JPH06122964A - Production of vapor deposited al-cr-ti plating material - Google Patents

Abstract

PURPOSE:To continuously or semicontinuously and stably produce the vapor deposited Al-Cr-Ti plating material. CONSTITUTION:Cr and Ti are simultaneously heated to evaporate from a Cr-Ti alloy bath 3a and while the Cr and the Ti of the amts. meeting the respective evaporation rates of the Cr and the Ti are continuously or intermittently supplied to this Cr-Ti alloy bath, the Cr content in the Cr-Ti alloy bath is controlled to 2 to 85% in the method of continuously forming the Al-Cr-Ti plating by heating Al, Cr and Ti to evaporate with an electron beam 9 and depositing the metal vapor by evaporation on a traveling material 1 to be treated. The Al and the Cr are otherwise simultaneously heated to evaporate from the Al-Cr alloy bath 2a and while the Al and Cr of the amts. meeting the respective evaporation rates of the Al and the Cr are continuously or intermittently supplied to this Al-Cr alloy bath, the Cr content in the Al-Cr alloy bath is controlled to 5 to 70% in the process for production of the vapor deposited Al-Cr-Ti plating.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、建築材料、家電製品、
電子機器材料、自動車部材等の広範囲な分野において利
用することのできる蒸着Ａｌ−Ｃｒ−Ｔｉ系めっき材を
安定して連続もしくは半連続的に製造する方法に関する
ものである。The present invention relates to a building material, a home electric appliance,
The present invention relates to a method for stably and continuously or semi-continuously producing a vapor-deposited Al-Cr-Ti-based plated material which can be used in a wide range of fields such as electronic device materials and automobile members.

【０００２】尚本発明の製造方法は、加熱源として電子
ビームを利用する全ての蒸着めっき方法に適用し得るも
のであって、該蒸着めっき方法としては真空蒸着めっき
法の他各種のイオンプレーティング法、イオンアシスト
蒸着法等も包合される。また本発明が適用される被処理
材の種類にも制限はなく、その用途に応じて金属、ガラ
ス、セラミックス、紙等に適用することができるが、以
下帯状鋼板を代表的に例示して本発明を説明する。The production method of the present invention can be applied to all vapor deposition plating methods using an electron beam as a heating source, and the vapor deposition plating method includes vacuum vapor deposition plating method and various ion plating methods. Methods, ion assisted vapor deposition methods, etc. are also included. Further, there is no limitation on the type of material to which the present invention is applied, and it can be applied to metals, glass, ceramics, paper, etc. according to its application. The invention will be described.

【０００３】[0003]

【従来の技術】蒸着めっき法は、真空中又は希薄ガス雰
囲気下にて、原料を高温に加熱して蒸発させ、蒸気とし
て被処理材表面に付着させる成膜方法であり、古くから
汎用されている電気めっき法や溶融めっき法に比べて加
工性、耐食性等が良好な皮膜を得ることができ、更に成
膜可能な蒸発原料の種類が広く、高融点金属や合金、一
部セラミックス等にも適用可能であるため近年注目を集
めている。2. Description of the Related Art The vapor deposition plating method is a film forming method in which a raw material is heated to a high temperature in a vacuum or in a dilute gas atmosphere to evaporate, and adhered to the surface of a material to be treated as vapor. Compared to the electroplating method and hot dip plating method, it is possible to obtain a film with better workability and corrosion resistance, and there are a wide variety of evaporation raw materials that can be used for film formation, including refractory metals, alloys, and some ceramics. Since it is applicable, it has been attracting attention in recent years.

【０００４】蒸発原料を高温に加熱する手段としては、
抵抗加熱、高周波誘導加熱、レーザー加熱、電子ビーム
加熱等を用いることが可能であるが、エネルギー密度が
高く蒸発原料の蒸発速度を大きくすることのできる電子
ビーム加熱が主流となっている。電子ビーム加熱方式で
蒸着めっきを行うに当たっては、加熱効率が高く、結果
として生産性が高いことから蒸発槽内に配した蒸発原料
の表面に電子ビームを直接照射することにより加熱蒸発
させる方法が広く採用されている。また、例えば帯状の
鋼板に連続して蒸着めっきを施す場合には、複数の蒸発
槽を帯状鋼板走行方向に並列に配置し、各々に蒸発原料
を装入して各蒸発槽内の蒸発原料を電子ビームで照射す
る。その際、磁場によって電子ビーム照射領域を制御
し、また照射する時間配分を制御することによって各蒸
発槽に投入されるパワーを調整して各蒸発原料の蒸発量
を制御する方法が採られている。As means for heating the evaporation raw material to a high temperature,
Although resistance heating, high frequency induction heating, laser heating, electron beam heating and the like can be used, electron beam heating, which has a high energy density and can increase the evaporation rate of the evaporation raw material, is predominant. In vapor deposition plating using the electron beam heating method, the heating efficiency is high and the productivity is high as a result.Therefore, the method of heating and evaporating by directly irradiating the surface of the evaporation raw material placed in the evaporation tank with the electron beam is widely used. Has been adopted. Further, for example, in the case of continuously performing vapor deposition plating on a strip-shaped steel plate, a plurality of evaporation tanks are arranged in parallel in the strip-shaped steel plate running direction, and the evaporation raw materials in each evaporation tank are charged with the evaporation raw materials. Irradiate with electron beam. At that time, a method is adopted in which the electron beam irradiation region is controlled by a magnetic field and the irradiation time distribution is controlled to adjust the power input to each evaporation tank to control the evaporation amount of each evaporation source. .

