子銃から発生し
た電子線を、各々の蒸発原料に対して非常に短い周期
（数１０ｍｓｅｃ等）で交互に照射させるための電子線
ジャンピング技術が不可欠となり、電子線照射の操作が
複雑になる。In the above method, it is necessary to individually adjust the evaporation rate (evaporation amount per unit time: kg / min) of each evaporation raw material so that the desired alloy plating film composition can be obtained. It is necessary to have a technique for properly controlling the energy of the heating source that is put into each evaporation material in consideration of the vapor pressure.
For example, when an electron beam is used as a heating source, the output of the electron beam applied to the surface of each evaporation raw material bath or the electron beam irradiation time ratio on the bath surface must be adjusted. In this way, in the method of individually evaporating each evaporation raw material, it is necessary to provide a plurality of evaporation tanks individually according to the alloy plating composition and to provide a plurality of heating evaporation sources such as electron beams, so that the industrial production From the viewpoint of, the equipment cost becomes high. Further, when one heating source is used, it is necessary to properly distribute heating energy to each evaporation raw material. For example, when an electron gun is used as a heating source, electrons generated from one electron gun are used. An electron beam jumping technique for alternately irradiating each evaporation raw material with a very short cycle (several tens of msec, etc.) becomes indispensable, and the operation of electron beam irradiation becomes complicated.
【０００５】しかも、所望の合金めっき皮膜組成を得る
ためには、その皮膜組成に応じた蒸発原料の各々の蒸発
速度をコントロールする必要があるため、加熱エネルギ
ーのトータル出力と各蒸発原料への照射時間配分の２つ
をうまく制御しなければならず、電子線の複雑な制御技
術を余儀なくされる。また、各蒸発原料と被処理基材と
の幾何学的配置によっては、特に大面積の被処理基材に
適用する場合、合金めっき皮膜組成が被処理基材の場所
によって不均一になり易い。しかも、被処理基材が鋼帯
やフィルム等の様に連続帯状材料である場合には、帯状
基材の幅方向の合金皮膜組成を安定させるために、必然
的に各蒸発原料槽（蒸発槽）を帯状基材の進行方向に対
して平行に並べて配置せざるを得ず、それに伴なって、
得られる合金めっき皮膜組成が皮膜厚さ方向で傾斜組成
となることがある。Moreover, in order to obtain a desired alloy plating film composition, it is necessary to control the evaporation rate of each evaporation raw material according to the coating composition, so the total output of heating energy and the irradiation of each evaporation raw material are required. Two of the time allocations have to be controlled well, and complicated electron beam control technology is forced. Further, depending on the geometrical arrangement of each evaporation material and the substrate to be treated, especially when applied to a substrate to be treated having a large area, the alloy plating film composition tends to be nonuniform depending on the location of the substrate to be treated. Moreover, when the substrate to be treated is a continuous strip material such as a steel strip or a film, in order to stabilize the alloy film composition in the width direction of the strip substrate, it is inevitable that each evaporation raw material tank (evaporation tank) ) Must be arranged in parallel to the traveling direction of the strip-shaped substrate, and accordingly,
The resulting alloy plating film composition may have a gradient composition in the film thickness direction.
【０００６】めっき皮膜の厚さ方向で皮膜組成が連続的
もしくは段階的に変化する所謂「傾斜機能材料」が最近
注目されているが、一般的には、めっき皮膜の厚さ方向
で皮膜組成が変化しないことを要求される場合がほとん
どであり、上述した様に、膜厚方向で傾斜組成なる蒸着
合金めっき皮膜が得られることは好ましくない。上記の
様な理由から、上記の個別蒸発法を利用して大面積な
いし連続帯状基材に蒸着合金めっき皮膜を形成する方法
には、工業的に多くの問題および技術的課題が指摘され
る。[0006] Recently, so-called "functionally graded materials", in which the coating composition changes continuously or stepwise in the thickness direction of the plating film, have recently attracted attention. In most cases, it is required not to change, and as described above, it is not preferable to obtain a vapor deposition alloy plating film having a gradient composition in the film thickness direction. For the reasons described above, many problems and technical problems are pointed out industrially in the method of forming a vapor deposition alloy plating film on a large area or continuous strip-shaped substrate using the above-mentioned individual evaporation method.
【０００７】一方、前記に示した様に合金浴から各々
の蒸発原料を混合状態で発生させ、被処理基材表面に所
望の蒸着合金めっき皮膜を形成させる方法では、蒸発槽
を１個用意すればよく且つ加熱源も１つで済むため、設
備コスト的に有利である。しかも加熱源として電子線等
を用いる場合でも、前記の方法で説明した様な電子線
等の各蒸発槽間での滞在時間比率の制御技術が全く不要
であり、成膜操作が非常に簡便となる。この様に、合金
浴から所望組成の混合蒸気を発生させて被処理基材表面
に蒸着合金めっき皮膜を形成する方法は、種々の利点を
有している。しかしながら本方法でも、得られる合金め
っき皮膜組成を長時間安定に維持するための技術が必要
となる。On the other hand, as described above, in the method in which the respective evaporation raw materials are generated in a mixed state from the alloy bath and the desired vapor deposition alloy plating film is formed on the surface of the substrate to be treated, one evaporation tank must be prepared. Since it is sufficient and only one heating source is required, it is advantageous in terms of equipment cost. Moreover, even when an electron beam or the like is used as a heating source, the technique for controlling the staying time ratio of the electron beam or the like between the evaporation tanks as described in the above method is completely unnecessary, and the film forming operation is very simple. Become. As described above, the method of forming the vapor deposition alloy plating film on the surface of the substrate to be treated by generating the mixed vapor of the desired composition from the alloy bath has various advantages. However, this method also requires a technique for maintaining the obtained alloy plating film composition stably for a long time.
【０００８】例えば、１つの蒸発槽内に金属Ａと金属Ｂ
からなるＡ−Ｂ合金浴を形成し、該合金浴を加熱して浴
表面から金属Ａと金属Ｂの混合蒸気を発生させて、蒸着
Ａ−Ｂ系合金めっき層を形成させる場合について考える
と、目的とする均一な合金めっき皮膜組成（即ちＡとＢ
の含有比率）に管理するには、Ａ−Ｂ合金浴組成を安定
に維持しなければならない。ところが金属Ａ、Ｂの同一
温度における蒸気圧には差があり、また該Ａ−Ｂ合金浴
組成と該合金浴表面から蒸発するＡ−Ｂ混合蒸気の組成
は、必ずしも一致するわけではないので、合金浴組成と
蒸気組成（即ち合金めっき組成）は異なる組成となる。
従って、得られる蒸着合金めっき組成を所定の管理範囲
内で安定に長時間維持するには、蒸発槽内の合金浴組成
を常に一定の管理範囲内に制御し続ける必要がある。For example, metal A and metal B are placed in one evaporation tank.
Considering the case of forming an AB alloy bath consisting of, and heating the alloy bath to generate a mixed vapor of metal A and metal B from the bath surface to form a vapor-deposited AB alloy plating layer, Desired uniform alloy coating composition (ie A and B)
In order to control the content ratio), the AB alloy bath composition must be maintained stable. However, there is a difference in vapor pressures of the metals A and B at the same temperature, and the composition of the AB alloy bath and the composition of the AB mixed vapor evaporated from the surface of the alloy bath do not necessarily match. The alloy bath composition and the vapor composition (that is, the alloy plating composition) are different compositions.