【０００５】一方Ａｌ系めっき材は、耐食性、耐熱性、
熱反射性等の点で優れた特性を有しているので、建材、
家電製品、自動車マフラー等に汎用されている。その製
造方法としては溶融めっき法と蒸着めっき法が実用化さ
れており、また電気めっき法も開発されつつある。On the other hand, the Al-based plating material has corrosion resistance, heat resistance,
As it has excellent properties such as heat reflectivity,
It is widely used in home appliances, automobile mufflers, etc. As a manufacturing method thereof, a hot dip plating method and a vapor deposition plating method have been put into practical use, and an electroplating method is being developed.

【０００６】しかしながら溶融Ａｌめっき鋼板は700 ℃
前後に加熱された溶融Ａｌめっき浴中に被処理材である
鋼材を浸漬して製造するために、素地鋼板とＡｌめっき
層との接合界面でＡｌとＦｅが反応して脆弱なＡｌ−Ｆ
ｅ金属間化合物層が生成し、曲げ加工等の成形加工を施
すとめっき層の剥離が起こりやすい。このＡｌ−Ｆｅ金
属間化合物の生成を抑制するために、通常溶融めっき浴
中に１０％程度のＳｉを添加する方法が採用されている
が、Ａｌめっき層中へのＳｉの添加によって耐食性が低
下するという問題が生じている。また耐食性の向上を図
るためにＡｌ系合金めっきを施す場合にも、製法上溶融
浴材料として比較的低融点の材料しかＡｌ浴中へ添加す
ることができないため、Ａｌ系合金めっきの種類が制御
されるという問題がある。However, the hot-dip Al-plated steel sheet is 700 ° C.
In order to manufacture by immersing a steel material as a material to be treated in a molten Al plating bath heated back and forth, Al and Fe react with each other at a bonding interface between a base steel sheet and an Al plating layer, and are fragile Al-F
e If an intermetallic compound layer is formed and a forming process such as a bending process is performed, the plating layer is easily peeled off. In order to suppress the formation of this Al-Fe intermetallic compound, a method of adding about 10% of Si to the hot dip plating bath is usually adopted, but the addition of Si to the Al plating layer lowers the corrosion resistance. There is a problem of doing. In addition, even when Al-based alloy plating is performed to improve corrosion resistance, only a material having a relatively low melting point can be added to the Al bath as a molten bath material due to the manufacturing method. Therefore, the type of Al-based alloy plating can be controlled. There is a problem that is.

【０００７】一方蒸着めっき法によれば、上記のような
Ａｌ−Ｆｅ金属間化合物の生成が起こらない比較的低温
で製造でき、かつ非常に多種類の蒸発原料を用いること
ができるために各種Ａｌ系合金めっき材を比較的容易に
製造できる。On the other hand, according to the vapor deposition plating method, it is possible to manufacture at a relatively low temperature at which the above-mentioned Al-Fe intermetallic compound does not occur, and it is possible to use a very large variety of evaporation raw materials, so that various Al A system alloy plated material can be manufactured relatively easily.

【０００８】こうした中で、本発明者らが提案したＡｌ
−Ｃｒ−Ｔｉ系めっき材（特開昭64−21063 号公報）
は、優れた耐食性を発揮するとともに、Ａｌ系めっき材
本来の耐熱性、加工性等を兼備しており、前述のような
用途に対する応用が実現しつつある。Under these circumstances, Al proposed by the present inventors
-Cr-Ti system plated material (Japanese Patent Laid-Open No. 64-21063)
Has excellent corrosion resistance and also has the heat resistance and workability inherent to the Al-based plating material, and is being applied to the above-mentioned applications.

【０００９】[0009]

【発明が解決しようとする課題】ところが、蒸着Ａｌ−
Ｃｒ−Ｔｉ系めっき材を連続もしくは半連続的に製造す
るにあたっては下記のような問題点がある。 電子ビーム加熱方式蒸着めっき法は、磁場によって電
子ビーム照射領域を制御するもので、例えば電子銃１基
で複数の蒸発槽を用いて蒸着を行う場合、１本の電子ビ
ームが各蒸発槽間をジャンピングしながら短いサイクル
で順に各蒸発槽内の蒸発原料を加熱する。ところが各蒸
発槽は最低限の容積と構造上の強度を必要とするため
に、蒸発室内に並列に配置する蒸発槽の数が増加するに
従って電子ビームを走査しなければならない領域が拡大
し、その制御精度も高いレベル要求されるようになる。However, vapor-deposited Al--
There are the following problems in the continuous or semi-continuous production of the Cr-Ti based plated material. The electron beam heating vapor deposition plating method controls the electron beam irradiation area by a magnetic field. For example, when vapor deposition is performed using a plurality of evaporation tanks with one electron gun, one electron beam is applied between the evaporation tanks. While jumping, the evaporation raw materials in each evaporation tank are heated in sequence in a short cycle. However, since each evaporation tank requires a minimum volume and structural strength, the area in which the electron beam must be scanned expands as the number of evaporation tanks arranged in parallel in the evaporation chamber increases. A high level of control accuracy is required.

【００１０】また各蒸発槽内の蒸発原料を電子ビームに
より加熱するサイクルは、電子ビームの磁場に対する追
従性に限界があるため一定の値以下に短くすることは困
難である。従ってある一つの蒸発槽内の蒸発原料を加熱
している間、他の蒸発槽内の蒸発原料は冷却される状態
にあり、蒸発量は急激に減少することは避けられない。
更にこの冷却を防止するために単位時間当たりのジャン
ピング回数を増加させると各蒸発槽間を加熱するという
ロスが増加する。Further, it is difficult to shorten the cycle of heating the evaporation raw material in each evaporation tank by the electron beam to a certain value or less because the followability to the magnetic field of the electron beam is limited. Therefore, while the evaporation raw material in one evaporation tank is being heated, the evaporation raw materials in the other evaporation tanks are in a state of being cooled, and it is inevitable that the evaporation amount sharply decreases.
Further, if the number of jumping operations per unit time is increased in order to prevent this cooling, the loss of heating between the evaporation tanks increases.

【００１１】これらの設備上の問題点を解決するため
に、複数の電子銃を導入し個別に蒸発原料を加熱する方
法もあるが、電子銃等の設備費の増加と複数の電子ビー
ムを同時に制御する磁場制御方式の問題等があるので、
工業上複数の電子銃を使用するのは困難である。In order to solve these problems in the equipment, there is also a method of introducing a plurality of electron guns and individually heating the evaporation raw materials, but the equipment cost of the electron guns and the like and the plurality of electron beams are simultaneously increased. Since there is a problem of the magnetic field control method to control,
It is difficult to use multiple electron guns in the industry.

【００１２】蒸着法は幅広い分野で応用されている技
術であり、純Ａｌ、純Ｚｎめっき等の一部の分野では既
に連続生産が実用化されている。言うまでもなくこのよ
うな連続生産においては、長期にわたって安定した蒸発
量を確保するために蒸発によって減少する蒸発原料を蒸
発槽内に供給する必要がある。The vapor deposition method is a technique applied in a wide range of fields, and continuous production has already been put into practical use in some fields such as pure Al and pure Zn plating. Needless to say, in such continuous production, it is necessary to supply the evaporation raw material, which is reduced by evaporation, into the evaporation tank in order to secure a stable evaporation amount for a long period of time.

【００１３】ところがＣｒは昇華性を示し、一定の原料
供給を行った場合でもその蒸発量が安定しない。即ち、
蒸発量は実際に蒸発が行なわれている蒸発原料表面積と
蒸発原料表面温度により決まるが、昇華性材料であるＣ
ｒは固体状態を維持するために蒸発によってその表面形
状が経時的に変形して蒸発原料表面積を一定に維持する
ことができない。また加熱源である電子ビームの入射角
度が蒸発原料形状の変化ととも変動するために電子ビー
ムの原料表面への吸収効率が変化して蒸発原料表面積温
度も変動するという問題がある。このように昇華性を示
すＣｒの蒸発速度は経時的に変動しやすく、結果として
得られる蒸着Ａｌ−Ｃｒ−Ｔｉ系めっき材付着量とＣｒ
含有量とが安定しにくいという問題点が残されている。However, Cr exhibits sublimability, and the amount of evaporation thereof is not stable even when a constant amount of raw material is supplied. That is,
The amount of evaporation is determined by the surface area of the evaporating material and the surface temperature of the evaporating material actually being evaporated.
Since r maintains a solid state, its surface shape is deformed over time due to evaporation, and the surface area of the evaporating raw material cannot be maintained constant. Further, since the incident angle of the electron beam, which is the heating source, changes with the change of the shape of the evaporation raw material, there is a problem that the absorption efficiency of the electron beam on the raw material surface changes and the surface area of the evaporation raw material changes. As described above, the evaporation rate of Cr exhibiting sublimability easily changes with time, and the resulting deposited Al-Cr-Ti-based plating material adhesion amount and Cr
The problem remains that the content is difficult to stabilize.

【００１４】本発明は以上の様な従来技術の問題点に着
目してなされたものであって、その目的は蒸着Ａｌ−Ｃ
ｒ−Ｔｉめっき材のトータルを安定して連続的に製造す
ることのできる方法を提供しようとするものである。The present invention was made by paying attention to the problems of the prior art as described above, and the purpose thereof is vapor-deposited Al--C.
An object of the present invention is to provide a method capable of stably and continuously producing a total of r-Ti plated materials.

【００１５】[0015]

【課題を解決するための手段】上記の課題を解決するこ
とのできた本発明の製造方法は、電子ビームによってＡ
ｌ，ＣｒおよびＴｉを加熱蒸発させ、走行する被処理材
に該金属蒸気を蒸着させてＡｌ−Ｃｒ−Ｔｉ系めっきを
連続的に形成する方法において、ＣｒとＴｉをＣｒ−Ｔ
ｉ合金浴から一斉に加熱蒸発させるとともに、該Ｃｒ−
Ｔｉ合金浴にＣｒとＴｉの各蒸発量に応じた量のＣｒと
Ｔｉを連続的もしくは間欠的に供給しつつ、該Ｃｒ−Ｔ
ｉ合金浴中のＣｒ含有量を２〜８５％（重量％、以下同
じ）に制御することに第１の要旨を有し、またＡｌとＣ
ｒをＡｌ−Ｃｒ合金浴から一斉に加熱蒸発させるととも
に、該Ａｌ−Ｃｒ合金浴にＡｌとＣｒの各蒸発量に応じ
た量のＡｌとＣｒを連続的もしくは間欠的に供給しつ
つ、該Ａｌ−Ｃｒ合金浴中のＣｒ含有量を５〜７０％に
制御することに第２の要旨を有する。The manufacturing method of the present invention, which has been able to solve the above-mentioned problems, uses an electron beam
In a method of evaporating 1, Cr and Ti by heating and vapor-depositing the metal vapor on a running material to be processed to continuously form an Al-Cr-Ti system plating, Cr and Ti are Cr-T.
While simultaneously heating and evaporating from the i alloy bath, the Cr-
While continuously supplying the Ti alloy bath with Cr and Ti in amounts corresponding to the respective evaporation amounts of Cr and Ti, or intermittently, the Cr-T
The first gist is to control the Cr content in the i alloy bath to 2 to 85% (weight%, the same hereinafter), and to control Al and C.
While simultaneously heating and evaporating r from the Al-Cr alloy bath, the Al-Cr alloy bath is continuously or intermittently supplied with an amount of Al and Cr corresponding to the respective evaporation amounts of Al and Cr. The second gist is to control the Cr content in the Cr alloy bath to 5 to 70%.