Therefore, in order to stably maintain the obtained vapor deposition alloy plating composition within a predetermined control range for a long time, it is necessary to always keep the alloy bath composition in the evaporation tank within a constant control range.
【０００９】このとき、ある任意のＡ−Ｂ合金浴組成に
制御したときに発生するＡ−Ｂ混合蒸気組成（即ちＡ−
Ｂ合金めっき組成）は、合金浴の表面温度が一定であれ
ば一義的に決まってくるもので、該Ａ−Ｂ合金浴の浴組
成をある管理範囲に制御すれば、得られる蒸着Ａ−Ｂ合
金めっき組成もある管理範囲内に制御することが原理的
には可能であり、こうした着想のもとで合金めっき組成
を安定に維持するための方法が、たとえば特開昭６０−
１９７８７２や特開平３−１３５６２等に開示されてい
る。At this time, the composition of the AB mixed vapor (that is, A-
B alloy plating composition) is uniquely determined if the surface temperature of the alloy bath is constant, and vapor deposition AB obtained by controlling the bath composition of the AB alloy bath within a certain control range. It is possible in principle to control the alloy plating composition within a certain control range, and a method for keeping the alloy plating composition stable under such an idea is disclosed in, for example, JP-A-60-
It is disclosed in 197872 and JP-A-3-13562.
【００１０】[0010]
【発明が解決しようとする課題】上記の様に、真空蒸着
法を利用して各種蒸着合金めっき皮膜を各種被処理基材
表面に付与する方法は、従来の電気めっき法や溶融めっ
き法に比較して、めっき可能な原料の種類に制約が少な
く、また電子線等の高エネルギー加熱源を用いれば成膜
速度も非常に高くすることができるので、帯状基材への
連続蒸着めっきを考えた場合、生産性を含めて工業的に
も非常に有利な方法といえる。As described above, the method of applying various vapor-deposited alloy plating films to the surface of various substrates to be treated by utilizing the vacuum vapor deposition method is compared with the conventional electroplating method and hot dipping method. Since there are few restrictions on the types of raw materials that can be plated, and the film formation rate can be made very high by using a high energy heating source such as an electron beam, we considered continuous vapor deposition plating on a strip substrate. In this case, it can be said that it is an industrially very advantageous method including productivity.
【００１１】しかしながら、高い生産性を得るべく電子
線等の照射出力を増大させ、合金浴表面温度を上昇させ
て該合金浴表面からの混合蒸気の蒸発速度を増加させる
と、合金浴最表面の組成がバルクの真の浴組成から外れ
たり、経時的に変動し易くなるため、得られる蒸着合金
めっき組成が所定の管理範囲から外れてしまう場合があ
る。蒸着合金めっき組成が管理範囲から外れると、製品
規格を逸することになるので、生産性を向上すべく蒸発
速度を上昇させたことが却って製品歩留まりの低下を招
き、生産性の減少につながる。However, if the irradiation output of an electron beam or the like is increased and the surface temperature of the alloy bath is increased to increase the evaporation rate of the mixed vapor from the surface of the alloy bath in order to obtain high productivity, the vaporization rate of the mixed vapor from the surface of the alloy bath is increased. The composition may deviate from the true bulk bath composition or may easily change over time, so that the vapor deposition alloy plating composition obtained may deviate from the predetermined control range. If the vapor deposition alloy plating composition deviates from the control range, the product standard will be deviated. Therefore, increasing the evaporation rate in order to improve the productivity will rather lower the product yield, leading to a decrease in productivity.
【００１２】また、合金浴組成を一定に維持するには、
複数の蒸発原料を合金浴へ連続的または間欠的に補給し
なければならないが、このとき、補給する蒸発原料の蒸
発槽内への補給位置や補給間隔等の補給条件によって
は、合金浴の表面組成が経時的に変動することもあり、
合金浴全体で均一な浴組成を常に維持することが困難な
ことも多い。殊に、蒸発槽内における合金浴の総量（総
容積）が蒸発量に対して相対的に少ない場合は、該合金
浴へ蒸発原料を連続的に補給したとしても、浴組成は変
動し易くなる。Further, in order to keep the alloy bath composition constant,
Multiple evaporation raw materials must be continuously or intermittently replenished to the alloy bath.At this time, depending on the replenishment conditions such as the replenishment position and replenishment interval of the evaporation raw materials to be replenished, the surface of the alloy bath may be replenished. The composition may change over time,
It is often difficult to maintain a uniform bath composition throughout the alloy bath. Particularly, when the total amount (total volume) of the alloy bath in the evaporation tank is relatively small with respect to the evaporation amount, the bath composition tends to fluctuate even if the evaporation raw material is continuously supplied to the alloy bath. .
【００１３】この様な諸事情のため、得られる蒸着合金
めっき組成を長時間に亘って安定に維持することは意外
にむずかしい。本発明は上記の様な事情に着目してなさ
れたものであって、その目的は、真空蒸着めっき法を利
用して合金浴から金属Ａ，Ｂの混合蒸気を発生させて蒸
着合金めっき皮膜を形成させる方法において、得られる
合金めっき皮膜の組成を長時間に亘り安定に維持するこ
とのできる蒸着めっき法を提供しようとするものであ
る。Under these circumstances, it is surprisingly difficult to maintain the obtained vapor-deposited alloy plating composition stably for a long time. The present invention has been made by paying attention to the above circumstances, and an object thereof is to generate a mixed vapor of metals A and B from an alloy bath by using a vacuum deposition plating method to form a deposited alloy plating film. In the forming method, it is an object of the present invention to provide a vapor deposition plating method capable of maintaining the composition of the obtained alloy plating film stably for a long time.
【００１４】[0014]
【課題を解決するための手段】上記課題を解決すること
のできた本発明に係る蒸着合金めっき法の構成は、蒸気
圧の異なる金属Ａと金属Ｂからなる溶融Ａ−Ｂ合金浴か
ら金属Ａと金属Ｂの混合蒸気を発生せしめ、基材表面に
蒸着Ａ−Ｂ合金めっき層を形成する蒸着合金めっき法に
おいて、 Ａ−Ｂ合金浴組成を［Ａ−Ｘ％Ｂ］（％は重量％を意味
する、以下同じ） Ａ−Ｂ合金めっき皮膜組成を［Ａ−Ｙ％Ｂ］（但し、Ｘ
＞Ｙ） とし、且つ 蒸着槽内のＡ−Ｂ合金浴重量を［Ｎ（ｋｇ）］ Ａ−Ｂ混合蒸気の蒸発速度を［Ｍ（ｋｇ／ｍｉｎ］ としたとき、下記（Ｉ）式の関係を満足する条件下に、
蒸発相当量の金属Ａと金属Ｂを蒸発槽へ連続的もしくは
間欠的に供給しながら蒸着めっきを行なうところに要旨
を有するものである。 （Ｘ×Ｎ）×１０-3≧（Ｙ×Ｍ）……（Ｉ）The structure of the vapor deposition alloy plating method according to the present invention, which has been able to solve the above-mentioned problems, is such that a molten A-B alloy bath composed of a metal A and a metal B having different vapor pressures changes from a molten AB alloy bath to a metal A. In a vapor deposition alloy plating method in which a vapor mixture of metal B is generated to form a vapor deposition AB alloy plating layer on the surface of a base material, an AB alloy bath composition is [AX% B] (% means% by weight). The same applies to the following) A-B alloy plating film composition [A-Y% B] (however, X
> Y), and the weight of the AB alloy bath in the vapor deposition tank is [N (kg)], and the evaporation rate of the AB mixed vapor is [M (kg / min]), the relation of the following formula (I) is satisfied. Under the condition that satisfies
The point is that vapor deposition plating is carried out while continuously or intermittently supplying metal A and metal B in amounts equivalent to evaporation to the evaporation tank. (X × N) × 10 −3 ≧ (Y × M) (I)
【００１５】尚、本発明において蒸着合金めっきを構成
する金属Ａ，Ｂの種類は、蒸気圧が異なるものの組み合
わせであれは一切制限されないが、実際面で利用価値の
最も高いのは、金属ＡがＡｌまたはＺｎであり、金属Ｂ
がＣｒ，Ｔｉ，Ｓｉ，Ｍｎ，Ｎｉ，Ｍｇ，Ｃｕ，Ｙより
なる群から選択されるものである。In the present invention, the types of the metals A and B that compose the vapor deposition alloy plating are not limited at all, even if they are combinations having different vapor pressures, but in practice, the most useful value is the metal A. Al or Zn, metal B
Is selected from the group consisting of Cr, Ti, Si, Mn, Ni, Mg, Cu, Y.