【００１６】[0016]

【作用】図２に３つの蒸発槽からＡｌ，Ｃｒ，Ｔｉを夫
々別々に蒸発させる従来の製造方法を模式的に示す。本
発明者らはこの従来の方法を採用することによって生じ
る製造上および品質上の問題点を解決すべく種々検討し
た結果、図１に模式的に示すようにＣｒ−Ｔｉ合金浴か
らＣｒとＴｉを、もしくはＡｌ−Ｃｒ合金浴からＡｌと
Ｃｒを夫々混合蒸気の状態で蒸発させることによってそ
れらの問題点を解決できることを見出したものである。FIG. 2 schematically shows a conventional manufacturing method in which Al, Cr, and Ti are separately evaporated from three evaporation tanks. The present inventors have conducted various studies to solve the problems in production and quality caused by adopting this conventional method, and as a result, as shown schematically in FIG. 1, Cr and Ti are removed from the Cr--Ti alloy bath. It has been found that these problems can be solved by evaporating Al and Cr from the Al—Cr alloy bath in a mixed vapor state, respectively.

【００１７】図１に示すＣｒを含む合金浴を用いる蒸発
方式を採用すれば、蒸発槽の数はＡｌ，Ｃｒ，Ｔｉの３
つの蒸発槽からＡｌ浴用蒸発槽とＣｒ−Ｔｉ合金浴用蒸
発槽の２つ、もしくはＡｌ−Ｃｒ合金浴用蒸発槽とＴｉ
浴用蒸発槽の２つにそれぞれ削減され、３つの蒸発槽間
の電子ビーム制御から、２つの蒸発槽間の電子ビーム制
御へと電子ビームジャンピング制御や各原料への照射時
間配分制御をより簡略化し、製造上の問題を解決するこ
とができる。また、Ｃｒの昇華性による蒸発速度の変動
の問題についても、Ｃｒをめっき構成元素であるＡｌ若
しくはＴｉと合金化させることによって夫々Ａｌ−Ｃｒ
合金浴若しくはＣｒ−Ｔｉ合金浴を形成させ、電子ビー
ムによって加熱される各合金溶融浴の蒸発面を常にほぼ
一定の水平状態に維持することによって解決可能であ
る。従って、Ａｌ浴とＣｒ−Ｔｉ合金浴の組み合わせ
か、Ａｌ−Ｃｒ合金浴とＴｉ浴の組み合わせを採用する
ことによって、電子ビーム制御技術とＣｒの蒸発量の安
定性の問題を同時に解決することができる。If the evaporation method using an alloy bath containing Cr shown in FIG. 1 is adopted, the number of evaporation tanks is 3 of Al, Cr and Ti.
Two evaporation tanks, one for Al bath and one for Cr-Ti alloy bath, or one for Al-Cr alloy bath and Ti
The number of bath evaporation tanks has been reduced to two, and electron beam jumping control and irradiation time distribution control to each raw material have been simplified from electron beam control between three evaporation tanks to electron beam control between two evaporation tanks. , Can solve manufacturing problems. Further, as for the problem of the fluctuation of the evaporation rate due to the sublimation property of Cr, by alloying Cr with Al or Ti which is a constituent element of the plating, respectively, Al-Cr
This can be solved by forming an alloy bath or a Cr-Ti alloy bath and keeping the evaporating surface of each alloy melting bath heated by an electron beam in a substantially constant horizontal state. Therefore, by adopting the combination of the Al bath and the Cr-Ti alloy bath or the combination of the Al-Cr alloy bath and the Ti bath, it is possible to simultaneously solve the problems of the electron beam control technique and the stability of the evaporation amount of Cr. it can.

【００１８】しかしながら、所望の付着量、Ｃｒ組成、
Ｔｉ組成を有する蒸着Ａｌ−Ｃｒ−Ｔｉめっきを得るた
めには、当然のことながら、蒸発槽を３つから２つに削
減してもＡｌ，Ｃｒ，Ｔｉの各蒸発量を制御することが
必要であることに変わりはない。例えばＡｌ−Ｃｒ合金
浴とＴｉ浴の組み合わせを用いた場合には、Ａｌ−Ｃｒ
合金浴からのＡｌ，Ｃｒの各蒸発量とＴｉ浴からのＴｉ
蒸発量を制御する必要がある。１基の電子銃により２つ
の蒸発槽を加熱する電子ビーム合金蒸着では、電子ビー
ムパワーと各蒸発槽内蒸発原料に電子ビームが滞在する
時間の比率、即ち電子ビームパワーの２つの蒸発槽内蒸
発原料への配分比（以下、配分比という）によって２つ
の蒸発槽からの蒸発量を制御する。ここでＴｉ浴からの
Ｔｉ蒸発量は、電子銃の電子ピームパワーと配分比だけ
で容易に制御することができる。ところがＡｌ−Ｃｒ合
金浴からのＡｌとＣｒの各蒸発量は、電子銃の電子ビー
ムパワーと配分比だけでは制御できない。However, the desired adhesion amount, Cr composition,
In order to obtain a vapor-deposited Al-Cr-Ti plating having a Ti composition, it is, of course, necessary to control each evaporation amount of Al, Cr, and Ti even if the evaporation tank is reduced from three to two. There is no change. For example, when a combination of Al-Cr alloy bath and Ti bath is used, Al-Cr
Evaporation amount of Al and Cr from alloy bath and Ti from Ti bath
It is necessary to control the amount of evaporation. In electron beam alloy evaporation in which two evaporation tanks are heated by one electron gun, the ratio of the electron beam power and the time that the electron beam stays in the evaporation source in each evaporation tank, that is, the evaporation in the two evaporation tanks with the electron beam power. The evaporation amount from the two evaporation tanks is controlled by the distribution ratio to the raw material (hereinafter referred to as the distribution ratio). Here, the amount of Ti evaporated from the Ti bath can be easily controlled only by the electron beam power of the electron gun and the distribution ratio. However, the evaporation amounts of Al and Cr from the Al-Cr alloy bath cannot be controlled only by the electron beam power of the electron gun and the distribution ratio.

【００１９】即ち、ある表面温度Ｔを有する複数の金属
元素からなる合金浴から複数の金属を同時蒸発させる場
合、各金属元素の蒸発量は各金属元素の温度Ｔにおける
飽和蒸気圧及び合金浴最表面の各金属元素の蒸発面積比
によってほぼ決まる。言い替えれば、合金浴構成金属元
素の温度Ｔにおける単位蒸発面積あたりの蒸発量と蒸発
面積比によってほぼ決まる。Ａｌ−Ｃｒ合金浴を用いた
場合についてより具体的に述べると、単位面積当たりの
ＡｌとＣｒの各蒸発量と蒸発面積比は次のようにして制
御する。まずＡｌ−Ｃｒ合金浴からの単位面積当たりの
ＡｌとＣｒの各蒸発量は、Ａｌ−Ｃｒ合金浴の最表面温
度の関数であるので、電子銃の電子ビームパワーと配分
比によって決められるＡｌ−Ｃｒ合金浴に投入する電子
ビームのパワーによって制御する。一方Ａｌ−Ｃｒ合金
浴表面のＣｒ蒸発面積比は合金浴中のＣｒ含有量によっ
て制御する。That is, when a plurality of metals are co-evaporated from an alloy bath composed of a plurality of metal elements having a certain surface temperature T, the evaporation amount of each metal element depends on the saturated vapor pressure at each temperature T and the alloy bath maximum. It is almost determined by the evaporation area ratio of each metal element on the surface. In other words, it is almost determined by the evaporation amount per unit evaporation area and the evaporation area ratio at the temperature T of the alloy bath constituent metal elements. More specifically, the case of using the Al-Cr alloy bath will be described. The evaporation amount of Al and Cr per unit area and the evaporation area ratio are controlled as follows. First, since the evaporation amounts of Al and Cr per unit area from the Al-Cr alloy bath are functions of the outermost surface temperature of the Al-Cr alloy bath, Al- determined by the electron beam power of the electron gun and the distribution ratio. It is controlled by the power of the electron beam introduced into the Cr alloy bath. On the other hand, the Cr evaporation area ratio on the surface of the Al-Cr alloy bath is controlled by the Cr content in the alloy bath.

【００２０】尚Ａｌ−Ｃｒ合金浴中のＣｒ含有量の制御
はＡｌ−Ｃｒ合金浴へのＡｌ、Ｃｒの供給速度を制御す
ることによって達成され、Ａｌ−Ｃｒ合金浴から蒸発す
るＡｌ、Ｃｒに相当する量だけのＡｌ、Ｃｒを連続的ま
たは間欠的に供給することによってＡｌ−Ｃｒ合金浴中
のＣｒ含有量を経時的に変化することなく安定させるこ
とができる。The control of the Cr content in the Al-Cr alloy bath is achieved by controlling the feed rate of Al and Cr to the Al-Cr alloy bath, and the Al and Cr vaporized from the Al-Cr alloy bath are controlled. By supplying a corresponding amount of Al and Cr continuously or intermittently, the Cr content in the Al-Cr alloy bath can be stabilized without changing with time.

【００２１】従って所望の付着量、Ｃｒ組成、Ｔｉ組成
を有する蒸着Ａｌ−Ｃｒ−Ｔｉめっきを得るためには、
Ａｌ−Ｃｒ合金浴用蒸発槽とＴｉ浴用蒸発槽に各々投入
する電子ビームパワーおよびＡｌ−Ｃｒ合金浴へのＡｌ
供給量とＣｒ供給量を制御すれば良い。Therefore, in order to obtain a vapor-deposited Al-Cr-Ti plating having a desired deposition amount, Cr composition and Ti composition,
Electron beam power to be fed into the evaporation tank for Al-Cr alloy bath and evaporation tank for Ti bath, and Al to Al-Cr alloy bath
It suffices to control the supply amount and the Cr supply amount.

【００２２】Ｃｒ−Ｔｉ合金浴とＡｌ浴の組み合わせを
用いた場合にも同様であり、所望の付着量、Ｃｒ組成、
Ｔｉ組成を有する蒸着Ａｌ−Ｃｒ−Ｔｉめっきを得るた
めには、Ｃｒ−Ｔｉ合金浴用蒸発槽とＡｌ浴用蒸発槽に
各々投入する電子ビームパワーおよびＣｒ−Ｔｉ合金浴
へのＴｉ供給量とＣｒ供給量を制御すれば良い。The same applies when a combination of a Cr-Ti alloy bath and an Al bath is used, and the desired adhesion amount, Cr composition,
In order to obtain a vapor-deposited Al-Cr-Ti plating having a Ti composition, electron beam powers are respectively fed to the Cr-Ti alloy bath evaporation tank and the Al bath evaporation tank, and the Ti supply amount and Cr supply to the Cr-Ti alloy bath. The amount should be controlled.

【００２３】ところでＡｌ、Ｃｒ、Ｔｉの実用的な蒸発
量が得られる温度範囲における飽和蒸気圧はＡｌ、Ｃ
ｒ、Ｔｉの順に小さくなり、ＣｒはＡｌの約１／１０、
ＴｉはＡｌの約１／１０００である。従って蒸着Ａｌ−
Ｃｒ−Ｔｉめっき材が期待される性能を発揮するために
必要なＣｒ組成およびＴｉ組成を得るためには、Ａｌ−
Ｃｒ合金浴中もしくはＣｒ−Ｔｉ合金浴中のＣｒ含有量
をある範囲内に制御しなくてはならない。更には、Ｃｒ
を含む合金浴の融点や流動性等の製造上の問題からも合
金浴組成の範囲を管理しなければならない。本発明者ら
はこの両者の点を考慮して実験により以下のような合金
浴組成範囲を規定した。By the way, the saturated vapor pressures in the temperature range where the practical evaporation amounts of Al, Cr and Ti are obtained are Al and C.
It becomes smaller in the order of r and Ti, Cr is about 1/10 of Al,
Ti is about 1/1000 of Al. Therefore, evaporated Al-
In order to obtain the Cr composition and Ti composition necessary for the Cr-Ti plated material to exhibit the expected performance, Al-
The Cr content in the Cr alloy bath or the Cr-Ti alloy bath must be controlled within a certain range. Furthermore, Cr
The composition range of the alloy bath must be controlled also from the viewpoint of manufacturing problems such as melting point and fluidity of the alloy bath containing. The present inventors defined the following alloy bath composition range by experiments in consideration of both of these points.