【００１６】[0016]
【作用】以下、実施例図面を参照しつつ本発明の構成お
よび作用効果を詳細に説明する。尚、本発明が適用され
る被めっき基材としては、各種金属材料をはじめとし、
各種フィルム、紙、プラスチック、セラミックス系材料
等の非金属材料等からなる板状、棒状、管状もしくはそ
の他各種の成形加工品の如く様々の素材および形状のも
のが非限定的に例示され、また加熱蒸発源としては、一
般の抵抗加熱、高周波加熱をはじめ、電子線加熱、レー
ザビーム加熱、アーク加熱等を採用することができ、更
に蒸着法とは、通常の真空蒸着法の他、各種イオンプレ
ーティングを含む広義の意味での蒸着法を包含するもの
であるが、以下の説明では最も代表的なものとして冷延
鋼帯の表面に電子線加熱法を利用して連続的に真空蒸着
めっきを施す場合を主体にして説明を進める。The structure and operation of the present invention will be described in detail below with reference to the accompanying drawings. The substrate to be plated to which the present invention is applied, including various metal materials,
Various materials and shapes such as plate-like, rod-like, tubular or other processed products made of non-metal materials such as various films, papers, plastics and ceramics materials are exemplified without limitation, and heating As the evaporation source, general resistance heating, high-frequency heating, electron beam heating, laser beam heating, arc heating, etc. can be adopted. It includes vapor deposition in a broad sense including coating, but in the following description, the most representative one is continuous vacuum vapor deposition plating on the surface of a cold rolled steel strip using an electron beam heating method. The explanation will proceed with the application mainly.
【００１７】図１は、本発明で用いられる連続真空蒸着
めっき設備を例示する概念図であり、鋼帯表面に連続的
に蒸着合金めっき層を形成する場合を示している。図１
においてまず被処理基材である鋼帯１は、真空蒸着室２
へ導入される。鋼帯１は、図示されていない各種方法に
よって予め表面の清浄化処理および活性化処理が行なわ
れ、必要に応じて蒸着めっきに適した温度に予熱された
状態で、真空シール室を経由して蒸着室２内へ導入され
る。蒸着室２内には、走行する鋼帯１の下側に１つの蒸
発槽３が配置されており、該蒸発槽３内には所望の合金
浴４が形成されている。そして蒸着室２の壁面適所には
合金浴４の加熱蒸発源として電子銃５が設けられてお
り、該電子銃５から発生した電子線６は、蒸発槽３周辺
の空間に形成された磁場（図示されていない）によって
偏向され、蒸発槽３内の合金浴４表面に向かって照射さ
れる。そして、電子線照射により加熱された該合金浴４
表面から各金属蒸気が混合状態で発生し、連続的に走行
する被処理鋼帯の表面に、所望の蒸着合金めっき層が形
成される。FIG. 1 is a conceptual diagram illustrating a continuous vacuum vapor deposition plating equipment used in the present invention, showing a case where vapor deposition alloy plating layers are continuously formed on the surface of a steel strip. Figure 1
First, the steel strip 1 as the substrate to be processed is placed in the vacuum deposition chamber 2
Be introduced to. The steel strip 1 is preliminarily subjected to a surface cleaning treatment and an activation treatment by various methods not shown in the drawings, and is preheated to a temperature suitable for vapor deposition plating, if necessary, via a vacuum seal chamber. It is introduced into the vapor deposition chamber 2. In the vapor deposition chamber 2, one evaporation tank 3 is arranged below the traveling steel strip 1, and a desired alloy bath 4 is formed in the evaporation tank 3. An electron gun 5 as a heating evaporation source of the alloy bath 4 is provided at a proper place on the wall surface of the vapor deposition chamber 2, and an electron beam 6 generated from the electron gun 5 is generated by a magnetic field (a magnetic field) formed in a space around the evaporation tank 3. It is deflected by (not shown) and is irradiated toward the surface of the alloy bath 4 in the evaporation tank 3. Then, the alloy bath 4 heated by electron beam irradiation
The respective metal vapors are generated in a mixed state from the surface, and a desired vapor-deposited alloy plating layer is formed on the surface of the steel strip to be processed which continuously runs.
【００１８】蒸発槽３内の合金浴４へは、ワイヤー状の
蒸発原料７ａ，７ｂもしくは粒状、塊状、小片状等の蒸
発原料８が連続的に補給される。これら蒸発原料の補給
手段は、合金浴や蒸発原料の種類によって適宜使い分け
る。下面側に蒸着合金めっき層が施された被処理鋼帯１
は、必要により他の面にも蒸着めっき処理が行われ、真
空シール装置（図示されていない）を経由して最終的に
大気中に取り出される。The alloy bath 4 in the evaporation tank 3 is continuously replenished with the evaporation materials 7a, 7b in the form of wire or the evaporation material 8 in the form of particles, lumps, flakes, or the like. The means for replenishing these evaporation raw materials is appropriately selected depending on the type of alloy bath and evaporation raw material. Steel strip to be treated 1 with a vapor-deposited alloy plating layer on the lower surface
If necessary, the other surface is also subjected to vapor deposition plating, and is finally taken out into the atmosphere via a vacuum sealing device (not shown).
【００１９】上記のめっき設備を使用し、合金浴４とし
てＡｌ−Ｃｒ合金浴、Ａｌ−Ｔｉ合金浴またはＡｌ−Ｓ
ｉ合金浴の３種類のＡｌ系合金浴を用いて、各々の蒸着
Ａｌ系合金めっき鋼板を連続的に作製し、その際の合金
めっき組成やめっき付着量の安定性について種々調査を
行なった。その結果、まずＡｌ系合金の蒸発量は、合金
浴組成が大きく変動しない限り電子線の照射出力を高め
るにつれて増加し、めっき付着量は電子線出力と鋼帯の
ラインスピードを調整することによって容易に制御でき
ることが確認された。Using the above plating equipment, the alloy bath 4 is an Al-Cr alloy bath, an Al-Ti alloy bath or an Al-S alloy bath.