【００２４】即ち、めっき製品の性能と、めっき組成の
関係の調査結果から蒸着Ａｌ−Ｃｒ−Ｔｉめっき層中に
はＣｒ及びＴｉは共に０．５％以上含有されることが必
要であるので、Ａｌ−Ｃｒ合金浴中のＣｒ含有量は５〜
７０％、より好ましくは５〜６０％にすることが必要で
ある。Ａｌ−Ｃｒ合金浴中のＣｒ含有量が５％を下回る
と蒸着Ａｌ−Ｃｒ−Ｔｉめっき層中に０．５％上のＣｒ
を含有させることが困難になる。逆に、６０％を超える
と浴の融点が上昇して浴全体の流動性が次第に低下し、
７０％を超えるＣｒ含有量では、Ａｌ−Ｃｒ−Ｔｉめっ
き層中のＣｒ含有率が４９．５％を超えてしまうので好
ましくない。またＣｒ−Ｔｉ浴中のＣｒ含有量は２％〜
８５％、より好ましくは２％〜７５％にすることが必要
である。Ｃｒ−Ｔｉ合金浴中のＣｒ含有量が２％を下回
ると蒸着Ａｌ−Ｃｒ−Ｔｉめっき層中に０．５％以上の
Ｃｒを含有させることが困難になる。逆に、７５％を超
えると浴全体の流動性が次第に低下し、８５％を超える
Ｃｒ含有量では逆にＡｌ−Ｃｒ−Ｔｉめっき層中に０．
５％以上のＴｉを含有させることが困難になる。That is, from the result of the investigation of the relationship between the performance of the plated product and the plating composition, it is necessary that both the Cr and Ti content in the deposited Al-Cr-Ti plated layer be 0.5% or more. The Cr content in the Al-Cr alloy bath is 5
It is necessary to set 70%, more preferably 5 to 60%. When the Cr content in the Al-Cr alloy bath is less than 5%, the Cr content in the vapor-deposited Al-Cr-Ti plating layer is 0.5% above Cr.
Becomes difficult to contain. On the contrary, if it exceeds 60%, the melting point of the bath rises and the fluidity of the entire bath gradually decreases,
When the Cr content exceeds 70%, the Cr content in the Al-Cr-Ti plating layer exceeds 49.5%, which is not preferable. The Cr content in the Cr-Ti bath is 2% to
It is necessary to set it to 85%, more preferably 2% to 75%. If the Cr content in the Cr-Ti alloy bath is less than 2%, it becomes difficult to contain 0.5% or more of Cr in the deposited Al-Cr-Ti plated layer. On the contrary, when it exceeds 75%, the fluidity of the entire bath gradually decreases, and when the Cr content exceeds 85%, conversely, the fluidity in the Al-Cr-Ti plating layer becomes 0.
It becomes difficult to contain Ti of 5% or more.

【００２５】なお、Ａｌ、Ｃｒ、Ｔｉ原料の浴中への供
給方法は様々な方法がある。例えばＡｌおよびＴｉは塑
性加工が容易な金属であるためワイヤー状の供給し易い
形状に加工可能であり、公知のワイヤーフィーダー等の
供給装置を使用して連続的に浴中に供給できる。またＣ
ｒは塑性加工が困難であるためにワイヤー状等の供給が
容易な形状に加工することができないが、粒状、粉状、
塊状等の形状で合金浴の上方よりバイブレーター等を用
いて投入する方式を採用することができる。また目標と
するＣｒ組成およびＴｉ組成が一定であれば、Ａｌ−Ｃ
ｒ合金浴の場合では、Ａｌワイヤー中に所定量のＣｒを
分散させたＣｒ分散Ａｌワイヤーの供給、また、Ｃｒ−
Ｔｉ合金浴の場合であれば、所定量のＣｒ組成Ｃｒ−Ｔ
ｉ合金を粒状、粉状、塊状等の形状でバイブレーター等
を用いて上方より投入するなどの方式を採ることもでき
る。従って供給方式としては本発明に一切の制限を設け
るものではない。There are various methods for supplying the Al, Cr, and Ti raw materials into the bath. For example, Al and Ti are metals that can be easily plastically processed, so that they can be processed into a wire-like shape that can be easily supplied, and can be continuously supplied into the bath by using a known wire feeder or other supply device. Also C
Since r is difficult to plastically process, it cannot be processed into a wire-like shape or the like that can be easily supplied, but granular, powdery,
It is possible to employ a method in which a lump or the like is introduced from above the alloy bath using a vibrator or the like. If the target Cr and Ti compositions are constant, Al-C
In the case of the r alloy bath, a Cr-dispersed Al wire in which a predetermined amount of Cr is dispersed in the Al wire is supplied, and Cr-
In the case of a Ti alloy bath, a predetermined amount of Cr composition Cr-T
It is also possible to adopt a method in which the i alloy is charged in the form of particles, powder, lumps or the like from above using a vibrator or the like. Therefore, the present invention does not impose any restrictions on the supply method.

【００２６】また蒸発槽についてはＡｌ浴もしくはＡｌ
−Ｃｒ合金浴では、特にるつぼ材質中に不純物が多量に
含有されていない限り通常のアルミナるつぼ等を用いる
ことができる。またＴｉ浴もしくはＣｒ−Ｔｉ合金浴で
は、水冷銅るつぼまたはグラファイトるつぼ等を用いる
ことができる。As for the evaporation tank, an Al bath or Al
In the -Cr alloy bath, a normal alumina crucible or the like can be used unless the crucible material contains a large amount of impurities. Further, in the Ti bath or the Cr-Ti alloy bath, a water-cooled copper crucible or a graphite crucible can be used.

【００２７】以下実施例を挙げて本発明を更に詳細に説
明するが、下記実施例は本発明を制限するものではな
く、前・後記の趣旨を逸脱しない範囲で変更実施するこ
とは全て本発明の技術的範囲に包合される。The present invention will be described in more detail with reference to the following examples, but the following examples are not intended to limit the present invention, and any modification or implementation is within the scope of the present invention without departing from the gist thereof. Included in the technical scope of.

【００２８】[0028]

【実施例】図１に示す方法により、下記の条件で帯状鋼
板の連続蒸着Ａｌ−Ｃｒ−Ｔｉ系めっき処理を行った。 実施例１＜Ａｌ−Ｃｒ合金浴の場合＞ Ａｌ−Ｃｒ合金浴中Ｃｒ含有量：５０％ Ａｌ−Ｃｒ合金蒸発槽：高純度電融アルミナるつぼ （アルミナ純度９８％以上） Ｔｉ蒸発槽 ：グラファイトるつぼ Ａｌ供給方法 ：ワイヤー状Ａｌをワイヤーフィ
ーダーにより供給 Ｃｒ供給方法 ：ブリケット状Ｃｒをバイブレー
ターにて上方より投入 Ｔｉ供給方法 ：ワイヤー状Ｔｉをワイヤーフィ
ーダーにより供給 電子銃 ：出力３００ｋｗのピアス型電子
銃を使用 Ａｌ−Ｃｒ合金浴、Ｔｉ浴に投入するパワーは各々の浴
に電子ビームを照射する時間配分により制御 上記の方法により、付着量１０ｇ／m²、Ｃｒ組成２０
％、Ｔｉ組成５％の蒸着Ａｌ−Ｃｒ−Ｔｉ合金めっきを
連続して安定的に製造することができ、付着量、Ｃｒ組
成、Ｔｉ組成も極めて安定していた。EXAMPLE Continuous vapor deposition Al—Cr—Ti system plating treatment of a strip steel sheet was carried out under the following conditions by the method shown in FIG. Example 1 <In the case of Al-Cr alloy bath> Cr content in Al-Cr alloy bath: 50% Al-Cr alloy evaporation tank: high-purity fused alumina crucible (alumina purity 98% or more) Ti evaporation tank: graphite crucible Al supply method: Wire-shaped Al is supplied by a wire feeder Cr supply method: Briquette-shaped Cr is charged from above by a vibrator Ti supply method: Wire-shaped Ti is supplied by a wire feeder Electron gun: A pierce type electron gun with an output of 300 kw is used al-Cr alloy bath, under control the above method by time allocation for irradiating an electron beam to power each of the baths to be introduced into the Ti bath deposition amount 10 g / m ^2, Cr composition 20
%, Ti composition 5%, vapor-deposited Al-Cr-Ti alloy plating could be continuously and stably produced, and the deposited amount, Cr composition, and Ti composition were also extremely stable.

【００２９】実施例２＜Ｃｒ−Ｔｉ合金浴の場合＞ Ｃｒ−Ｔｉ合金浴中Ｃｒ含有量：１０％ Ａｌ蒸発槽 ：高純度電融アルミナるつぼ （アルミナ純度９８％以上） Ｃｒ−Ｔｉ合金蒸発槽：グラファイトるつぼ Ａｌ供給方法 ：ワイヤー状Ａｌをワイヤーフィ
ーダーにより供給 Ｃｒ供給方法 ：ブリケット状Ｃｒをバイブレー
ターにて上方より投入 Ｔｉ供給方法 ：ワイヤー状Ｔｉをワイヤーフィ
ーダーにより供給 電子銃 ：出力３００ｋｗのピアス型電子
銃を使用 Ａｌ浴、Ｃｒ−Ｔｉ合金浴に投入するパワーは各々の浴
に電子ビームを照射する時間配分により制御 上記の方法により、付着量２０ｇ／m²、Ｃｒ組成１５
％、Ｔｉ組成３％の蒸着Ａｌ−Ｃｒ−Ｔｉ合金めっきを
連続して安定的に製造することができ、付着量、Ｃｒ組
成、Ｔｉ組成も極めて安定していた。Example 2 <In case of Cr-Ti alloy bath> Cr content in Cr-Ti alloy bath: 10% Al evaporation tank: High-purity fused alumina crucible (alumina purity 98% or more) Cr-Ti alloy evaporation tank : Graphite crucible Al supply method: Wire-shaped Al is supplied by a wire feeder Cr supply method: Briquette-shaped Cr is charged from above by a vibrator Ti supply method: Wire-shaped Ti is supplied by a wire feeder Electron gun: Pierce type electron with output of 300 kw Use a gun. Power applied to Al bath and Cr-Ti alloy bath is controlled by time distribution of irradiating each bath with electron beam. Adhesion amount 20 g / m ² , Cr composition 15 by the above method.
%, Ti composition 3%, vapor-deposited Al-Cr-Ti alloy plating could be continuously and stably produced, and the adhesion amount, Cr composition, and Ti composition were also extremely stable.