Using three kinds of Al alloy baths, i alloy baths, each vapor-deposited Al alloy plated steel sheet was continuously prepared, and various investigations were performed on the stability of the alloy plating composition and the amount of plating deposit at that time. As a result, first, the evaporation amount of the Al-based alloy increases as the irradiation output of the electron beam is increased unless the composition of the alloy bath changes significantly, and the plating adhesion amount can be easily adjusted by adjusting the electron beam output and the line speed of the steel strip. It was confirmed that it can be controlled.
【００２０】一方、得られる蒸着Ａｌ系合金めっき皮膜
の組成に関しては、次の様な傾向が得られた。 原料補給を停止した状態で連続めっき処理を継続する
と、得られるめっき層中の合金元素（Ｃｒ、Ｔｉおよび
Ｓｉ）の含有量が経時的に増加する。この様なめっき層
中の合金元素の増加傾向は、蒸発槽内の合金浴総量（重
量）が元々小さいものほど、短時間で顕著に表われてく
る。 混合蒸気の蒸発速度（kg／分）と当該混合蒸気組成に
相当する蒸発原料の補給を連続的に行ないながらめっき
処理を継続すると、合金めっき組成は長時間ほぼ安定し
た推移を示す。また合金めっき組成の経時的変動は、合
金浴総量（重量）が大きいほど少ない。 蒸着めっき付着量の増大および生産性の向上を目的と
して、合金浴表面に照射する電子線出力を増加させ、混
合蒸気の蒸発速度を増大させた場合、各蒸発原料を合金
浴中に連続補給していても、蒸発速度が大きくなるほ
ど、得られる蒸着合金めっき層のめっき組成は変動し易
くなる。On the other hand, regarding the composition of the vapor-deposited Al-based alloy plating film obtained, the following tendencies were obtained. When the continuous plating treatment is continued with the supply of raw materials stopped, the content of alloy elements (Cr, Ti and Si) in the obtained plated layer increases with time. Such an increase tendency of the alloy elements in the plating layer becomes more remarkable in a shorter time as the total amount (weight) of the alloy bath in the evaporation tank is originally small. When the plating treatment is continued while continuously replenishing the evaporation raw material corresponding to the evaporation rate (kg / min) of the mixed vapor and the mixed vapor composition, the alloy plating composition shows a substantially stable transition for a long time. Further, the change with time of the alloy plating composition decreases as the total amount (weight) of the alloy bath increases. In order to increase the deposition amount of vapor-deposited plating and improve productivity, when the electron beam output to the alloy bath surface is increased and the evaporation rate of the mixed vapor is increased, each evaporation raw material is continuously replenished into the alloy bath. However, the higher the evaporation rate, the more easily the plating composition of the vapor deposition alloy plating layer obtained changes.
【００２１】以上の様な実験結果から、本発明者らは次
のことを確認および考察した。 (a) Ｃｒ、Ｔｉ、Ｓｉ等の金属は、Ａｌよりも同一温度
での蒸気圧が小さいため、蒸発速度は当然Ａｌよりも小
さくなる。そのため、合金浴組成と混合蒸気組成は一致
せず、蒸気中のＡｌ含有量は合金浴中のＡｌ含有量より
も大きくなる。そのため、Ａｌ合金浴内へＡｌおよび合
金元素を補給しない場合には、めっき処理時間が経過す
るにつれて次第に合金浴中の合金元素（Ｃｒ、Ｔｉ、Ｓ
ｉ等）の含有量が増大し、結果として得られる蒸着Ａｌ
系合金めっき層中の合金元素の含有量も経時的に増加し
てくる。このとき、合金浴の総重量（kg）が元々少ない
場合は、蒸発原料の補給なしに蒸発を続けたときの、混
合蒸気の蒸発に伴なう合金浴組成の変化も比較的短時間
で顕著に表われ、結果として合金めっき組成の変化も著
しくなるものと考えられる。From the above experimental results, the present inventors confirmed and considered the following. (a) Metals such as Cr, Ti, and Si have a smaller vapor pressure at the same temperature than Al, so the evaporation rate is naturally smaller than that of Al. Therefore, the composition of the alloy bath does not match the composition of the mixed vapor, and the Al content in the vapor becomes larger than the Al content in the alloy bath. Therefore, when Al and alloy elements are not replenished into the Al alloy bath, the alloy elements (Cr, Ti, S) in the alloy bath gradually increase as the plating treatment time elapses.
i), etc., and the resulting evaporated Al
The content of alloying elements in the system alloy plating layer also increases with time. At this time, if the total weight (kg) of the alloy bath is originally small, the change in the alloy bath composition due to the evaporation of the mixed vapor is remarkable in a relatively short time when the evaporation is continued without supplementing the evaporation raw materials. It is considered that the alloy plating composition changes significantly as a result.
【００２２】(b) 合金浴から発生する混合蒸気の組成お
よび蒸発速度（kg／分）に対応する様に、Ａｌと合金元
素（Ｃｒ、Ｔｉ、Ｓｉ等）の双方を連続的に浴中へ補給
すれば、浴表面温度が大きく変動しない限り、発生する
混合蒸気の蒸発速度と原料の補給速度がバランスし、結
果として得られる蒸着Ａｌ合金めっき皮膜の組成は、原
理的に一定値を示すはずである。(B) Both Al and alloying elements (Cr, Ti, Si, etc.) are continuously introduced into the bath so as to correspond to the composition and evaporation rate (kg / min) of the mixed vapor generated from the alloy bath. If replenished, unless the bath surface temperature fluctuates significantly, the evaporation rate of the generated mixed vapor and the replenishment rate of the raw materials are balanced, and the composition of the resulting vapor-deposited Al alloy plating film should in principle show a constant value. Is.
【００２３】ところが、前述の如くたとえ電子線照射出
力を一定に保ったとしても、混合蒸気の蒸発速度（めっ
き付着量）は他の要因で微妙に増減し、それに伴なって
めっき組成もある範囲内で変動する。また、合金浴中へ
補給された原料は、補給位置でまず溶解し、そこから移
流ないし拡散によって合金浴中へ３次元的に移動すると
考えられるが、蒸発原料は、通常、合金浴表面のある一
端から補給されるので、合金浴重量が元々少ない場合に
は、原料補給と蒸発速度のバランスが微妙にずれると、
それが直ちにめっき組成の変動となって表われる。However, as described above, even if the electron beam irradiation output is kept constant, the evaporation rate of the mixed vapor (coating adhesion amount) slightly changes due to other factors, and the plating composition also falls within a certain range. Fluctuates within. Further, it is considered that the raw material replenished into the alloy bath first melts at the replenishment position and then moves three-dimensionally into the alloy bath by advection or diffusion, but the vaporized raw material is usually present on the surface of the alloy bath. Since it is replenished from one end, if the weight of the alloy bath is originally small, the balance between the replenishment of raw materials and the evaporation rate may deviate slightly,
This immediately appears as a change in the plating composition.
【００２４】特に合金浴重量が少ない場合は、被処理鋼
帯の板幅方向に対して、補給される側とそうでない側の
浴組成が傾斜組成を示すことがあり、結果として板幅方
向で蒸着Ａｌ系合金層組成に傾斜を生じることがある。
この様な板幅方向に生じるめっき組成の傾斜傾向は、蒸
発速度を高めるにつれて顕著に表われてくる。これに対
し、合金浴重量が十分大きい場合には、浴全体が一種の
緩衝機能を発揮し、原料補給速度と蒸発速度とのバラン
スに一時的なずれが生じても、得られる蒸着合金めっき
組成が急激に変動することはない。Particularly when the weight of the alloy bath is small, the bath composition on the side to be replenished and the bath composition on the side not to be inclined may have a gradient composition with respect to the plate width direction of the steel strip to be treated, and as a result, in the plate width direction The composition of the vapor-deposited Al-based alloy layer may be inclined.
Such an inclination tendency of the plating composition occurring in the plate width direction becomes more remarkable as the evaporation rate is increased. On the other hand, when the weight of the alloy bath is sufficiently large, the entire bath exerts a kind of buffer function, and even if there is a temporary deviation in the balance between the raw material replenishment rate and the evaporation rate, the vapor deposition alloy plating composition obtained Does not change rapidly.
【００２５】以上の様な知見および考察を基にして、本
発明者らは容積の異なる蒸発槽を用いて合金浴の重量を
変化させると共に、合金浴への電子線照射出力を増減さ
せ、混合蒸気の蒸発速度を変化せしめ、その際に得られ
る蒸着Ａｌ合金めっき皮膜組成の経時的変動の程度を調
査した。Based on the above knowledge and consideration, the inventors of the present invention changed the weight of the alloy bath by using the evaporation tanks having different volumes, and increased or decreased the electron beam irradiation output to the alloy bath to perform mixing. The evaporation rate of the vapor was changed, and the degree of temporal variation of the vapor deposited Al alloy plating film composition obtained at that time was investigated.
【００２６】その結果、合金浴重量が大きいほど、また
は／および蒸発速度が小さいほど、得られる蒸着合金め
っき組成の変動幅が小さくなることが判明した。本発明
者らはこうした知見を基に更に追求研究の結果、蒸着合
金めっき層の組成変動を小さく抑えると共に、長時間に
亘って安定した合金めっき組成を維持するには、下記の
条件設定が極めて有効であることを見い出し、本発明に
至ったものである。As a result, it was found that the larger the alloy bath weight and / or the smaller the evaporation rate, the smaller the fluctuation range of the vapor deposition alloy plating composition obtained. As a result of further pursuit research based on these findings, the present inventors have found that the following condition setting is extremely necessary in order to keep the composition variation of the vapor deposition alloy plating layer small and maintain a stable alloy plating composition for a long time. The present invention has been found out that it is effective.
【００２７】即ち、金属Ａと金属ＢなるＡ−Ｂ合金浴か
ら蒸着Ａ−Ｂ合金めっき皮膜を形成するに当たり、合金
浴組成をＡ−Ｘ％Ｂ、めっき皮膜組成：Ａ−Ｙ％Ｂ（但
し、Ｘ＞Ｙ）とし、更に合金浴重量をＮ（kg）、混合蒸
気の蒸発速度をＭ（kg／分）とした場合、 （Ｘ×Ｎ）×１０-3≧（Ｙ×Ｍ） を満たす様に条件設定を行なえば、めっき皮膜組成を長
時間に亘って安定に接続することができ、均一な組成の
めっき製品を得ることができる。That is, in forming a vapor-deposited AB alloy plating film from an A-B alloy bath composed of metal A and metal B, the alloy bath composition is A-X% B, the plating film composition is A-Y% B (however, , X> Y), the alloy bath weight is N (kg), and the evaporation rate of the mixed vapor is M (kg / min), (X × N) × 10 −3 ≧ (Y × M) is satisfied. By setting the conditions in this way, the plating film composition can be stably connected for a long time, and a plated product having a uniform composition can be obtained.
【００２８】ここで、「Ｘ＞Ｙの要件」は、めっき層中
の金属Ｂの含有量が合金浴中の含有量よりも小さいこと
を意味し、換言すると金属Ａよりも金属Ｂの方が、同一
温度における蒸気圧（蒸発速度）が小さいことを意味す
る。ちなみに、「Ｘ＝Ｙ」では、合金浴組成と同一組成
のめっき皮膜が得られるので、本発明を適用するまでも
なく、均一な蒸着合金めっき皮膜を得ることができる。
また、上記関係式中に示した（Ｘ×Ｎ）は、合金浴組成
と合金浴重量の積であり、即ちＡ−Ｂ合金浴中に占める
金属Ｂの重量を意味し、同様に（Ｙ×Ｎ）は、混合蒸気
組成と蒸発速度の積、即ち単位時間当たりに発生する混
合蒸気中に含まれる金属Ｂの含有量を意味する。Here, the "requirement of X>Y" means that the content of the metal B in the plating layer is smaller than the content in the alloy bath, in other words, the metal B is more preferable than the metal A. , Means that the vapor pressure (evaporation rate) at the same temperature is small. By the way, with "X = Y", a plating film having the same composition as the alloy bath composition can be obtained, so that a uniform vapor-deposited alloy plating film can be obtained without applying the present invention.
Further, (X × N) shown in the above relational expression is the product of the alloy bath composition and the weight of the alloy bath, that is, the weight of the metal B in the AB alloy bath, and similarly (Y × N). N) means the product of the mixed vapor composition and the evaporation rate, that is, the content of the metal B contained in the mixed vapor generated per unit time.
【００２９】従って上記関係式では、合金浴中の金属Ｂ
の総重量と混合蒸気中の金属Ｂの含有量の関係を規定し
たものであり、両者が上記関係式を満たす条件で蒸着め
っき処理を行なうことが、本発明の要旨であり、選択さ
れた任意の金属Ａと金属Ｂよりなる蒸着合金めっきを行
なうに際し、あるＡ−Ｂ合金浴組成（Ａ−Ｘ％Ｂ）に対
して、めっき組成（Ａ−Ｙ％Ｂ）はある範囲内に決まる
ので、上記関係式を満たす様に合金浴重量：（Ｎ）と蒸
発速度（Ｍ）を適宜設定すれば、安定しためっき組成が
得られることになる。Therefore, in the above relational expression, the metal B in the alloy bath is
Is to define the relationship between the total weight of the above and the content of the metal B in the mixed vapor, and it is the gist of the present invention to carry out vapor deposition plating under the condition that both satisfy the above relational expression. When performing the vapor deposition alloy plating consisting of the metal A and the metal B, the plating composition (A-Y% B) is determined within a certain range with respect to a certain AB alloy bath composition (A-X% B). If the alloy bath weight: (N) and the evaporation rate (M) are appropriately set so as to satisfy the above relational expression, a stable plating composition can be obtained.
【００３０】そして、上記関係式から外れる蒸発条件で
蒸着Ａ−Ｂ合金めっきを行なった場合、即ち合金浴重量
が非常に小さい場合や、用いた合金浴重量に対して蒸発
速度を非常に大きくした場合には、合金浴表面の組成が
不安定になり易く、結果として蒸着Ａ−Ｂ合金めっき皮
膜の組成の変動が大きくなり、場合によってはこれがめ
っき付着量の変動にまで影響を及ぼして、均質な蒸着め
っき製品が得られなくなる。Then, when the vapor deposition AB alloy plating is performed under the evaporation condition which deviates from the above relational expression, that is, when the weight of the alloy bath is very small, or the evaporation rate is made very large with respect to the weight of the alloy bath used. In this case, the composition of the surface of the alloy bath is likely to be unstable, resulting in a large variation in the composition of the vapor-deposited AB alloy plating film. A vapor-deposited plated product cannot be obtained.