【００３０】[0030]

【発明の効果】本発明は以上のように構成されており、
連続蒸着Ａｌ−Ｃｒ−Ｔｉめっきにおけるめっき組成お
よび付着量の安定性などの問題点を、２つの蒸発槽から
３元蒸着を可能にすることによって電子ビーム制御技術
を簡略化し、かつ、Ｃｒの昇華性による蒸発量変動の問
題を他のめっき成分であるＡｌもしくはＴｉと合金溶融
化させて、Ｃｒを含む合金浴の状態からＣｒ蒸発を図る
ことにより解決したものである。本発明により、蒸着Ａ
ｌ−Ｃｒ−Ｔｉ系めっき材を安定して連続もしくは半連
続的に製造することができる。The present invention is configured as described above,
The problems such as the stability of the plating composition and the amount of deposition in the continuous vapor deposition Al-Cr-Ti plating are simplified by enabling the ternary vapor deposition from the two evaporation tanks, and the sublimation of Cr is performed. This is a solution to the problem of variation in the evaporation amount due to the property by melting the alloy with Al or Ti, which is another plating component, and evaporating Cr from the state of the alloy bath containing Cr. According to the present invention, vapor deposition A
The l-Cr-Ti-based plated material can be stably and continuously or semi-continuously manufactured.

【図面の簡単な説明】[Brief description of drawings]

【図１】本発明の製造方法を模式的に示す概略図であ
る。FIG. 1 is a schematic view schematically showing a manufacturing method of the present invention.

【図２】従来の製造方法を模式的に示す概略図である。FIG. 2 is a schematic view schematically showing a conventional manufacturing method.

【符号の説明】[Explanation of symbols]

１ 被処理材 ２ Ａｌ蒸発槽 ２ａ Ａｌ−Ｃｒ蒸発槽 ３ Ｃｒ蒸発槽 ３ａ Ｃｒ−Ｔｉ蒸発槽 ４ Ｔｉ蒸発槽 ５ Ａｌ原料 ５ａ Ａｌ−Ｃｒ原料 ６ Ｃｒ原料 ６ａ Ｃｒ−Ｔｉ原料 ７ Ｔｉ原料 ８ 電子銃 ９ 電子ビーム 1 processed material 2 Al evaporation tank 2a Al-Cr evaporation tank 3 Cr evaporation tank 3a Cr-Ti evaporation tank 4 Ti evaporation tank 5 Al raw material 5a Al-Cr raw material 6 Cr raw material 6a Cr-Ti raw material 7 Ti raw material 8 electron gun 9 electron beam

フロントページの続き (72)発明者 綾部 東太 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 (72)発明者 加藤 淳 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 (72)発明者 三宅 昭二 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 Tota Ayabe 1 Kanazawa-machi, Kakogawa-shi, Hyogo Kamido Steel Works Co., Ltd. Kakogawa Steel Works (72) Inventor Jun Kato 1-Kanazawa-machi, Kakogawa-shi Hyogo Kamido Steel Works, Ltd. Inside the Kakogawa Works (72) Inventor Shoji Miyake 1 Kanazawa-machi, Kakogawa-shi, Hyogo Kadogawa Works Kakogawa Works

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】 電子ビームによってＡｌ，ＣｒおよびＴ
ｉを加熱蒸発させ、走行する被処理材に該金属蒸気を蒸
着させてＡｌ−Ｃｒ−Ｔｉ系めっきを連続的に形成する
方法において、ＣｒとＴｉをＣｒ−Ｔｉ合金浴から一斉
に加熱蒸発させるとともに、該Ｃｒ−Ｔｉ合金浴にＣｒ
とＴｉの各蒸発量に応じた量のＣｒとＴｉを連続的もし
くは間欠的に供給しつつ、該Ｃｒ−Ｔｉ合金浴中のＣｒ
含有量を２〜８５％（重量％、以下同じ）に制御するこ
とを特徴とする蒸着Ａｌ−Ｃｒ−Ｔｉ系めっき材の製造
方法。1. Al, Cr and T by electron beam
In a method of evaporating i by heating and vapor-depositing the metal vapor on a running material to be processed to continuously form an Al-Cr-Ti-based plating, Cr and Ti are heated and evaporated all together from a Cr-Ti alloy bath. Together with Cr in the Cr-Ti alloy bath
Cr in the Cr-Ti alloy bath while continuously or intermittently supplying Cr and Ti in amounts corresponding to the respective evaporation amounts of Ti and Ti.
A method for producing a vapor-deposited Al-Cr-Ti based plated material, characterized in that the content is controlled to 2 to 85% (weight%, the same applies hereinafter). 【請求項２】 電子ビームによってＡｌ、ＣｒおよびＴ
ｉを加熱蒸発させ、走行する被処理材に該金属蒸気を蒸
着させてＡｌ−Ｃｒ−Ｔｉ系めっきを連続的に形成する
方法において、ＡｌとＣｒをＡｌ−Ｃｒ合金浴から一斉
に加熱蒸発させるとともに、該Ａｌ−Ｃｒ合金浴にＡｌ
とＣｒの各蒸発量に応じた量のＡｌとＣｒを連続的もし
くは間欠的に供給しつつ、該Ａｌ−Ｃｒ合金浴中のＣｒ
含有量を５〜７０％に制御することを特徴とする蒸着Ａ
ｌ−Ｃｒ−Ｔｉ系めっき材の製造方法。2. Al, Cr and T by electron beam
In the method of heating and evaporating i and vapor-depositing the metal vapor on a running material to continuously form an Al-Cr-Ti-based plating, Al and Cr are heated and evaporated all at once from an Al-Cr alloy bath. Together with Al in the Al-Cr alloy bath
Cr in the Al-Cr alloy bath while continuously or intermittently supplying Al and Cr in amounts corresponding to the respective evaporation amounts of Cr and Cr.
Vapor deposition A characterized by controlling the content to 5 to 70%
A method for manufacturing an l-Cr-Ti-based plated material.