【００３１】尚、本発明において合金めっきを構成する
金属Ａ，Ｂは、蒸気圧の異なるものであればその種類の
如何は問わないが、本発明の特徴が実際面でより効果的
に発揮されるのは、ＡｌまたはＺｎを一方の金属とし、
他の金属をＣｒ，Ｔｉ，Ｓｉ，Ｍｎ，Ｎｉ，Ｍｇ，Ｃ
ｕ，Ｙ等とする合金めっきである。In the present invention, the metals A and B constituting the alloy plating may be of any type as long as they have different vapor pressures, but the characteristics of the present invention are more effectively exhibited in practice. One of the metals is Al or Zn,
Other metals such as Cr, Ti, Si, Mn, Ni, Mg, C
It is an alloy plating such as u and Y.
【００３２】[0032]
【実施例】次に、実施例を挙げて本発明の構成および作
用効果をより具体的に説明するが、本発明はもとより下
記実施例によって制限を受けるものではなく、前後記の
趣旨に適合し得る範囲で適当に変更を加えて実施するこ
とも可能であり、それらはいずれも本発明の技術的範囲
に含まれる。EXAMPLES Next, the constitution and effects of the present invention will be described more specifically by way of examples, but the present invention is not limited by the following examples, and is compatible with the spirit of the preceding and following paragraphs. It is also possible to carry out appropriate modifications within the range to be obtained, and all of them are included in the technical scope of the present invention.
【００３３】実施例１ 冷延鋼板を被処理基材として使用し、下記の条件で蒸着
Ａｌ−Ｃｒ合金めっきを行なった。 （蒸着めっき条件） 被処理材：冷延鋼帯（低炭素Ｔｉキルド鋼） 被処理鋼帯の前処理：アルカリ電解脱脂、水洗、乾燥後
に、Ｈ2 −Ｎ2 混合ガス雰囲気下のガス還元炉へ導入
し、鋼帯表面の還元による清浄化前処理を行ない、次い
で非酸化性雰囲気下で冷却した後、非酸化性希薄雰囲気
の真空シール装置を経由して、所定真空度に保持された
真空蒸着室へ導入 蒸着室導入時の被処理鋼帯の予熱温度：２５０℃ 蒸発原料浴：Ａｌ−Ｃｒ合金浴（図１の４に相当） 蒸発槽材質：高純度電融アルミナ（純度９８％以上）製
蒸発槽（図１の３に相当） 蒸発原料の合金浴への補給： Ａｌ：純Ａｌワイヤー（純度９９．８５％以上、直径
９．４mm）をワイヤー供給装置にて連続補給 Ｃｒ：純Ｃｒブリケット（純度９９．５％以上、１０mm
φ）をブリケットフィーダにて間欠補給 蒸発原料の加熱蒸発源：ピアス型電子銃（最大出力３０
０ｋＷ） 蒸着室真空度：２×１０-2Ｐａ以下Example 1 A cold-rolled steel sheet was used as a substrate to be treated, and vapor deposition Al—Cr alloy plating was performed under the following conditions. (Deposition plating conditions) workpiece: cold-rolled steel strip (low carbon Ti killed steel) pretreatment of the processed steel strip: alkaline electrolytic degreasing, washing with water, after drying, H 2 -N 2 gas reducing furnace under a mixed gas atmosphere After pre-cleaning by reducing the surface of the steel strip, and then cooling in a non-oxidizing atmosphere, a vacuum kept at a predetermined vacuum degree is passed through a vacuum sealing device in a non-oxidizing dilute atmosphere. Introduction into vapor deposition chamber Preheating temperature of steel strip to be treated when vapor deposition chamber is introduced: 250 ° C Evaporation raw material bath: Al-Cr alloy bath (corresponding to 4 in Fig. 1) Evaporation tank material: High-purity fused alumina (purity 98% or more) ) Evaporation tank (corresponding to 3 in Fig. 1) Replenishment of evaporation raw material to alloy bath: Al: Pure Al wire (purity 99.85% or more, diameter 9.4 mm) is continuously replenished with a wire feeder Cr: Pure Cr briquette (purity 99.5% or more, 10 mm
φ) intermittently replenished with briquette feeder Heating evaporation source of evaporation material: Pierce type electron gun (maximum output 30
Degree of vacuum in the deposition chamber: 2 × 10 -2 Pa or less
【００３４】結果は表１に示す通りであり、本発明で規
定する関係式の要件を満たす実施例（No. １〜５，７〜
１０）では、得られる蒸着Ａｌ−Ｃｒ合金めっきの皮膜
組成が長時間安定しており、均質で安定な皮膜組成のめ
っき製品が得られているのに対し、本発明で規定する関
係式を外れる比較例（No. ６，１１）では、めっき皮膜
組成の変動が大きく、安定した皮膜組成のめっき製品が
得られていない。The results are shown in Table 1, and the results (Examples Nos. 1-5 and 7-
In 10), the film composition of the vapor-deposited Al-Cr alloy plating obtained is stable for a long time, and a plated product having a homogeneous and stable film composition is obtained, whereas the relational expression defined by the present invention is deviated. In the comparative example (No. 6, 11), the plating film composition varies greatly, and a plated product having a stable film composition is not obtained.
【００３５】[0035]
【表１】 [Table 1]
【００３６】実施例２ 冷延鋼板を被処理基材として使用し、下記の条件で蒸着
Ｚｎ−Ｍｇ合金めっきを行なった。 （蒸着めっき条件） 被処理材：冷延鋼帯（低炭素Ｔｉキルド鋼） 被処理鋼帯の前処理：アルカリ電解脱脂、水洗、乾燥後
に、Ｈ2 −Ｎ2 混合ガス雰囲気下のガス還元炉へ導入
し、鋼帯表面の還元による清浄化前処理を行ない、次い
で非酸化性雰囲気下で冷却した後、非酸化性希薄雰囲気
に保った真空シール装置を経由して、所定真空度に保持
された真空蒸着室へ導入 蒸着室導入時の被処理鋼帯の予熱温度：２００℃ 蒸発原料浴：Ｚｎ−Ｍｇ合金浴（図１の４に相当） 蒸発槽材質：ＣＩＰ成形型黒鉛製蒸発槽（図１の３に相
当） 蒸発原料の合金浴への補給： Ｚｎ：純Ｚｎワイヤー（純度９９．８％以上、直径８m
m）をワイヤー供給装置にて連続補給 Ｍｇ：純Ｍｇ粒（純度９９．５％以上、１０mmφ）をブ
リケットフィーダにて間欠補給 蒸発原料の加熱蒸発源：高周波誘導加熱方式（最大出力
１００ｋＷ） 蒸着室真空度：５×１０-2〜１×１０-1Ｐａ（不活性ガ
スにて真空度調整）Example 2 Using a cold rolled steel sheet as a substrate to be treated, vapor deposition Zn-Mg alloy plating was performed under the following conditions. (Deposition plating conditions) workpiece: cold-rolled steel strip (low carbon Ti killed steel) pretreatment of the processed steel strip: alkaline electrolytic degreasing, washing with water, after drying, H 2 -N 2 gas reducing furnace under a mixed gas atmosphere The steel strip surface is subjected to a pre-cleaning treatment by reduction, then cooled in a non-oxidizing atmosphere, and then kept at a predetermined vacuum degree via a vacuum sealing device kept in a non-oxidizing dilute atmosphere. Pre-heating temperature of the steel strip to be treated at the time of introducing the vapor deposition chamber: 200 ° C. Evaporating raw material bath: Zn-Mg alloy bath (corresponding to 4 in FIG. 1) Evaporating tank material: CIP molded graphite vaporizing tank ( (Corresponding to 3 in Fig. 1) Replenishment of evaporation raw material to alloy bath: Zn: pure Zn wire (purity 99.8% or more, diameter 8 m)
m) continuous replenishment with wire feeder Mg: Pure Mg particles (purity 99.5% or more, 10 mmφ) intermittently replenished with briquette feeder Heating evaporation source of evaporation material: high frequency induction heating method (maximum output 100 kW) Deposition chamber Degree of vacuum: 5 × 10 -2 to 1 × 10 -1 Pa (degree of vacuum adjustment with inert gas)
【００３７】結果は表２に示す通りであり、本発明で規
定する関係式の要件を満たす実施例（No. １〜５，８，
９）では、得られる蒸着Ｚｎ−Ｍｇ合金めっきの皮膜組
成が長時間安定しており、均質で安定な皮膜組成のめっ
き製品が得られているのに対し、本発明で規定する関係
式を外れる比較例（No. ６，７，１０，１１）では、め
っき皮膜組成の変動が大きく、安定した皮膜組成のめっ
き製品が得られていない。The results are shown in Table 2, and the results are shown in Examples (Nos. 1 to 5, 8,
In 9), the film composition of the obtained vapor-deposited Zn-Mg alloy plating is stable for a long time, and a plated product having a uniform and stable film composition is obtained, whereas the relational expression defined by the present invention is not satisfied. In the comparative examples (No. 6, 7, 10, 11), the plating film composition fluctuates greatly and a plated product having a stable film composition cannot be obtained.
【００３８】[0038]
【表２】 [Table 2]
【００３９】実施例３ 冷延鋼板を被処理基材として使用し、下記の条件で蒸着
Ａｌ−Ｙ（イットリウム）合金めっきを行なった。 （蒸着めっき条件） 被処理材：冷延鋼帯（低炭素Ｔｉキルド鋼） 被処理鋼帯の前処理：アルカリ電解脱脂、水洗、乾燥後
にＨ2 −Ｎ2 混合ガス雰囲気下のガス還元炉へ導入し、
鋼帯表面の還元による清浄化前処理を行ない、次いで非
酸化性雰囲気下で冷却した後、非酸化性希薄雰囲気に保
った真空シール装置を経由して、所定真空度に保持され
た真空蒸着室へ導入 蒸着室導入時の非処理鋼帯の予熱温度：２５０℃ 蒸発原料浴：Ａｌ−Ｙ合金浴（図１の４に相当） 蒸発槽材質：高純度電融アルミナ（純度９８％以上）製
蒸発槽（図１の３に相当） 蒸発原料の合金浴への補給： Ａｌ：純Ａｌワイヤー（純度９９．８５％以上、直径
９．４mm）をワイヤー供給装置にて連続補給 Ｙ ：粒状純Ｙ（純度９９．９％以上、５〜１０mmφ）
をブリケットフィーダにて連続補給 蒸発原料の加熱蒸発源：ピアス型電子銃（最大出力３０
０ｋＷ） 蒸着室真空度：２×１０-2Ｐａ以下Example 3 Using a cold-rolled steel sheet as a substrate to be treated, vapor deposition Al-Y (yttrium) alloy plating was performed under the following conditions. (Deposition plating conditions) workpiece: cold-rolled steel strip (low carbon Ti killed steel) treated steel strip Pretreatment: alkali electrolytic degreasing, washing with water, drying after H 2 -N 2 mixed gas atmosphere to the gas reduction furnace Introduced,
A vacuum deposition chamber where the steel strip surface is pre-cleaned by reduction, then cooled in a non-oxidizing atmosphere, and then kept at a predetermined vacuum degree via a vacuum sealing device kept in a non-oxidizing dilute atmosphere. Introduced into the pre-heating temperature of the untreated steel strip at the time of introducing into the deposition chamber: 250 ° C. Evaporating raw material bath: Al-Y alloy bath (corresponding to 4 in FIG. 1) Evaporating tank material: Made of high-purity fused alumina (purity 98% or more) Evaporation tank (corresponding to 3 in Fig. 1) Replenishment of evaporation raw material to alloy bath: Al: Pure Al wire (purity 99.85% or more, diameter 9.4 mm) is continuously replenished by a wire feeder Y: Granular pure Y (Purity 99.9% or more, 5-10 mmφ)
Is continuously replenished with a briquette feeder Heating evaporation source of evaporation material: Pierce type electron gun (maximum output 30
Degree of vacuum in the deposition chamber: 2 × 10 -2 Pa or less
【００４０】結果は表３に示す通りであり本発明で規定
する関係式の要件を満たす実施例（No. １〜４，６〜
９）では、得られる蒸着Ａｌ−Ｙ合金めっきの皮膜組成
が長時間安定しており、均質で安定な皮膜組成のめっき
製品が得られているのに対し、本発明で規定する関係式
を外れる比較例（No. ５，１０）では、めっき皮膜組成
の変動が大きく、安定した皮膜組成のめっき製品が得ら
れていない。The results are as shown in Table 3 and the examples satisfying the requirements of the relational expression defined in the present invention (No. 1 to 4, 6 to
In 9), the film composition of the vapor-deposited Al-Y alloy plating obtained is stable for a long time, and a plated product having a uniform and stable film composition is obtained, whereas the relational expression defined by the present invention is deviated. In the comparative examples (Nos. 5 and 10), the plating film composition fluctuates greatly, and a plated product having a stable film composition cannot be obtained.
【００４１】[0041]
【表３】 [Table 3]
【００４２】[0042]
【発明の効果】本発明は以上のように構成されており、
合金浴および蒸着めっき層の合金組成に応じて蒸着槽の
合金浴重量と蒸発速度の関係を適正に制御することによ
ってめっき皮膜組成を長時間に亘って安定に維持するこ
とができ、均一な組成の蒸着合金めっき製品を安定に製
造し得ることになった。The present invention is configured as described above,
By properly controlling the relationship between the weight of the alloy bath in the vapor deposition tank and the evaporation rate according to the alloy composition of the alloy bath and the vapor-deposited plating layer, the plating film composition can be stably maintained for a long time, and a uniform composition can be obtained. It has become possible to stably manufacture the vapor-deposited alloy plated product of.
【図１】本発明で使用される蒸着めっき設備を例示する
概念図である。FIG. 1 is a conceptual diagram illustrating a vapor deposition plating facility used in the present invention.
１ 被処理材（鋼帯） ２ 真空蒸着室 ３ 蒸発槽 ４ 合金浴 ５ 電子銃 ６ 電子線 ７ａ，７ｂ ワイヤー状補給原料 ８ 粒状補給原料 1 processed material (steel strip) 2 vacuum deposition chamber 3 evaporation tank 4 alloy bath 5 electron gun 6 electron beam 7a, 7b wire-shaped replenishing raw material 8 granular replenishing raw material
フロントページの続き (72)発明者 荒賀 邦康 兵庫県加古川市尾上町池田字池田開拓2222 番地１ 株式会社神戸製鋼所加古川研究地 区内 (72)発明者 入江 広司 兵庫県加古川市金沢町１番地 株式会社神 戸製鋼所加古川製鉄所内Front page continuation (72) Inventor Kuniyasu Araga 2222 Ikeda, Ikeda, Onoe-machi, Kakogawa, Kakogawa, Hyogo Pref., Kakogawa Research Area, Kobe Steel Co., Ltd. (72) Koji Irie, Kanazawa, Kakogawa, Hyogo Company Kado Steel Works Kakogawa Steel Works
Claims (3)
溶融Ａ−Ｂ合金浴から金属Ａと金属Ｂの混合蒸気を発生
せしめ、基材表面に蒸着Ａ−Ｂ合金めっき層を形成する
蒸着合金めっき法において、 Ａ−Ｂ合金浴組成を［Ａ−Ｘ％Ｂ］（％は重量％を意味
する、以下同じ） Ａ−Ｂ合金めっき皮膜組成を［Ａ−Ｙ％Ｂ］（但し、Ｘ
＞Ｙ） とし、且つ 蒸着槽内のＡ−Ｂ合金浴重量を［Ｎ（ｋｇ）］ Ａ−Ｂ混合蒸気の蒸発速度を［Ｍ（ｋｇ／ｍｉｎ］ としたとき、下記（Ｉ）式の関係を満足する条件下に、
蒸発相当量の金属Ａと金属Ｂを連続もしくは間欠的に蒸
発槽へ供給しながら蒸着めっきを行なうことを特徴とす
る蒸着合金めっき法。 （Ｘ×Ｎ）×１０-3≧（Ｙ×Ｍ）……（Ｉ）1. A vapor deposition method in which a mixed vapor of metal A and metal B is generated from a molten AB alloy bath composed of metal A and metal B having different vapor pressures to form a vapor-deposited AB alloy plating layer on the surface of a base material. In the alloy plating method, the AB alloy bath composition is [AX% B] (% means% by weight; the same applies hereinafter). The AB alloy plating film composition is [AYYB] (however, X
> Y), and the weight of the AB alloy bath in the vapor deposition tank is [N (kg)], and the evaporation rate of the AB mixed vapor is [M (kg / min]), the relation of the following formula (I) is satisfied. Under the condition that satisfies
A vapor deposition alloy plating method characterized by performing vapor deposition plating while continuously or intermittently supplying metal A and metal B in amounts equivalent to evaporation to an evaporation tank. (X × N) × 10 −3 ≧ (Y × M) (I)
に記載の蒸着合金めっき法。2. The metal A is Al or Zn.
The vapor deposition alloy plating method described in.
がＣｒ，Ｔｉ，Ｓｉ，Ｍｎ，Ｎｉ，Ｍｇ，Ｃｕ，Ｙより
なる群から選択されるものである請求項２に記載の蒸着
合金めっき法。3. The metal A is Al or Zn and the metal B is
The vapor deposition alloy plating method according to claim 2, wherein is selected from the group consisting of Cr, Ti, Si, Mn, Ni, Mg, Cu and Y.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29369093A JPH07145473A (en) | 1993-11-24 | 1993-11-24 | Method for plating of vapor deposited alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29369093A JPH07145473A (en) | 1993-11-24 | 1993-11-24 | Method for plating of vapor deposited alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07145473A true JPH07145473A (en) | 1995-06-06 |
Family
ID=17797977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29369093A Withdrawn JPH07145473A (en) | 1993-11-24 | 1993-11-24 | Method for plating of vapor deposited alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07145473A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016535173A (en) * | 2013-11-05 | 2016-11-10 | タタ、スティール、ネダーランド、テクノロジー、ベスローテン、フェンノートシャップＴａｔａ Ｓｔｅｅｌ Ｎｅｄｅｒｌａｎｄ Ｔｅｃｈｎｏｌｏｇｙ Ｂｖ | Method and apparatus for controlling the composition of a liquid metal in an evaporator device |
| JP2022514266A (en) * | 2018-12-19 | 2022-02-10 | ポスコ | Plating layer control device and method in PVD plating process |
-
1993
- 1993-11-24 JP JP29369093A patent/JPH07145473A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016535173A (en) * | 2013-11-05 | 2016-11-10 | タタ、スティール、ネダーランド、テクノロジー、ベスローテン、フェンノートシャップＴａｔａ Ｓｔｅｅｌ Ｎｅｄｅｒｌａｎｄ Ｔｅｃｈｎｏｌｏｇｙ Ｂｖ | Method and apparatus for controlling the composition of a liquid metal in an evaporator device |
| JP2022514266A (en) * | 2018-12-19 | 2022-02-10 | ポスコ | Plating layer control device and method in PVD plating process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3791852A (en) | High rate deposition of carbides by activated reactive evaporation | |
| US4655893A (en) | Cubic boron nitride preparation utilizing a boron and nitrogen bearing gas | |
| US10787733B2 (en) | Device for forming coatings on surfaces of a component, band-shaped material, or tool | |
| US4505948A (en) | Method of coating ceramics and quartz crucibles with material electrically transformed into a vapor phase | |
| US4412899A (en) | Cubic boron nitride preparation utilizing nitrogen gas | |
| US9108276B2 (en) | Hardface coating systems and methods for metal alloys and other materials for wear and corrosion resistant applications | |
| KR20090122247A (en) | Method for coating a substrate and metal alloy vacuum deposition facility | |
| JPH0543782B2 (en) | ||
| RU2139948C1 (en) | Method of formation of deformed metal product from consumable electrode, its version, ingot, deformed metal product and consumable electrode | |
| JPH02125866A (en) | Device for applying alloy plating by vapor deposition | |
| JPH07145473A (en) | Method for plating of vapor deposited alloy | |
| CN1049688A (en) | Have workpiece and production method, production unit and the application of sosoloid coated layer | |
| JP7179291B2 (en) | TiCN with reduced growth defects using HiPIMS | |
| US9051642B2 (en) | Process for coating a substrate, plant for implementing the process and feeder for feeding such a plant with metal | |
| JPH0297663A (en) | Production of steel sheet plated with zn-mg by vapor deposition | |
| JPH03170661A (en) | Method for evaporating sublimable metal | |
| JPH062137A (en) | Vapor deposition plating method | |
| JPH1068071A (en) | Formation of compound thin coating film | |
| JPH06101022A (en) | Vapor-deposition plating method | |
| JPH0681130A (en) | Production of al-ti alloy vapor deposition plated metallic material | |
| JPH06116717A (en) | Vapor deposition plating method for sublimatable material | |
| JPH07166330A (en) | Cr stock for plating by vacuum deposition and plating method with al-cr alloy by vacuum deposition | |
| KR100193365B1 (en) | How to Form Titanium Nitride Film on Metal Surface | |
| JPH06122964A (en) | Production of vapor deposited al-cr-ti plating material | |
| JPH0233786B2 (en) | KAGOBUTSUMAKUNOKEISEIHOHO |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20010130 |